JP4027220B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

【００６２】
【外８】

【００６３】
【外９】

【００６４】
導電性粒子の表面処理方法としては、導電性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。次いで、この分散溶液から溶剤を除去し、導電性粒子表面に固着させればよい。
【００６５】
また、必要に応じて、この後更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。更に、必要に応じて表面処理後の導電性粒子に更に粉砕処理を施すことができる。
【００６６】
導電性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、形状及び表面積などに影響を受けるが、表面処理済みの導電性粒子全質量に対し、１〜６５質量％が好ましく、更には１〜５０質量％が好ましい。
【００６７】
更に、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（１）で示される構造を有するシロキサン化合物を導電性粒子分散時に添加したり、または、下記式（１）で示される構造を有するシロキサン化合物で表面処理を施した導電性粒子を混合することにより、更に環境安定性により優れた保護層を得ることができる。
【００６８】
【外１０】

【００６９】
（式（１）中、Ａ^１１〜Ａ^１８は、それぞれ独立に、水素原子またはメチル基である。ただし、Ａの総数（ａ）に対する該水素原子の総数（ｂ）の割合（ｂ／ａ）は０．００１以上０．５以下である。ｎ^１１は、０以上の整数である。）
シロキサン化合物を添加後分散した塗工液、または、シロキサン化合物を表面処理した導電性金属酸化物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、更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。
【００７０】
上記式（１）で示される構造を有す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過ぎない方がよく、重量平均分子量で１００〜５００００が好ましく、特にその中でも表面処理の処理効率から、５００〜１００００が好ましい。
【００７１】
表面処理の方法としては、湿式と乾式の２通りがある。
【００７２】
湿式処理では、導電性粒子である導電性金属酸化物粒子を、上記式（１）で示される構造を有す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。
【００７３】
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粒子表面に固着させる。
【００７４】
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、導電性金属酸化物粒子表面がこの網状構造で包まれる。
【００７５】
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化物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粒子に粉砕処理を施してもよい。
【００７６】
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。
【００７７】
本発明の電子写真感光体の保護層に使用する電荷輸送物質としては、分子内にヒドロキシル基を少なくとも１つ有する化合物、特には、分子内にヒドロキシアルキル基、ヒドロキシアルコキシル基、または、ヒドロキシフェニル基を少なくとも１つ有する化合物である。
【００７８】
分子内にヒドロキシアルキル基及びヒドロキシアルコキシル基の少なくとも一方を有する電荷輸送物質としては、下記式（２）〜（４）のいずれかの式で示される構造を有する電荷輸送物質である。
【００７９】
【外１１】

【００８０】
（式（２）中、Ｒ^２１、Ｒ^２２及びＲ^２３は、それぞれ独立に、炭素数１〜８の枝分かれしてもよい２価の炭化水素基を示す。α、β及びγのベンゼン環は、それぞれ独立に、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシル基、置換または無置換の芳香族炭化水素環基、または、置換または無置換の芳香族複素環基を置換基として有してもよい。ａ、ｂ、ｄ、ｍ及びｎは、それぞれ独立に、０または１を示す。）
【外１２】

【００８１】
（式（３）中、Ｒ^３１、Ｒ^３２及びＲ^３３は、それぞれ独立に、炭素数１〜８の枝分かれしてもよい２価の炭化水素基を示す。δ及びεのベンゼン環は、それぞれ独立に、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシル基、置換または無置換の芳香族炭化水素環基、または、置換または無置換の芳香族複素環基を置換基として有してもよい。ｅ、ｆ及びｇは、それぞれ独立に、０または１を示す。ｐ、ｑ及びｒは、それぞれ独立に、０または１であるが、総てが同時に０になることはない。Ｚ^３１及びＺ^３２は、それぞれ独立に、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシル基、置換または無置換の芳香族炭化水素環基、または、置換または無置換の芳香族複素環基を示し、または、共同で環をなしてもよい。）
【外１３】

【００８２】
（式（４）中、Ｒ^４１、Ｒ^４２、Ｒ^４３及びＲ^４４は、それぞれ独立に、炭素数１〜８の枝分かれしてもよい２価の炭化水素基を示す。ζ、η、θ及びιのベンゼン環は、それぞれ独立に、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシル基、置換または無置換の芳香族炭化水素環基、または、置換または無置換の芳香族複素環基を置換基として有してもよい。ｈ、ｉ、ｊ、ｋ、ｓ、ｔ及びｕは、それぞれ独立に、０または１を示す。Ｚ^４１及びＺ^４２は、それぞれ独立に、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシル基、置換または無置換の芳香族炭化水素環基、または、置換または無置換の芳香族複素環基を示し、または、共同で環をなしてもよい。）
また、分子内にヒドロキシフェニル基を有する電荷輸送物質としては、下記式（５）〜（７）のいずれかの式で示される構造を有する電荷輸送物質である。
【００８３】
【外１４】

【００８４】
（式（５）中、Ｒ^５１は、炭素数１〜８の枝分かれしてもよい２価の炭化水素基を示す。Ｒ^５２は、水素原子、置換または無置換のアルキル基、置換または無置換のアラルキル基、または、置換または無置換のフェニル基を示す。Ａｒ^５１及びＡｒ^５２は、それぞれ独立に、置換または無置換のアルキル基、置換または無置換のアラルキル基、置換または無置換の芳香族炭化水素環基、または、置換または無置換の芳香族複素環基を示す。Ａｒ^５３は、置換または無置換の２価の芳香族炭化水素環基、または、置換または無置換の２価の芳香族複素環基を示す。ｖ及びｗは、それぞれ独立に、０または１を示す。ただし、ｖ＝０のときは、ｗ＝０である。κ及びλのベンゼン環は、それぞれ独立に、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシル基、置換または無置換の芳香族炭化水素環基、または、置換または無置換の芳香族複素環基を置換基として有してもよい。）
【外１５】

【００８５】
（式（６）中、Ｒ^６１は、炭素数１〜８の枝分かれしてもよい２価の炭化水素基を示す。Ａｒ^６１及びＡｒ^６２は、それぞれ独立に、置換または無置換のアルキル基、置換または無置換のアラルキル基、置換または無置換の芳香族炭化水素環基、または、置換または無置換の芳香族複素環基を示す。ｘは、０または１を示す。μ及びνのベンゼン環は、それぞれ独立に、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシル基、置換または無置換の芳香族炭化水素環基、または、置換または無置換の芳香族複素環基を置換基として有してもよいし、また、μとνのベンゼン環は、置換基を介して共同で環をなしてもよい。）
【外１６】

【００８６】
（式（７）中、Ｒ^７１及びＲ^７２は、それぞれ独立に、炭素数１〜８の枝分かれしてもよい２価の炭化水素基を示す。Ａｒ^７１は、置換または無置換のアルキル基、置換または無置換のアラルキル基、置換または無置換の芳香族炭化水素環基、または、置換または無置換の芳香族複素環基を示す。ｙ及びｚは、それぞれ独立に、０または１を示す。ξ、π、ρ及びσのベンゼン環は、それぞれ独立に、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシル基、置換または無置換の芳香族炭化水素環基、または、置換または無置換の芳香族複素環基を置換基として有してもよいし、ξとπのベンゼン環、及び、ρとσのベンゼン環は、それぞれ独立に、置換基を介して共同で環をなしてもよい。）
上記式（２）〜（７）中、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^４１、Ｒ^４２、Ｒ^４３、Ｒ^４４、Ｒ^５１、Ｒ^６１、Ｒ^７１及びＲ^７２の炭素数１〜８の枝分かれしてもよい２価の炭化水素基としては、メチレン基、エチレン基、プロピレン基及びブチレン基などのアルキレン基、イソプロピレン基、シクロヘキシリデン基などが挙げられる。
【００８７】
また、Ｒ^５２のアルキル基としては、メチル基、エチル基、プロピル基及びブチル基などが挙げられ、アラルキル基としては、ベンジル基、フェネチル基及びナフチルメチル基などが挙げられる。
【００８８】
また、α、β、γ、δ、ε、ζ、η、θ、ι、κ、λ、μ、ν、ξ、π、ρ及びσのベンゼン環が有してもよい置換基のうち、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子などが挙げられ、アルキル基としては、メチル基、エチル基、プロピル基及びブチル基などが挙げられ、アルコキシル基としては、メトキシ基、エトキシ基、プロポキシ基及びブトキシ基などが挙げられ、芳香族炭化水素環基としては、フェニル基、ナフチル基、アンスリル基及びピレニル基などが挙げられ、芳香族複素環基としては、ピリジル基、チエニル基、フリル基及びキノリル基などが挙げられる。
【００８９】
また、μとνのベンゼン環、ξとπのベンゼン環、及び、ρとσのベンゼン環が、置換基を介して共同で環をなす場合は、その置換基としては、プロピリデン基、エチレン基などが挙げられ、それらの基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する。
【００９０】
また、Ｚ^３１、Ｚ^３２、Ｚ^４１及びＺ^４２のハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子などが挙げられ、アルキル基としては、メチル基、エチル基、プロピル基及びブチル基などが挙げられ、アルコキシル基としては、メトキシ基、エトキシ基、プロポキシ基及びブトキシ基などが挙げられ、芳香族炭化水素環基としては、フェニル基、ナフチル基、アンスリル基及びピレニル基などが挙げられ、芳香族複素環基としては、ピリジル基、チエニル基、フリル基及びキノリル基などが挙げられる。
【００９１】
また、Ａｒ^５１、Ａｒ^５２、Ａｒ^６１、Ａｒ^６２及びＡｒ^７１のアルキル基としては、メチル基、エチル基、プロピル基及びブチル基などが挙げられ、アラルキル基としては、ベンジル基、フェネチル基及びナフチルメチル基などが挙げられ、芳香族炭化水素環基としては、フェニル基、ナフチル基、アンスリル基及びピレニル基などが挙げられ、芳香族複素環基としては、ピリジル基、チエニル基、フリル基及びキノリル基などが挙げられる。
【００９２】
また、Ａｒ^５３の２価の芳香族炭化水素環基としては、フェニレン基、ナフチレン基、アンスリレン基及びピレニレン基などが挙げられ、２価の芳香族複素環基としては、ピリジレン基及びチエニレン基などが挙げられる。
【００９３】
上記各基が有してもよい置換基としては、メチル基、エチル基、プロピル基及びブチル基などのアルキル基や、ベンジル基、フェネチル基及びナフチルメチル基などのアラルキル基や、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、ジベンゾフリル基及びジベンゾチオフェニル基などの芳香族炭化水素環基、芳香族複素環基や、メトキシ基、エトキシ基及びプロポキシ基などのアルコキシル基や、フェノキシ基及びナフトキシ基などのアリールオキシ基や、フッ素原子、塩素原子、臭素原子及びヨウ素原子などのハロゲン原子や、ニトロ基及びシアノ基などが挙げられる。
【００９４】
上記式（２）〜（７）のいずれかの式で示される構造を有する電荷輸送物質は、フェノール樹脂との相溶性が良好で、均一に分散された保護層の膜を容易に作製できる。
【００９５】
その相溶性を更に良好にするためには、上記式（２）〜（４）中のＲ^２１、Ｒ^２２、Ｒ^２３、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^４１、Ｒ^４２、Ｒ^４３、Ｒ^４４の２価の炭化水素基は炭素数４以下であることが好ましく、また、ヒドロキシアルキル基及びヒドロキシアルコキシル基の数が２個以上であることが好ましい。
【００９６】
また、上記式（５）〜（７）においては、電荷輸送物質に含まれるヒドロキシフェニル基がフェノール樹脂と反応して、保護層マトリックス中に電荷輸送物質が取り込まれ、保護層としての強度がより強くなる。
【００９７】
上記式（２）〜（７）のいずれかの式で示される構造を有する電荷輸送物質は、保護層を作製するための塗工液中に均一に溶解または分散させ、塗布して形成する。
【００９８】
上記式（２）〜（７）のいずれかの式で示される構造を有する電荷輸送物質と結着樹脂の混合割合は、質量比で、電荷輸送物質／結着樹脂＝０．１／１０〜２０／１０が好ましく、特には０．５／１０〜１０／１０がより好ましい。結着樹脂に対して電荷輸送物質が少な過ぎると残留電位低下の効果が小さくなり、多過ぎると保護層の強度を弱める場合がある。
【００９９】
以下、上記式（２）〜（７）のいずれかの式で示される構造を有する電荷輸送物質の具体例を示す。ただし、本発明は、これらに限定されるものではない。
【０１００】
【外１７】

【０１０１】
【外１８】

【０１０２】
【外１９】

【０１０３】
【外２０】

【０１０４】
【外２１】

【０１０５】
【外２２】

【０１０６】
【外２３】

【０１０７】
【外２４】

【０１０８】
【外２５】

【０１０９】
【外２６】

【０１１０】
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【０１１１】
【外２８】

【０１１２】
【外２９】

【０１１３】
これらの中でも、（３）、（４）、（５）、（８）、（１１）、（１２）、（１３）、（１７）、（２１）、（２４）、（２５）、（２６）、（２７）、（２８）、（３０）、（３１）、（３４）、（３５）、（３９）、（４４）、（４８）、（４９）、（５０）、（５２）、（５５）、（５６）、（５８）、（５９）が好ましく、更には、（３）、（８）、（１２）、（２５）、（３１）、（３９）、（４４）、（４９）、（５６）がより好ましい。
【０１１４】
保護層の塗工液を分散する溶剤としては、結着樹脂を十分に溶解し、上記式（２）〜（７）で示される構造を有する電荷輸送物質も十分に溶解し、導電性粒子を用いる場合はその分散性が良く、フッ素原子含有化合物、フッ素原子含有樹脂粒子及びシロキサン化合物などの潤滑性粒子を用いる場合は相溶性や処理性が良好で、更に、保護層の塗工液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。
【０１１５】
従って、溶剤としては、メタノール、エタノール及び２−プロパノールなどのアルコール類、アセトン及びメチルエチルケトンなどのケトン類、酢酸メチル及び酢酸エチルなどのエステル類、テトラヒドロフラン及びジオキサンなどのエーテル類、トルエン及びキシレンなどの芳香族炭化水素類、クロロベンゼン及び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、更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、エタノール及び２−プロパノールなどのアルコール類である。
【０１１６】
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、本発明に用いる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工液への分散が可能となる。
【０１１７】
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及びブレードコーティング法などの塗工方法を用いることができる。
【０１１８】
本発明における保護層は、上述の化合物を含有する溶液を感光層上に塗布し、乾燥することによって得ることができる。含有する結着樹脂が、熱硬化型の硬化性樹脂である場合は、硬化温度は、１００℃〜３００℃であることが好ましく、特には１２０℃〜２００℃ことが好ましい。
【０１１９】
また、保護層の膜厚は、電荷の移動の点から１〜５．５μｍであることが好ましい。
【０１２０】
本発明においては、上記保護層中に、帯電時に発生するオゾンや窒素酸化物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。
【０１２１】
次に、電子写真感光体が有する感光層などについて以下に説明する。
【０１２２】
本発明における感光層は、電荷発生物質と電荷輸送物質の両方を同一の層に含有する単層型でも電荷発生物質を含有する電荷発生層と電荷輸送物質を含有する電荷輸送層とを有する積層型でもよいが、導電性支持体上に電荷発生層及び電荷輸送層を順次積層した積層型であることが好ましい。この例を図１に示す。
【０１２３】
図１（ａ）に示す電子写真感光体は、導電性支持体４の上に電荷発生層３、電荷輸送層２が順に設けられており、更に表面層として保護層１が設けられている。
【０１２４】
導電性支持体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、アルミニウム合金及び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、アルミニウム合金及び酸化インジウム−酸化スズ合金などを真空蒸着によって被膜形成したプラスチック、導電性粒子（例えばカーボンブラック、酸化スズ、酸化チタン及び銀粒子など）を適当なバインダーとともにプラスチックや紙に含浸した支持体、並びに導電性バインダーを有するプラスチックなどを用いることができる。
【０１２５】
導電性支持体４の形状は、円筒形のドラムタイプやベルト状などあるが、特に制限されるものではない。
【０１２６】
本発明においては、導電性支持体４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）５を設けることができる（図１（ｂ））。
【０１２７】
結着層５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、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５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、酸化アルミニウムなどによって形成できる。結着層５の膜厚は、５μｍ以下であることが好ましく、特には０．１〜３μｍであることが好ましい。
【０１２８】
また、本発明においては、図１（ｃ）のように導電性支持体４と電荷発生層３の間に、結着層５、更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。
【０１２９】
電荷発生層３は、電荷発生物質及び必要に応じて結着樹脂を含有する。
【０１３０】
電荷発生物質としては、モノアゾ、ジスアゾ及びトリスアゾなどのアゾ系顔料、金属フタロシアニン及び非金属フタロシアニンなどのフタロシアニン系顔料、インジゴ及びチオインジゴなどのインジゴ系顔料、ペリレン酸無水物及びペリレン酸イミドなどのペリレン系顔料、アンスラキノン及びピレンキノンなどの多環キノン系顔料、スクワリリウム色素、ピリリウム塩及びチアピリリウム塩類などの塩類、トリフェニルメタン系色素、セレン、セレン−テルル及びアモルファスシリコンなどの無機物質、キナクリドン顔料、アズレニウム塩顔料、シアニン染料、キサンテン色素、キノンイミン色素、スチリル色素、硫化カドミウム、並びに酸化亜鉛などが挙げられる。本発明においては、中でもガリウムフタロシアニン化合物であることが好ましく、特にはヒドロキシガリウムフタロシアニンであることが好ましく、更にはＣｕＫαの特性Ｘ線回折におけるブラッグ角（２θ±０．２°）の７．４°及び２８．２°に強いピークを有するヒドロキシガリウムフタロシアニンであることが好ましい。
【０１３１】
結着樹脂としては、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、尿素樹脂及び塩過ビニル−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。
【０１３２】
電荷発生層３は、電荷発生物質を質量比で０．３〜４倍量の結着剤樹脂及び溶剤と共に、ホモジナイザー、超音波、ボールミル、サンドミル、アトライター及びロールミルなどの方法で分散することによって得られた溶液を、塗布し、乾燥することにより形成される。その膜厚は、５μｍ以下であることが好ましく、特には０．０１〜１μｍであることが好ましい。
【０１３３】
用いられる溶剤は、使用する電荷発生物質や結着樹脂の溶解性や分散安定性を考慮して選択されるが、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。
【０１３４】
また、電荷発生層３には、種々の増感剤、酸化防止剤、紫外線吸収剤及び可塑剤などを必要に応じて添加することもできる。
【０１３５】
電荷輸送層２は、電荷輸送物質及び必要に応じて結着樹脂を含有する。
【０１３６】
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及び各種トリアリールメタン系化合物などが挙げられる。
【０１３７】
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、アルキド樹脂及び不飽和樹脂などが挙げられる。これらの中では、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及びジアリルフタレート樹脂が特に好ましい。
【０１３８】
電荷輸送層２は、電荷輸送物質と結着樹脂を溶剤に溶解することによって得られた溶液を、塗布し、乾燥することにより形成される。電荷輸送物質と結着樹脂との混合割合は質量比で２：１〜１：２程度である。
【０１３９】
溶剤としてはアセトン及びメチルエチルケトンなどのケトン類、酢酸メチル及び酢酸エチルなどのエステル類、トルエン及びキシレンなどの芳香族炭化水素類、並びにクロロベンゼン、クロロホルム及び四塩化炭素などの塩素系炭化水素類などが挙げられる。
【０１４０】
この溶液を塗布する際には、例えば浸漬塗布法、スプレー塗布法及びスピンナー塗布法などの塗布法を用いることができる。
【０１４１】
また、乾燥温度は１０℃〜２００℃であることが好ましく、特には２０℃〜１５０℃であることが好ましい。また、乾燥時間は５分〜５時間であることが好ましく、特には１０分〜２時間であることが好ましい。
【０１４２】
更に、電荷輸送層２には、酸化防止剤、紫外線吸収剤及び可塑剤などを必要に応じて添加することもできる。
【０１４３】
本発明においては、この電荷輸送層２の上に更に保護層１を上記の方法によって形成するのである。
【０１４４】
以下に、本発明にかかる電子写真感光体を用いた電子写真装置の具体的な実施形態を示す。
【０１４５】
＜実施形態１＞
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備えた電子写真装置の概略構成を示す。
【０１４６】
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。
【０１４７】
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度変調された露光光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。
【０１４８】
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送された転写材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。
【０１４９】
トナー画像の転写を受けた転写材１７は、電子写真感光体表面から分離されて定着手段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。
【０１５０】
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る。また、クリーニング手段を有さずに（クリーナーレス）、転写残りトナーを直接、現像手段などで回収することもできる。更に、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、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。
【０１５１】
本発明においては、上述の電子写真感光体１１、帯電手段１３、現像手段１５及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、帯電手段１３、現像手段１５及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２１とすることができる。
【０１５２】
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み取り、信号化し、この信号に従って行われるレーザービームの走査、ＬＥＤアレイの駆動または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。また、必要に応じて他の補助プロセスを加えてもよい。
【０１５３】
＜実施形態２＞
図３に帯電粒子供給手段を備えた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具備した電子写真装置の概略構成を示す。
【０１５４】
ドラム形状の電子写真感光体３１は矢印方向に一定速度をもって回転駆動される。
【０１５５】
帯電手段が有する帯電ローラー３２は、帯電粒子３３（電子写真感光体を帯電するための導電性粒子）と、粒子担持体としての中抵抗層３２ｂ及び芯金３２ａにより構成される。帯電ローラー３２は、電子写真感光体３１に所定の侵入量をもって当接し、接触部ｎを形成する。
【０１５６】
本実施形態における帯電ローラー３２は、芯金３２ａ上にゴムあるいは発泡体の中抵抗層３２ｂを形成し、更にその表層に帯電粒子３３を担持して構成される。
【０１５７】
中抵抗層３２ｂは、樹脂（例えばウレタン）、導電性粒子（例えばカーボンブラック）、硫化剤及び発泡剤などにより処方され、芯金３２ａの上にローラー状に形成される。その後、表面を研磨される。
【０１５８】
本実施形態における帯電ローラーは、実施形態１における帯電ローラー（放電用の帯電ローラー）に対し、以下の点で特に異なる。
（１） 表層に高密度の帯電粒子を担持するための表面構造や粗さ特性
（２） 注入帯電に必要な抵抗特性（体積抵抗率、表面抵抗）
放電用の帯電ローラーの表面は平坦であって、表面の平均粗さＲａでサブμｍ以下であり、ローラー硬度も高い。放電を用いた帯電において、放電現象は帯電ローラーと電子写真感光体の接触部から少し離れた数十μｍの隙間で放電現象が起きる。帯電ローラー及び電子写真感光体表面に凹凸が存在する場合、部分的に電界強度が異なるため放電現象が不安定になり、帯電ムラを生じる。従って、放電用の帯電ローラーは平坦で高硬度な表面を必要とする。
【０１５９】
ではなぜ放電用の帯電ローラーでは注入帯電できないのかというと、前述のような表面構造では外観上ドラムと密着しているように見えるが、電荷注入に必要な分子レベルでのミクロな接触性という意味ではほとんど接触していないのである。
【０１６０】
一方、注入帯電用の帯電ローラー３２は、帯電粒子３３を高密度に担持する必要からある程度の粗さが要求される。平均粗さＲａにして、１μｍ〜５００μｍが好ましい。１μｍ未満では帯電粒子３３を担持するための表面積が不足すると共に、絶縁物（例えばトナー）などがローラー表層に付着した場合、その周辺が電子写真感光体３１に接触できにくくなり、帯電性能が低下しやすくなる。逆に、５００μｍを超えると帯電ローラー表面の凹凸が電子写真感光体の面内帯電均一性を低下しやすくなる。
【０１６１】
平均粗さＲａの測定は、キーエンス社製表面形状測定顕微鏡ＶＦ−７５００、ＶＦ７５１０を用い対物レンズ１２５０倍から２５００倍を用い非接触にてローラー表面の形状及びＲａの測定を行うことができる。
【０１６２】
放電用の帯電ローラーは、芯金に低抵抗の基層を形成した後、表面を高抵抗層で被覆している。放電によるローラー帯電は印加電圧が高く、ピンホール（膜の損傷による支持体の露出）があるとその周辺にまで電圧降下が及び、帯電不良を生じる。従って、１０^１１Ω□以上にすることが好ましい。
【０１６３】
一方、注入帯電方式においては、低電圧による帯電を可能とするため表層を高抵抗にする必要がなく、帯電ローラーを単層で構成することができる。むしろ、注入帯電においては、帯電ローラーの表面抵抗は１０^４〜１０^１０Ωであることが好ましい。１０^１０Ωを超えると帯電面内の均一性が低下し、帯電ローラーの摺擦によるムラが中間調画像にスジ状となって現れ、画像品位の低下が見られやすくなる。一方、１０^４Ω未満の場合は、注入帯電であっても電子写真感光体のピンホールによる周辺の電圧降下を生じやすくなる。
【０１６４】
更に、体積抵抗率については１０^４〜１０^７Ω・ｃｍの範囲であることが好ましい。１０^４Ω・ｃｍ未満の場合は、ピンホールリークによる電源の電圧降下を生じやすくなる。一方、１０^７Ω・ｃｍを超える場合は、帯電に必要な電流が確保できにくくなり、帯電電圧が低下しやすくなる。
【０１６５】
帯電ローラーの抵抗測定は以下の手順で行った。
【０１６６】
ローラー抵抗は、帯電ローラー３２の芯金３２ａに総圧１ｋｇの荷重がかかるよう外径３０ｍｍの絶縁体ドラムに電極を施し測定した。電極は、主電極の周りにガード電極を配して測定を行った。主電極とガード電極間の距離はおよそ弾性層３２ｂの厚さ程度に調整し、主電極がガード電極に対し十分な幅を確保した。測定は、主電極に電源から＋１００Ｖを印加して、電流計Ａｖ及びＡｓに流れる電流を測定し、それぞれ体積抵抗率、表面抵抗を測定した。
【０１６７】
注入帯電方式においては、帯電部材は柔軟な電極として機能することが重要である。磁気ブラシにおいては、磁性粒子層自体がもつ柔軟性により実現している。本実施形態においては、中抵抗層３２ｂの弾性特性を調整して達成している。アスカーＣ硬度は、１５度〜５０度が好ましい範囲であり、２５〜４０度がより好ましい範囲である。硬度が高過ぎると必要な侵入量が得られず、電子写真感光体との間に接触部ｎを確保できないため、帯電性能が低下する。また、物質の分子レベルの接触性が得られないため、異物の混入などによりその周辺への接触が妨げられる。一方、硬度が低過ぎると形伏が安定しないため、被帯電体との接触圧にムラを生じて帯電ムラを生じる。あるいは、長期放置によるローラーの永久変形ひずみによる帯電不良を生じる。
【０１６８】
帯電ローラー３２の材質としては、ＥＰＤＭ、ウレタン、ＮＢＲ、シリコーンゴムや、ＩＲなどに抵抗調整のためのカーボンブラックや金属酸化物などの導電性物質を分散したゴム材が挙げられる。導電性物質を分散せずにイオン導電性の材料を用いて抵抗調整をすることも可能である。その後、必要に応じて表面の粗さ調整、研磨などによる成型を行う。また、機能分離した複数層による構成も可能である。
【０１６９】
ローラーの形態としては多孔体構造がより好ましい。前述の表面粗さをローラーの成型と同時に得られるという点で製造的にも有利である。発泡体のセル径としては、１〜５００μｍが適切である。発泡成形した後に、その表面を研摩することにより多孔体表面を露出させ、前述の粗さを持った表面構造を作製可能である。
【０１７０】
帯電ローラー３２は、電子写真感光体３１に対して侵入量を配設し、接触部ｎを形成させて、この接触部ｎにおいて電子写真感光体３１の回転方向と逆方向（カウンター）で回転駆動され、電子写真感光体３１面に対して速度差を持って接触することができる。また、プリンターの画像記録時には帯電ローラー３２に帯電バイアス印加電源Ｓ１から所定の帯電バイアスが印加されるこれにより電子写真感光体１の周面が注入帯電方式で所定の極性・電位に一様に帯電処理される。
【０１７１】
帯電粒子３３は、トナーに添加して蓄積され、トナーの現像と共に電子写真感光体３１を介して帯電ローラー３２に供給される。
【０１７２】
供給手段として、規制ブレード３４を帯電ローラー３２に当接させ、帯電ローラー３２と規制ブレード３４の間に帯電粒子３３を保持する構成を採る。そして、電子写真感光体３１の回転に伴い一定量の帯電粒子３３が帯電ローラー３２に塗布され、次いで、帯電ローラー３２と電子写真感光体３１との間の当接部ｎに至る。
【０１７３】
更に帯電粒子３３の粒径は、高い帯電効率と帯電均一性を得るために１０μｍ以下が好ましい。本発明においては、帯電粒子が凝集体を構成している場合の粒径は、その凝集体としての平均粒径として定義した。粒径の測定には、電子顕微鏡による観察から１００個以上抽出し、水平方向最大弦長を持って体積粒径分布を算出し、その５０％平均粒径を持って決定した。
【０１７４】
帯電粒子３３は、一次粒子の状態で存在するばかりでなく、二次粒子の凝集した状態で存在することもなんら問題はない。どのような凝集状態であれ、凝集体として帯電粒子としての機能が実現できればその形態は重要ではない。
【０１７５】
帯電粒子３３は、特に電子写真感光体の帯電に用いる場合に潜像露光の妨げにならないよう白色または透明に近いことが好ましい。更に、帯電粒子が電子写真感光体３１上から転写材Ｐに一部転写されてしまうことを考えると、カラー記録では無色あるいは白色のものが好ましい、また、画像露光時に帯電粒子３３による光散乱を防止するためにもその粒径は構成画素サイズ以下、更にはトナー粒径以下であることが好ましい。粒径の下限値としては、粒子として安定に得られるものとして１０ｎｍが限界と考えられる。
【０１７６】
３６は現像装置である。電子写真感光体３１表面の静電潜像は、この現像装置３６により現像部位ａにてトナー画像として現像される。現像装置３６内にはトナーに帯電粒子を添加した混合剤が備えられている。
【０１７７】
また、本実施形態の電子写真装置（プリンター）は、トナーリサイクルプロセスであり、画像転写後の電子写真感光体３１表面上に残留した転写残トナーは専用のクリーニング手段（クリーナー）で除去されるのではなく、電子写真感光体３１の回転に伴いカウンター回転する帯電ローラー３２に一時的に回収され、帯電ローラー３２外周を周回するにつれて、反転したトナー電荷が正規化されて順次電子写真感光体３１に吐き出されて現像部位ａに至り、マグネットローラー３６ａと現像スリーブ３６ｂを有する現像手段３６において現像同時クリーニングにて回収・再利用される。Ｓ２は現像手段３６に現像バイアスを印加する電源である。
【０１７８】
３５はレーザーダイオード・ポリゴンミラーなどを含むレーザービームスキャナー（露光手段）である。このレーザービームスキャナー３５は、目的の画像情報の時系列デジタル画像信号に対応して強度変調されたレーザー光を出力し、該レーザー光で上記電子写真感光体３１の一様帯電面を走査露光Ｌする。この走査露光光Ｌにより電子写真感光体３１の表面に目的の画像情報に対応した静電潜像が形成される。
【０１７９】
３８は熱定着方式などの定着手段である。電子写真感光体３１と転写ローラー３７との間の転写当接部ｂに給紙されて電子写真感光体３１側のトナー画像の転写を受けた転写材Ｐは、電子写真感光体３１の表面から分離されてこの定着手段３８に導入され、トナー画像の定着を受けて画像形成物（プリント・コピー）として装置外へ排出される。Ｓ３は転写ローラー３７に転写バイアスを印加する電源である。
【０１８０】
３９はプロセスカートリッジである。この実施形態においては、電子写真感光体、帯電手段および現像手段が一体に支持されている。プロセスカートリッジ３９は、電子写真装置に設けられたレール４０などの案内手段により、電子写真装置本体に着脱自在となっている。
【０１８１】
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、液晶プリンター及びレーザー製版などの電子写真応用分野にも幅広く適用し得るものである。
【０１８２】
【実施例】
以下、本発明の実施例を説明するが、本発明は以下の実施例に限定されない。なお、実施例中の「部」、「％」は、それぞれ質量部、質量％を示す。
【０１８３】
（参考例１）
導電性支持体としてのφ３０ｍｍ×２６１ｍｍのアルミニウムシリンダー上にポリアミド樹脂（商品名：アミランＣＭ８０００、東レ（株）製）の５質量％メタノール溶液を浸漬塗布法で塗布し、乾燥することによって、膜厚が０．５μｍの結着層を形成した。
【０１８４】
次に、ＣｕＫαの特性Ｘ線回折におけるブラッグ角（２θ±０．２°）の７．４°及び２８．２°に強いピークを有するヒドロキシガリウムフタロシアニン結晶３．５部とポリビニルブチラール樹脂（商品名：エスレックＢＸ−１、積水化学工業（株）製）１部をシクロヘキサノン１２０部に添加し、φ１ｍｍガラスビーズを用いたサンドミルで３時間分散し、更に酢酸エチル１２０部を加えて希釈して電荷発生層用塗工液を調製した。この電荷発生層用塗工液を上記結着層上に浸漬塗布し、１００℃で１０分間乾燥することによって、膜厚が０．１５μｍの電荷発生層を形成した。
【０１８５】
図４に上記ヒドロキシガリウムフタロシアニン結晶の粉末Ｘ線回折図を示す。粉末Ｘ線回折の測定にはＣｕＫα線を用い、次の条件で行った。
【０１８６】
使用測定機：マック・サイエンス社製、全自動Ｘ線回折装置ＭＸＰ１８
Ｘ線管球：Ｃｕ
管電圧：５０ｋＶ
管電流：３００ｍＡ
スキャン方法：２θ／θスキャン
スキャン速度：２ｄｅｇ．／ｍｉｎ
サンプリング間隔：０．０２０ｄｅｇ．
スタート角度（２θ）：５ｄｅｇ．
ストップ角度（２θ）：４０ｄｅｇ．
ダイバージェンススリット：０．５ｄｅｇ．
スキャッタリングスリット：０．５ｄｅｇ．
レシービングスリット：０．３ｄｅｇ．
湾曲モノクロメーター使用
次いで、電荷輸送物質として下記式で示される化合物１０部及び結着樹脂としてビスフェノールＺ型ポリカーボネート（商品名：ユーピロンＺ−２００、三菱ガス化学（株）製）１０部を、モノクロロベンゼン１００部及びテトラヒドロフラン（ＴＨＦ）６０部に溶解して電荷輸送層用塗工液を調製した。
【０１８７】
【外３０】

【０１８８】
この塗工液を電荷発生層上に塗布し、１０５℃で１時間をかけて熱風乾燥して、膜厚が２０μｍの電荷輸送層を形成した。
【０１８９】
次に、下記式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超微粒子２０部、
【外３１】

【０１９０】
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（株）製）で表面処理した（処理量２０％）アンチモンドープ酸化スズ微粒子３０部及びエタノール１５０部を、サンドミル装置にて６６時間かけて分散を行い、更に、ポリテトラフルオロエチレン微粒子（平均粒径０．１８μｍ）２０部を加えて２時間分散を行った。その後、レゾール型熱硬化型フェノール樹脂（商品名：ＰＬ−４８０４、アミン系化合物を含む、群栄化学工業（株）製）を樹脂成分として３０部溶解し、保護層用塗工液とした。
【０１９１】
この塗工液を上記電荷輸送層上に浸漬塗布し、１４５℃で１時間熱風乾燥することによって、保護層を形成した。
【０１９２】
この保護層の膜厚を、光の干渉による瞬間マルチ測光システムＭＣＰＤ−２０００（大塚電子（株）製）を用いて測定したところ、３μｍであった。また、保護層用塗工液の分散性は良好で、保護層表面を目視によって観察したところ、ムラがなく均一であった。
【０１９３】
得られた電子写真感光体のＶｓｌ（０．２）及びＶｓｌ（０．５）を、ドラム試験機（ジェンテック（株）製））を用いて測定した。測定環境は、２３℃／５％ＲＨで、電子写真感光体の表面を−７００Ｖに帯電し、１０ｌｕｘ・ｓｅｃの光量の白色光を照射した。白色光を照射した位置から９０°及び２２４．５°の位置に電位測定プローブを設置し、９０°の位置の電位プローブでＶｓｌ（０．２）を、２２４．５°の位置に電位測定プローブでＶｓｌ（０．５）を測定した。
【０１９４】
また、上述のようにして得た電子写真感光体を上記実施形態１と同様の電子写真システムである電子写真装置（商品名：レーザージェット４０００、ヒューレットパッカード（株）製）の改造機に搭載し、画像を評価した。主な改造点は、システムを実施形態２の構成にしたところである。
【０１９５】
用いた帯電粒子Ｍの体積抵抗は１Ω・ｃｍであり、初期の担持量は５ｍｇ／ｃｍ^２であった。また、電源Ｓ１から帯電部材に印加する電圧は、−７００ＶのＤＣ電圧のみとした。
【０１９６】
以上の条件で、常温低湿環境（２３℃／５％ＲＨ）下で初期の暗部電位（Ｖｄ）を測定し、また、画像を目視により評価した。更に、耐久試験として常温低湿環境（２３℃／５％ＲＨ）下で及び高温高湿環境（３２℃／８５％ＲＨ）下で５０００枚の画像出し後に得られた画像を目視にて評価した。耐久時には印字率６％の文字画像を用い、評価時には感光体の最初の１／３回転分がベタ黒で、残りが１２００ｄｐｉの１ドットの黒が１ドットの白で囲まれている状態が連続しているハーフトーンである画像を用いた。
【０１９７】
それぞれの結果を表１に示す。
【０１９８】
（参考例２）
電子写真装置を実施形態２の構成に改造しないで用いた以外は参考例１と同様にして電子写真感光体を評価した。結果を表１に示す。
【０１９９】
（参考例３及び４）
レゾール型フェノール樹脂（商品名：ＰＬ−４８０４）をレゾール型フェノール樹脂ＰＬ−４８５２（群栄化学工業（株）製、アミン系化合物含有）（参考例３）及びＰＬ−５２９４（群栄化学工業（株）製、アルカリ金属含有）（参考例４）に変えた以外は参考例１と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２０１】
（参考例５及び６）
レゾール型フェノール樹脂（商品名：ＰＬ−４８０４）をビスフェノールＡ型エポキシ樹脂（商品名：Ｒ３０９：三井石油化学（株）製）に変え、溶剤をエタノールからテトラヒドロフランに変え、塗布方法を浸漬塗布法からスプレー塗布法に変えて保護層を形成した以外は参考例１と同様にして電子写真感光体を作成し、参考例１（参考例５）及び参考例２（参考例６）と同様にして評価した。結果を表１に示す。
【０２０２】
（参考例７及び８）
ビスフェノールＡ型エポキシ樹脂の使用量を３０部から４０部に変えた以外は参考例５及び参考例６と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２０３】
（参考例９及び１０）
保護層の膜厚を３μｍから５μｍに変えた以外は参考例７及び参考例８と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２０４】
（参考例１１及び１２）
保護層の膜厚を３μｍから５．５μｍに変えた以外は参考例７及び参考例８と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２０５】
（比較例１及び２）
ビスフェノールＡ型エポキシ樹脂を４０部から５０部に変え、保護層の膜厚を３μｍから６．５μｍに変えた以外は参考例７及び参考例８と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２０６】
（比較例３及び４）
ビスフェノールＡ型エポキシ樹脂を３０部から５５部に変えた以外は参考例５及び参考例６と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２０７】
（比較例５及び６）
ビスフェノールＡ型エポキシ樹脂を３０部から１０部に変えた以外は参考例５及び参考例６と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２０８】
（実施例１）
酸化スズ粒子を添加せず、その代わりに下記式で示される電荷輸送物質を３０部添加して保護層を形成した以外は参考例２と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２０９】
【外３２】

【０２１０】
（実施例２）
レゾール型フェノール樹脂（商品名ＰＬ−４８５２）を硬化型シロキサン樹脂ＫＰ−８５４（信越化学（株）製）に変えた以外は実施例１と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２１１】
（実施例３）
保護層の膜厚を３μｍから５．５μｍに変えた以外は実施例２と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２１２】
（比較例７）
硬化型シロキサン樹脂の使用量を３０部から４０部に変え、保護層の膜厚を３μｍから６．５μｍに変えた以外は実施例２と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２１３】
（比較例８）
電荷輸送物質の添加量を３０部から７０部に変えた以外は実施例２と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２１４】
（比較例９）
電荷輸送物質の添加量を３０部から１０部に変え、保護層の膜厚を３μｍから６．５μｍに変えた以外は実施例２と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２１５】
（比較例１０）
電荷発生物質をヒドロキシガリウムフタロシアニン結晶ＣｕＫαの特性Ｘ線回折におけるブラッグ角（２θ±０．２°）の７．６°、１０．２°、２５．３°及び２８．６°に強いピークを有するオキシチタニウムフタロシアニン結晶を用いた以外は実施例３と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２１６】
（参考例１３）
帯電ローラーに印加する電圧をＤＣのみから−７００ＶのＤＣ電圧にピーク間電圧が５００ＶのＡＣ電圧を重畳した電圧に変えた以外は、参考例５と同様にして電子写真感光体を評価した。結果を表１に示す。
【０２１７】
（比較例１１）
帯電ローラーに印加する電圧をＤＣのみから−７００ＶのＤＣ電圧にピーク間電圧が５００ＶのＡＣ電圧を重畳した電圧に変えた以外は、比較例２と同様にして電子写真感光体を評価した。結果を表１に示す。
【０２１８】
（比較例１２）
硬化型シロキサン樹脂の使用量を３０部から４５部にかえ、保護層の膜厚を３μｍから２μｍに変えた以外は実施例２と同様にして電子写真感光体を作成し、評価した。結果を表１に示す。
【０２１９】
【表１】

【０２２０】
【表２】

【０２２１】
【発明の効果】
以上のように、本発明によれば、繰り返し使用の耐久によるポジゴーストやネガゴーストも殆どなく、更に画像ボケもなく、安定して高品位な画像を得ることができる電子写真感光体、該電子写真感光体を有するプロセスカートリッジ及び電子写真装置を提供することが可能となった。
【図面の簡単な説明】
【図１】本発明にかかる電子写真感光体の層構成の一例を示す断面図である。
【図２】本発明にかかる電子写真感光体を有するプロセスカートリッジを具備した電子写真装置である実施形態１の概略構成を示す図である。
【図３】本発明にかかる電子写真感光体を有するプロセスカートリッジを具備した電子写真装置である実施形態２の概略構成の一例を示す図である。
【図４】本発明の実施例に用いたヒドロキシガリウムフタロシアニンのＣｕＫαの特性Ｘ線回折図である。[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 having at least a charge generation layer, a charge transport layer, and a protective layer in this order on a conductive support, and the electrophotographic photosensitive member. The present invention relates to a process cartridge provided with a body and an electrophotographic apparatus.
[0002]
[Prior art]
In recent years, electrophotographic photosensitive members have been required to have higher durability. For example, JP-A-5-173350 discloses that a protective layer containing a curable resin is provided on a photosensitive layer. It has been disclosed to provide an electrophotographic photoreceptor having excellent durability.
[0003]
Further, for example, Japanese Patent Application Laid-Open No. 7-5748 discloses so-called injection charging in which an electrophotographic photosensitive member is charged by injecting electric charge into a protective layer on the photosensitive layer without substantial discharge. Yes.
[0004]
Thus, in the electrophotographic field, providing a protective layer on the photosensitive layer of the electrophotographic photosensitive member is one of the very important technologies.
[0005]
[Patent Document 1]
JP 05-173350 A [Patent Document 2]
Japanese Patent Application Laid-Open No. 07-005748
[Problems to be solved by the invention]
However, although the electrophotographic photosensitive member having the protective layer has the advantages as described above, positive ghosts and negative ghosts are easily generated. In addition, these phenomena are particularly prominent when the protective layer contains a curable resin as a binder resin.
[0007]
On the other hand, with the recent progress in colorization of electrophotography and high definition such as 1200 dpi (dot per inch), higher image quality is required.
[0008]
An object of the present invention is to provide an electrophotographic photosensitive member that is less likely to cause positive ghost, negative ghost, and image blur even when used repeatedly, and that can stably obtain a high-quality image.
[0009]
Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having such an electrophotographic photosensitive member.
[0010]
[Means for Solving the Problems]
That is, the present invention provides an electrophotographic photosensitive member having a conductive support, a photosensitive layer and a protective layer in this order.
The surface of the electrophotographic photosensitive member is charged to −700 V in an environment of 23 ° C./5% RH and irradiated with white light having a light quantity of 10 lux · sec. The surface potential Vsl of the electrophotographic photosensitive member when the surface potential Vsl (0.2) satisfies the following formula (1) and 0.5 seconds have elapsed after irradiation with the Vsl (0.2) and white light. The electrophotographic photosensitive member is characterized in that the difference from (0.5) satisfies the following formula (2).
20 (V) ≦ | Vsl (0.2) | ≦ 80 (V) (1)
10 (V) ≦ | Vsl (0.2) −Vsl (0.5) | ≦ 30 (V) (2)
The present invention also provides a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0012]
As described above, the electrophotographic photosensitive member having the protective layer easily generates positive ghosts and negative ghosts, and image blurring easily occurs in a high temperature and high humidity environment. In addition, these phenomena are particularly prominent when the protective layer contains a curable resin as a binder resin.
[0013]
The present inventors have speculated that these causes are charges accumulated at the interface formed between the photosensitive layer and the protective layer.
[0014]
In recent years, although the development of a protective layer for an electrophotographic photosensitive member has been progressing rapidly, there is no change in the formation of an interface between the photosensitive layer and the protective layer. In particular, when a curable resin is used for the protective layer, the tendency becomes stronger.
[0015]
The charge generated in the photosensitive layer moves in the photosensitive layer, reaches the interface, and then enters the protective layer. Usually, it is considered that there is some charge accumulation at the interface. The present inventors considered that charge accumulation at this interface may be the cause of the positive ghost and the negative ghost.
[0016]
That is, in the case of an electrophotographic photosensitive member having a protective layer, the charge that has moved through the photosensitive layer after exposure reaches the interface with the protective layer and accumulates, or the charge stays in the protective layer. If the second charge on the photosensitive member is charged at that location, the absolute value of the surface potential is lowered due to the accumulated and retained charge, and a positive ghost is observed when the halftone image is reversely developed.
[0017]
On the other hand, if the charge accumulation and retention are more conspicuous, a large amount of charge remains accumulated and retained even after charging on the second circumference of the photoconductor, and exposure is performed to form a halftone image. Coupled with newly generated charge accumulation / stagnation, the absolute value of the surface potential is not sufficiently lowered, and a halftone image is observed as negative ghost when it is reversely developed.
[0018]
Therefore, the present inventors, by finely controlling the accumulation and retention of the charges, specifically, the potential characteristics of the electrophotographic photosensitive member satisfy the relationship of the above formulas (1) and (2). The present inventors have found that the above technical problem can be solved by controlling to the present invention, and have reached the present invention. Formulas (1) and (2) in the present invention are derived empirically as a result of various studies by the present inventors based on the above viewpoint.
[0019]
The potential characteristic of the electrophotographic photosensitive member in the present invention is defined by the surface potential of the electrophotographic photosensitive member after the surface of the electrophotographic photosensitive member is charged to −700 V and irradiated with white light having a light quantity of 10 lux · sec. .
[0020]
In the present invention, the residual potential Vsl (0.2) of the electrophotographic photosensitive member when 0.2 seconds have elapsed after light irradiation is 20 (V) or more and 80 (V) or less in absolute value. V) or more and 70 (V) or less is preferable, and 20 (V) or more and 60 (V) or less is particularly preferable. If | Vsl (0.2) | is less than 20 (V), a positive ghost is likely to occur, and if it exceeds 80 (V), a negative ghost is likely to occur.
[0021]
However, it is not sufficient to define only the range of | Vsl (0.2) |. In the present invention, the electrophotographic photosensitivity when 0.5 seconds elapses after irradiation with Vsl (0.2) is further applied. The difference | Vsl (0.2) −Vsl (0.5) | of the residual potential Vsl (0.5) of the body needs to be 10 (V) or more and 30 (V) or less. If | Vsl (0.2) −Vsl (0.5) | is less than 10 (V), the potential attenuation in a short time is too small, that is, the charge is very likely to accumulate and stay, In this case, a negative ghost will occur. On the other hand, if the voltage exceeds 30 (V), the potential decay in a short time is too large, that is, the absolute value of the surface potential during charging of the second circumference of the photoreceptor is too low, and a positive ghost is generated. In the present invention, | Vsl (0.2) −Vsl (0.5) | is preferably 12 (V) or more and 25 (V) or less.
[0022]
These surface potentials were measured under an environment of 23 ° C./5% RH. By evaluating the state of charge accumulation and retention under such low humidity, more essential electrophotographic characteristics can be evaluated.
[0023]
From the viewpoint of the interface, the configuration of the protective layer is a factor that greatly affects the potential characteristics.
[0024]
The constitution of the protective layer having a great influence on the potential characteristics includes the types of compounds contained in the protective layer, the compounding ratio of these compounds, the degree of crosslinking of the binder resin, the thickness of the protective layer, and the compounds contained in the photosensitive layer. In the present invention, it is important that the electrophotographic photosensitive member has the above-mentioned potential characteristics.
[0025]
It described in detail below configuration form status for realizing the potential characteristics.
[0026]
Protective layer of the electrophotographic photosensitive member of the present invention, Ru layers der containing a binder resin and a conductive charge transport material quality.
[0027]
Binder resins for the protective layer is a curable resins. Among them, phenol resin is used. Phenolic resins resistance environmental change is small again in the protective layer. In particular, a thermosetting resol-type phenol resin is more preferable because it has a high surface hardness, excellent wear resistance, and excellent dispersibility of fine particles and stability after dispersion.
[0028]
The curable phenol resin is a resin generally obtained by a reaction between phenols and formaldehyde.
[0029]
There are two types of phenolic resins: a resole type obtained by reacting with phenol with an excess of formaldehyde and an alkali catalyst, and a novolak obtained by reacting with an acid catalyst with an excess of phenol with respect to formaldehyde Divided into types.
[0030]
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 if heated as it is, but forms a cured product by adding a formaldehyde source such as paraformaldehyde or hexamethylenetetramine and heating.
[0031]
In general and industrially, the resol type is used as a varnish for paints, adhesives, castings and laminates, and the novolak type is mainly used as a molding material or a binder.
[0032]
In the present invention, as the phenol resin, either a resol type or a novolac type can be used, but it is preferable to use a resol type from the viewpoint of curing without adding a curing agent, operability as a paint, and the like.
[0033]
In the present invention, when a phenol resin is used, one or two or more phenol resins can be mixed and used, and a resol type and a novolak type can also be mixed and used. Any known phenolic resin may be used.
[0034]
Usually, a resol type phenol resin is produced by using a phenol compound and an aldehyde compound in the presence of an alkali catalyst.
[0035]
The main phenols used include, but are not limited to, phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, resorcin, and bisphenol.
[0036]
Examples of aldehydes include formaldehyde, paraformaldehyde, furfural and acetaldehyde, but are not limited thereto.
[0037]
These phenols and aldehydes are reacted in the presence of an alkali catalyst, and monomers of monomethylolphenols, dimethylolphenols, trimethylolphenols, and mixtures thereof, or oligomers thereof, and monomers and oligomers Make a mixture. Among these, relatively large molecules having a repeating molecular structural unit of about 2 to 20 are oligomers and one is a monomer.
[0038]
Examples of the alkali catalyst used include metal-based alkali compounds and amine compounds. Examples of metal-based alkali compounds include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide. However, examples of the amine compound include, but are not limited to, ammonia, hexamethylenetetramine, trimethylamine, triethylamine, and triethanolamine.
[0039]
In the present invention, it is preferable to use an amine compound in consideration of fluctuations in resistance under a high-humidity environment, but in consideration of other electrophotographic characteristics, a mixture using a metal-based alkali compound is mixed. You may use.
[0040]
The protective layer of the electrophotographic photosensitive member of the present invention is preferably formed by applying a coating solution obtained by dissolving or diluting a curable phenolic resin with a solvent or the like onto the photosensitive layer, whereby after coating A polymerization reaction occurs to form a cured layer.
[0041]
The form of polymerization proceeds by heat addition and condensation reaction, and after the protective layer is applied, it is heated to cause a polymerization reaction to produce a polymer cured layer.
[0042]
In the present invention, “resin is cured” means that the resin does not dissolve even when the resin is wetted with an alcohol solvent such as methanol or ethanol.
[0043]
The conductive particles for the protective layer play an auxiliary role of adjusting the volume resistivity of the protective layer, and are not necessarily used if not necessary.
[0044]
Examples of the conductive particles that can be used in the protective layer of the electrophotographic photosensitive member of the present invention include metals and metal oxides.
[0045]
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.
[0046]
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. .
[0047]
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.
[0048]
In the present invention, among conductive particles, it is preferable to use a metal oxide in terms of transparency. Further, among these metal oxides, it is particularly preferable to use tin oxide. Tin oxide may be surface-treated as described later for the purpose of improving dispersibility and liquid stability, and may be doped with antimony or tantalum for the purpose of improving resistance controllability.
[0049]
From the viewpoint of transparency of the protective layer, the average particle size of the conductive particles for the protective layer is preferably 0.3 μm or less, particularly preferably 0.1 μm or less. On the other hand, from the viewpoint of dispersibility and dispersion stability, 0.001 μm or more is preferable.
[0050]
From the viewpoint of the film strength of the protective layer, the amount of conductive particles becomes weaker as the amount of conductive particles increases. Therefore, the amount of conductive particles should be reduced within a range where the volume resistivity and residual potential of the protective layer are acceptable. preferable.
[0051]
The protective layer of the electrophotographic photosensitive member of the present invention is preferably a layer containing lubricating particles.
[0052]
The lubricating particles for the protective layer are preferably fluorine atom-containing resin particles, silicone resin particles, silica particles, and alumina particles, and more preferably fluorine atom-containing resin particles. Furthermore, you may mix these 2 or more types.
[0053]
As fluorine atom-containing resin particles, resin particles of tetrafluoroethylene resin, trifluoroethylene chloride resin, hexafluoroethylenepropylene resin, vinyl fluoride resin, vinylidene fluoride resin and difluoroethylene dichloride resin, One or more of these resin copolymer resin particles are preferably selected as appropriate, and tetrafluoroethylene resin particles and vinylidene fluoride resin particles are particularly preferable.
[0054]
The molecular weight of the lubricating particles and the particle size of the particles can be appropriately selected and are not particularly limited. However, the average molecular weight is preferably 3000 to 5000000, and the average particle size is preferably 0.01 to 10 μm. Is more preferably 0.05 to 2.0 μm.
[0055]
In addition, inorganic particles such as silica particles and alumina particles may not function as lubricating particles as particles alone, but by dispersing and adding these, the surface roughness of the protective layer increases, resulting in It has been clarified by the present inventors that the lubricity of the protective layer is increased. In the present invention, the lubricating particles include particles that impart lubricity.
[0056]
When both lubricating particles such as fluorine atom-containing resin particles and conductive particles are dispersed in the resin solution, a fluorine atom-containing compound may be added during dispersion of the conductive particles so that the particles do not aggregate. Further, the surface of the conductive particles may be surface-treated with a fluorine atom-containing compound.
[0057]
Dispersibility and dispersion stability of conductive particles and fluorine atom-containing resin particles in the resin solution compared to the case without fluorine atom-containing compounds by adding fluorine atom-containing compounds or surface treatment of conductive particles Is significantly improved.
[0058]
Also, secondary particles of dispersed particles can be obtained by dispersing fluorine atom-containing resin particles in a liquid in which conductive particles are dispersed by adding a fluorine atom-containing compound or in a liquid in which conductive particles subjected to surface treatment are dispersed. Thus, a coating solution having excellent dispersibility that is very stable over time can be obtained.
[0059]
Examples of the fluorine atom-containing compound include a fluorine-containing silane coupling agent, a fluorine-modified silicone oil, and a fluorine-based surfactant.
[0060]
Examples of preferred compounds are listed below, but the present invention is not limited to these compounds.
[0061]
[Outside 7]

[0062]
[Outside 8]

[0063]
[Outside 9]

[0064]
As a surface treatment method for the conductive particles, the conductive 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 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 particles.
[0065]
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 particles after the surface treatment can be further pulverized.
[0066]
The ratio of the fluorine atom-containing compound to the conductive particles is affected by the particle size, shape, and surface area of the particles, but is preferably 1 to 65% by mass with respect to the total mass of the surface-treated conductive particles, and more preferably 1 -50 mass% is preferable.
[0067]
Furthermore, in the present invention, in order to obtain a more environmentally stable protective layer, a siloxane compound having a structure represented by the following formula (1) is added at the time of dispersing conductive particles, or the following formula (1) By mixing conductive particles that have been surface-treated with a siloxane compound having a structure represented by the following, a protective layer that is more excellent in environmental stability can be obtained.
[0068]
[Outside 10]

[0069]
(In formula (1), A ^{11 to} A ¹⁸ are each independently a hydrogen atom or a methyl group, provided that the ratio of the total number of hydrogen atoms (b) to the total number of A (a) (b / a) ^.n is 0.001 to 0.5 ¹¹ is an integer of 0 or more.)
Dispersion in the coating solution in which the siloxane compound is added or dispersed in the binder resin in which the conductive metal oxide particles whose surface is treated with the siloxane compound is dissolved in a solvent, eliminates the formation of secondary particles of the dispersed particles. A coating solution that is stable over time and has good dispersibility can be obtained, and a protective layer formed from this coating solution has high transparency and a film that is particularly excellent in environmental resistance.
[0070]
The molecular weight of the siloxane compound having the structure represented by the above formula (1) is not particularly limited. However, in the case of surface treatment, the viscosity should not be too high because of its ease, and the weight average molecular weight 100 to 50000 are preferable, and among them, 500 to 10000 is particularly preferable from the viewpoint of surface treatment efficiency.
[0071]
There are two surface treatment methods, wet and dry.
[0072]
In the wet treatment, conductive metal oxide particles, which are conductive particles, are dispersed in a solvent with a siloxane compound having a structure represented by the above formula (1), and the siloxane compound is adhered to the surface of the fine particles.
[0073]
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 particles.
[0074]
In this heat treatment, Si—H bonds in 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 particles is covered with this network structure.
[0075]
As described above, the surface treatment is completed by fixing the siloxane compound to the surface of the conductive metallized particles. However, the treated particles may be pulverized as necessary.
[0076]
In the dry treatment, the siloxane compound and the conductive metal oxide particles are mixed and kneaded without using a solvent, and the siloxane compound is adhered to the particle surface. Thereafter, heat treatment and pulverization are performed in the same manner as the wet treatment to complete the surface treatment.
[0077]
The charge transport material used in the protective layer of the electrophotographic photoreceptor of the present invention is a compound having at least one hydroxyl group in the molecule, particularly a hydroxyalkyl group, hydroxyalkoxyl group, or hydroxyphenyl group in the molecule. which is a compound having at least one.
[0078]
Examples of the charge transporting material having at least one of the hydroxyalkyl groups and hydroxyalkoxyl groups in the molecule, a charge transport material having the structure represented by any of the formulas formula (2) to (4).
[0079]
[Outside 11]

[0080]
(In formula (2), R ²¹ , R ²² and R ²³ each independently represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. The benzene rings of α, β and γ are Each independently substituted with a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group A, b, d, m and n each independently represents 0 or 1.
[Outside 12]

[0081]
(In the formula (3), R ³¹ , R ³² and R ³³ each independently represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Independently, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group as a substituent E, f and g each independently represent 0 or 1. p, q and r are each independently 0 or 1, but all of them may be 0 at the same time. Z ³¹ and Z ³² are each independently a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted group. Aromatic heterocyclic group Or they may form a ring together.)
[Outside 13]

[0082]
(In the formula (4), R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ζ, η, θ and The benzene ring of i is independently a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic group It may have a heterocyclic group as a substituent, h, i, j, k, s, t and u each independently represent 0 or 1. Z ⁴¹ and Z ⁴² each independently represent a halogen atom. An atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group, or a ring together May be made.)
Further, as the charge-transporting material having a hydroxyphenyl group in the molecule, a charge transport material having the structure represented by any of the following formulas (5) to (7).
[0083]
[Outside 14]

[0084]
(In formula (5), R ⁵¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. R ⁵² represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Ar ⁵¹ and Ar ⁵² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted phenyl group. A hydrocarbon ring group or a substituted or unsubstituted aromatic heterocyclic group, Ar ⁵³ represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group, or a substituted or unsubstituted divalent aromatic group. And v and w each independently represent 0 or 1. However, when v = 0, w = 0, and the benzene rings of κ and λ each independently represent a halogen atom. Atom, substituted or unsubstituted al Group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group or a substituted or unsubstituted aromatic heterocyclic group which may have a substituent.)
[Outside 15]

[0085]
(In Formula (6), R ⁶¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁶¹ and Ar ⁶² are each independently a substituted or unsubstituted alkyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group, x represents 0 or 1. A benzene ring of μ and ν Each independently represents a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group. It may have as a substituent, and the benzene ring of μ and ν may form a ring jointly via a substituent.)
[Outside 16]

[0086]
(In Formula (7), R ⁷¹ and R ⁷² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁷¹ represents a substituted or unsubstituted alkyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group, and y and z each independently represent 0 or 1. The benzene rings of ξ, π, ρ and σ are each independently a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted Alternatively, it may have an unsubstituted aromatic heterocyclic group as a substituent, and the ξ and π benzene rings and the ρ and σ benzene rings each independently form a ring through a substituent. May be done.)
In the above formulas (2) to (7), R ²¹ , R ²² , R ²³ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁵¹ , R ⁶¹ , R ⁷¹ and Examples of the divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched in R ⁷² include alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group, an isopropylene group, and a cyclohexylidene group. It is done.
[0087]
^Examples of the alkyl group for R ⁵² include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group.
[0088]
Among the substituents that the benzene ring of α, β, γ, δ, ε, ζ, η, θ, ι, κ, λ, μ, ν, ξ, π, ρ, and σ may have, halogen Atoms include fluorine, chlorine, bromine and iodine atoms, alkyl groups include methyl, ethyl, propyl and butyl groups, and alkoxyl groups include methoxy and ethoxy. Group, propoxy group, butoxy group, etc., aromatic hydrocarbon ring group includes phenyl group, naphthyl group, anthryl group, pyrenyl group, etc., and aromatic heterocyclic group includes pyridyl group, thienyl group, etc. , Furyl group, quinolyl group and the like.
[0089]
In addition, when the benzene ring of μ and ν, the benzene ring of ξ and π, and the benzene ring of ρ and σ form a ring through a substituent, the substituents include a propylidene group, an ethylene group A cyclic structure such as a fluorene skeleton or a dihydrophenanthrene skeleton is formed through these groups.
[0090]
Examples of the halogen atom for Z ³¹ , Z ³² , Z ⁴¹ and Z ⁴² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the aromatic hydrocarbon ring group include a phenyl group, a naphthyl group, an anthryl group, and a pyrenyl group. Examples of the aromatic heterocyclic group include a pyridyl group, a thienyl group, a furyl group, and a quinolyl group.
[0091]
^Examples of the alkyl group of Ar ⁵¹ , Ar ⁵² , Ar ⁶¹ , Ar ⁶² and Ar ⁷¹ include a methyl group, an ethyl group, a propyl group and a butyl group, and the aralkyl group includes a benzyl group, a phenethyl group and a naphthyl group. Examples thereof include a methyl group, examples of the aromatic hydrocarbon ring group include a phenyl group, a naphthyl group, an anthryl group, and a pyrenyl group. Examples of the aromatic heterocyclic group include a pyridyl group, a thienyl group, a furyl group, and a quinolyl group. Groups and the like.
[0092]
Examples of the divalent aromatic hydrocarbon ring group of Ar ⁵³ include a phenylene group, a naphthylene group, an anthrylene group, and a pyrenylene group. Examples of the divalent aromatic heterocyclic group include a pyridylene group and a thienylene group. Is mentioned.
[0093]
The substituents that each of the above groups may have include alkyl groups such as methyl, ethyl, propyl and butyl, aralkyl groups such as benzyl, phenethyl and naphthylmethyl, phenyl, naphthyl and the like. Groups, anthryl groups, pyrenyl groups, fluorenyl groups, carbazolyl groups, dibenzofuryl groups, dibenzothiophenyl groups and other aromatic hydrocarbon ring groups, aromatic heterocyclic groups, and methoxy groups, ethoxy groups, and propoxy groups such as propoxy groups And aryloxy groups such as phenoxy group and naphthoxy group, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, nitro group and cyano group.
[0094]
The charge transport material having the structure represented by any one of the above formulas (2) to (7) has good compatibility with the phenol resin, and can easily produce a uniformly dispersed protective layer film.
[0095]
In order to further improve the compatibility, R ²¹ , R ²² , R ²³ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² , R ⁴³ in the above formulas (2) to (4), The divalent hydrocarbon group for R ⁴⁴ preferably has 4 or less carbon atoms, and preferably has 2 or more hydroxyalkyl groups and hydroxyalkoxyl groups.
[0096]
In the above formulas (5) to (7), the hydroxyphenyl group contained in the charge transport material reacts with the phenol resin, the charge transport material is taken into the protective layer matrix, and the strength as the protective layer is further increased. Become stronger.
[0097]
The charge transport material having a structure represented by any one of the above formulas (2) to (7) is uniformly dissolved or dispersed in a coating solution for producing a protective layer, and is formed by coating.
[0098]
The mixing ratio of the charge transport material having the structure represented by any one of the above formulas (2) to (7) and the binder resin is a mass ratio of charge transport material / binder resin = 0.1 / 10 to 10. 20/10 is preferable, and 0.5 / 10 to 10/10 is particularly preferable. If the amount of the charge transport material is too small relative to the binder 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.
[0099]
Hereinafter, specific examples of the charge transport material having the structure represented by any one of the above formulas (2) to (7) will be shown. However, the present invention is not limited to these.
[0100]
[Outside 17]

[0101]
[Outside 18]

[0102]
[Outside 19]

[0103]
[Outside 20]

[0104]
[Outside 21]

[0105]
[Outside 22]

[0106]
[Outside 23]

[0107]
[Outside 24]

[0108]
[Outside 25]

[0109]
[Outside 26]

[0110]
[Outside 27]

[0111]
[Outside 28]

[0112]
[Outside 29]

[0113]
Among these, (3), (4), (5), (8), (11), (12), (13), (17), (21), (24), (25), (26 ), (27), (28), (30), (31), (34), (35), (39), (44), (48), (49), (50), (52), (55), (56), (58), (59) are preferable, and (3), (8), (12), (25), (31), (39), (44), ( 49) and (56) are more preferable.
[0114]
As a solvent for dispersing the coating liquid for the protective layer, the binder resin is sufficiently dissolved, and the charge transporting material having the structure represented by the above formulas (2) to (7) is also sufficiently dissolved. When used, the dispersibility is good, and when lubricating particles such as fluorine atom-containing compounds, fluorine atom-containing resin particles and siloxane compounds are used, compatibility and processability are good, and further, contact with the coating liquid of the protective layer A solvent that does not adversely affect the charge transport layer is preferred.
[0115]
Accordingly, the solvent includes 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, halogen hydrocarbons such as chlorobenzene and dichloromethane can be used, and these may be used in combination. Among these, the most suitable solvents for the form of the phenol resin are alcohols such as methanol, ethanol and 2-propanol.
[0116]
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 most of the charge transport materials used in the present invention are alcohols. Since it is soluble in a solvent containing as a main component, it can be dispersed in a phenol resin coating solution.
[0117]
As a method for applying the protective layer, a coating method 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.
[0118]
The protective layer in the present invention can be obtained by applying a solution containing the above compound on the photosensitive layer and drying it. When the binder resin to be contained is a thermosetting curable resin , the curing temperature is preferably 100 ° C to 300 ° C, particularly preferably 120 ° C to 200 ° C.
[0119]
Moreover, it is preferable that the film thickness of a protective layer is 1-5.5 micrometers from the point of the movement of an electric charge.
[0120]
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 an active substance such as ozone or nitrogen oxide generated during charging.
[0121]
Next, the photosensitive layer and the like possessed by the electrophotographic photoreceptor will be described below.
[0122]
The photosensitive layer in the present invention is a single layer type containing both a charge generating material and a charge transporting material in the same layer, but having a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material. Although it may be a mold, it is preferably a laminate type in which a charge generation layer and a charge transport layer are sequentially laminated on a conductive support. An example of this is shown in FIG.
[0123]
In the electrophotographic photosensitive member shown in FIG. 1A, a charge generation layer 3 and a charge transport layer 2 are sequentially provided on a conductive support 4, and a protective layer 1 is further provided as a surface layer.
[0124]
As the conductive support 4, a support itself having conductivity, for example, aluminum, an aluminum alloy, and stainless steel can be used. In addition, aluminum, an aluminum alloy, an indium oxide-tin oxide alloy, or the like can be used by vacuum deposition. It is possible to use a plastic with a coating, a support in which plastic or paper is impregnated with a suitable binder with conductive particles (such as carbon black, tin oxide, titanium oxide and silver particles), and a plastic with a conductive binder. .
[0125]
The shape of the conductive support 4 includes a cylindrical drum type and a belt shape, but is not particularly limited.
[0126]
In the present invention, a binder layer (adhesive layer) 5 having a barrier function and an adhesive function can be provided between the conductive support 4 and the photosensitive layer (FIG. 1B).
[0127]
The binder layer 5 is used for improving adhesion of the photosensitive layer, improving coating properties, protecting the support, covering defects on the support, improving charge injection from the support, and protecting the photosensitive layer from electrical breakdown. It is formed. The binder layer 5 can be formed of casein, polyvinyl alcohol, ethyl cellulose, ethylene-acrylic acid copolymer, polyamide, modified polyamide, polyurethane, gelatin, aluminum oxide, or the like. The thickness of the binder layer 5 is preferably 5 μm or less, and particularly preferably 0.1 to 3 μm.
[0128]
In the present invention, as shown in FIG. 1C, a binder layer 5 and an undercoat layer 6 for preventing interference fringes are provided between the conductive support 4 and the charge generation layer 3. May be.
[0129]
The charge generation layer 3 contains a charge generation material and, if necessary, a binder resin.
[0130]
Examples of charge generation materials include azo pigments such as monoazo, disazo and trisazo, phthalocyanine pigments such as metal phthalocyanine and nonmetal phthalocyanine, indigo pigments such as indigo and thioindigo, and perylenes such as perylene anhydride and perylene imide. Pigments, polycyclic quinone pigments such as anthraquinone and pyrenequinone, salts such as squarylium dyes, pyrylium salts and thiapyrylium salts, triphenylmethane dyes, inorganic substances such as selenium, selenium-tellurium and amorphous silicon, quinacridone pigments, and azurenium salts Examples thereof include pigments, cyanine dyes, xanthene dyes, quinoneimine dyes, styryl dyes, cadmium sulfide, and zinc oxide. In the present invention, a gallium phthalocyanine compound is particularly preferable, hydroxygallium phthalocyanine is particularly preferable, and 7.4 ° is the Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα. And hydroxygallium phthalocyanine having a strong peak at 28.2 °.
[0131]
As binder resins, 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, silicone resin, polysulfone resin, styrene -A butadiene copolymer resin, an alkyd resin, an epoxy resin, a urea resin, a salted vinyl-vinyl acetate copolymer resin, and the like are exemplified, but not limited thereto. These may be used alone, as a mixture or as a copolymer polymer, or one or more of them may be used.
[0132]
The charge generation layer 3 is obtained by dispersing the charge generation material by a method such as a homogenizer, an ultrasonic wave, a ball mill, a sand mill, an attritor and a roll mill together with a binder resin and a solvent having a mass ratio of 0.3 to 4 times. The resulting solution is formed by applying and drying. The film thickness is preferably 5 μm or less, and particularly preferably 0.01 to 1 μm.
[0133]
The solvent used is selected in consideration of the solubility and dispersion stability of the charge generating material and binder resin to be used. As the organic solvent, alcohols, sulfoxides, ketones, ethers, esters, fatty acids are used. Group halogenated hydrocarbons or aromatic compounds can be used.
[0134]
In addition, various sensitizers, antioxidants, ultraviolet absorbers, plasticizers, and the like can be added to the charge generation layer 3 as necessary.
[0135]
The charge transport layer 2 contains a charge transport material and, if necessary, a binder resin.
[0136]
Examples of charge transport materials 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. Can be mentioned.
[0137]
Examples of the binder resin include acrylic resin, styrene resin, polyester, polycarbonate resin, polyarylate, polysulfone, polyphenylene oxide, epoxy resin, polyurethane resin, alkyd resin, and unsaturated resin. Among these, polymethyl methacrylate, polystyrene, styrene-acrylonitrile copolymer, polycarbonate resin and diallyl phthalate resin are particularly preferable.
[0138]
The charge transport layer 2 is formed by applying and drying a solution obtained by dissolving a charge transport material and a binder resin in a solvent. The mixing ratio of the charge transport material and the binder resin is about 2: 1 to 1: 2 by mass ratio.
[0139]
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, and chlorinated hydrocarbons such as chlorobenzene, chloroform and carbon tetrachloride. It is done.
[0140]
When this solution is applied, for example, a coating method such as a dip coating method, a spray coating method, or a spinner coating method can be used.
[0141]
Moreover, it is preferable that drying temperature is 10 to 200 degreeC, and it is especially preferable that it is 20 to 150 degreeC. Further, the drying time is preferably 5 minutes to 5 hours, and particularly preferably 10 minutes to 2 hours.
[0142]
Furthermore, an antioxidant, an ultraviolet absorber, a plasticizer, and the like can be added to the charge transport layer 2 as necessary.
[0143]
In the present invention, the protective layer 1 is further formed on the charge transport layer 2 by the above method.
[0144]
Specific embodiments of the electrophotographic apparatus using the electrophotographic photosensitive member according to the present invention are shown below.
[0145]
<Embodiment 1>
FIG. 2 shows a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.
[0146]
In the figure, reference numeral 11 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotated about a shaft 12 in the direction of an arrow at a predetermined peripheral speed.
[0147]
In the rotation process, the electrophotographic photosensitive member 11 is subjected to uniform charging at a predetermined positive or negative potential on the peripheral surface thereof by the (primary) charging unit 13, and then exposed to exposure means (non-exposure) such as slit exposure or laser beam scanning exposure. The exposure light 14 intensity-modulated in response to the time-series electric digital image signal of the target image information outputted from the figure 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.
[0148]
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 unit 16 to the transferred transfer material 17.
[0149]
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 fixing means 18, and subjected to image fixing, thereby being printed out as an image formed product (print, copy). .
[0150]
The surface of the electrophotographic photosensitive member 11 after the image transfer is cleaned by receiving the transfer residual toner by the cleaning means 19. Further, without the cleaning means (cleanerless), the transfer residual toner can be directly collected by the developing means. Further, after being subjected to charge removal processing by pre-exposure light 20 from a pre-exposure means (not shown), it is repeatedly used for image formation. When the charging unit 13 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary.
[0151]
In the present invention, among the components such as the electrophotographic photosensitive member 11, the charging unit 13, the developing unit 15 and the cleaning unit 19 described above, a plurality of components are housed in a container 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 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 detachable from the apparatus main body using a guide unit 22 such as a rail of the apparatus main body. A simple process cartridge 21.
[0152]
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 is read by a document by a sensor, and laser beam scanning performed according to this signal is performed. The light emitted by driving the LED array or the liquid crystal shutter array. Moreover, you may add another auxiliary | assistant process as needed.
[0153]
<Embodiment 2>
FIG. 3 shows a schematic configuration of an electrophotographic apparatus provided with a process cartridge having an electrophotographic photosensitive member of the present invention provided with charged particle supply means.
[0154]
The drum-shaped electrophotographic photosensitive member 31 is rotationally driven at a constant speed in the direction of the arrow.
[0155]
The charging roller 32 included in the charging unit includes charged particles 33 (conductive particles for charging the electrophotographic photosensitive member), a medium resistance layer 32b as a particle carrier, and a cored bar 32a. The charging roller 32 abuts the electrophotographic photosensitive member 31 with a predetermined penetration amount to form a contact portion n.
[0156]
The charging roller 32 in this embodiment is configured by forming a middle resistance layer 32b of rubber or foam on a core metal 32a, and further carrying charged particles 33 on the surface layer.
[0157]
The middle resistance layer 32b is formulated with a resin (for example, urethane), conductive particles (for example, carbon black), a sulfurizing agent, a foaming agent, and the like, and is formed in a roller shape on the core metal 32a. Thereafter, the surface is polished.
[0158]
The charging roller in the present embodiment is particularly different from the charging roller (charging charging roller) in the first embodiment in the following points.
(1) Surface structure and roughness characteristics for carrying high-density charged particles on the surface layer (2) Resistance characteristics required for injection charging (volume resistivity, surface resistance)
The surface of the charging roller for discharge is flat, the average roughness Ra of the surface is sub μm or less, and the roller hardness is high. In charging using discharge, a discharge phenomenon occurs in a gap of several tens of μm that is slightly apart from the contact portion between the charging roller and the electrophotographic photosensitive member. When unevenness exists on the surface of the charging roller and the electrophotographic photosensitive member, the electric field strength is partially different, so that the discharge phenomenon becomes unstable and charging unevenness occurs. Therefore, the charging roller for discharge requires a flat and high hardness surface.
[0159]
The reason why injection charging cannot be performed by a charging roller for discharge is that, in the surface structure as described above, it appears to be in close contact with the drum in appearance, but it means the microscopic contact at the molecular level necessary for charge injection. Then there is almost no contact.
[0160]
On the other hand, the charging roller 32 for injection charging is required to have a certain degree of roughness because it needs to carry the charged particles 33 at a high density. The average roughness Ra is preferably 1 μm to 500 μm. If the thickness is less than 1 μm, the surface area for supporting the charged particles 33 is insufficient, and when an insulator (for example, toner) adheres to the roller surface layer, it becomes difficult to contact the periphery of the electrophotographic photoreceptor 31 and the charging performance decreases. It becomes easy to do. On the other hand, if the thickness exceeds 500 μm, the unevenness on the surface of the charging roller tends to reduce the in-plane charging uniformity of the electrophotographic photosensitive member.
[0161]
The average roughness Ra can be measured by using a surface shape measuring microscope VF-7500, VF7510 manufactured by Keyence Corporation, and measuring the shape of the roller surface and Ra in a non-contact manner using an objective lens 1250 to 2500 times.
[0162]
In the charging roller for discharge, a low resistance base layer is formed on a core metal, and then the surface is covered with a high resistance layer. Roller charging by discharge has a high applied voltage, and if there is a pinhole (exposed support due to film damage), the voltage drops to the periphery and a charging failure occurs. Therefore, it is preferable to set it to 10 ¹¹ Ω □ or more.
[0163]
On the other hand, in the injection charging method, since charging with a low voltage is possible, it is not necessary to make the surface layer have a high resistance, and the charging roller can be composed of a single layer. Rather, in the injection charging, the surface resistance of the charging roller is preferably 10 ⁴ to 10 ¹⁰ Ω. If it exceeds 10 ¹⁰ Ω, the uniformity in the charged surface is lowered, and unevenness due to the rubbing of the charging roller appears as a streak in the halftone image, so that it is easy to see a reduction in image quality. On the other hand, if it is less than 10 ⁴ Ω, a peripheral voltage drop is likely to occur due to pinholes in the electrophotographic photosensitive member even with injection charging.
[0164]
Furthermore, the volume resistivity is preferably in the range of 10 ⁴ to 10 ⁷ Ω · cm. If it is less than 10 ⁴ Ω · cm, a voltage drop of the power supply due to pinhole leakage is likely to occur. On the other hand, if it exceeds 10 ⁷ Ω · cm, it becomes difficult to secure a current necessary for charging, and the charging voltage tends to decrease.
[0165]
The resistance of the charging roller was measured according to the following procedure.
[0166]
The roller resistance was measured by applying an electrode to an insulator drum having an outer diameter of 30 mm so that a total pressure of 1 kg was applied to the core metal 32 a of the charging roller 32. The electrode was measured by arranging a guard electrode around the main electrode. The distance between the main electrode and the guard electrode was adjusted to approximately the thickness of the elastic layer 32b, and the main electrode secured a sufficient width with respect to the guard electrode. In the measurement, +100 V was applied from the power source to the main electrode, currents flowing through the ammeters Av and As were measured, and volume resistivity and surface resistance were measured, respectively.
[0167]
In the injection charging method, it is important that the charging member functions as a flexible electrode. The magnetic brush is realized by the flexibility of the magnetic particle layer itself. In the present embodiment, this is achieved by adjusting the elastic characteristics of the intermediate resistance layer 32b. The Asker C hardness is preferably in the range of 15 to 50 degrees, and more preferably in the range of 25 to 40 degrees. If the hardness is too high, the necessary penetration amount cannot be obtained, and the contact portion n cannot be secured between the electrophotographic photosensitive member and the charging performance is deteriorated. In addition, since the contact property of the substance at the molecular level cannot be obtained, the contact with the surroundings is hindered by foreign matters. On the other hand, when the hardness is too low, the shape is not stable, so that the contact pressure with the object to be charged becomes uneven, resulting in uneven charging. Alternatively, charging failure occurs due to permanent deformation distortion of the roller due to long-term standing.
[0168]
Examples of the material of the charging roller 32 include EPDM, urethane, NBR, silicone rubber, and a rubber material in which a conductive material such as carbon black or metal oxide for resistance adjustment is dispersed in IR or the like. It is also possible to adjust the resistance using an ion conductive material without dispersing the conductive substance. Thereafter, molding is performed by adjusting the roughness of the surface, polishing, or the like as necessary. Moreover, the structure by the function-separated multiple layer is also possible.
[0169]
The form of the roller is more preferably a porous structure. This is also advantageous in terms of manufacturing in that the above surface roughness can be obtained simultaneously with the molding of the roller. The cell diameter of the foam is suitably 1 to 500 μm. After foam molding, the surface of the porous body is exposed by polishing the surface, and a surface structure having the aforementioned roughness can be produced.
[0170]
The charging roller 32 has an intrusion amount with respect to the electrophotographic photosensitive member 31 to form a contact portion n, and is driven to rotate in a direction (counter) opposite to the rotation direction of the electrophotographic photosensitive member 31 at the contact portion n. Then, it can come into contact with the surface of the electrophotographic photosensitive member 31 with a speed difference. Further, during image recording by the printer, a predetermined charging bias is applied to the charging roller 32 from the charging bias application power source S1, whereby the peripheral surface of the electrophotographic photosensitive member 1 is uniformly charged to a predetermined polarity and potential by an injection charging method. It is processed.
[0171]
The charged particles 33 are added and accumulated in the toner, and are supplied to the charging roller 32 via the electrophotographic photosensitive member 31 together with the development of the toner.
[0172]
As a supply means, a configuration is adopted in which the regulating blade 34 is brought into contact with the charging roller 32 and the charged particles 33 are held between the charging roller 32 and the regulating blade 34. As the electrophotographic photosensitive member 31 rotates, a certain amount of charged particles 33 is applied to the charging roller 32, and then reaches the contact portion n between the charging roller 32 and the electrophotographic photosensitive member 31.
[0173]
Further, the particle size of the charged particles 33 is preferably 10 μm or less in order to obtain high charging efficiency and charging uniformity. In the present invention, the particle diameter in the case where the charged particles constitute an aggregate is defined as the average particle diameter as the aggregate. For the measurement of the particle size, 100 or more samples were extracted from observation with an electron microscope, the volume particle size distribution was calculated with the maximum horizontal chord length, and the 50% average particle size was determined.
[0174]
There is no problem that the charged particles 33 exist not only in the state of primary particles but also in the state of aggregation of secondary particles. In any aggregated state, the form is not important as long as the function as a charged particle can be realized as an aggregate.
[0175]
The charged particles 33 are preferably white or nearly transparent so as not to hinder latent image exposure, particularly when used for charging an electrophotographic photosensitive member. Further, considering that the charged particles are partially transferred from the electrophotographic photosensitive member 31 to the transfer material P, colorless or white particles are preferable for color recording, and light scattering by the charged particles 33 during image exposure is preferred. In order to prevent this, it is preferable that the particle size is smaller than the constituent pixel size, and more preferably smaller than the toner particle size. As the lower limit of the particle size, 10 nm is considered to be the limit as a particle that can be stably obtained.
[0176]
Reference numeral 36 denotes a developing device. The electrostatic latent image on the surface of the electrophotographic photosensitive member 31 is developed as a toner image at the development site a by the developing device 36. The developing device 36 is provided with a mixture obtained by adding charged particles to toner.
[0177]
The electrophotographic apparatus (printer) of the present embodiment is a toner recycling process, and the transfer residual toner remaining on the surface of the electrophotographic photosensitive member 31 after image transfer is removed by a dedicated cleaning means (cleaner). Rather, the toner charge is temporarily collected by the counter-rotating charging roller 32 as the electrophotographic photosensitive member 31 rotates, and the reversed toner charges are normalized as they circulate around the outer periphery of the charging roller 32, and are sequentially applied to the electrophotographic photosensitive member 31. It is discharged and reaches the development site a, and is collected and reused by the development simultaneous cleaning in the development means 36 having the magnet roller 36a and the development sleeve 36b. S2 is a power source for applying a developing bias to the developing means 36.
[0178]
Reference numeral 35 denotes a laser beam scanner (exposure means) including a laser diode and a polygon mirror. This laser beam scanner 35 outputs a laser beam whose intensity is modulated in accordance with a time-series digital image signal of target image information, and scans and exposes the uniformly charged surface of the electrophotographic photosensitive member 31 with the laser beam. To do. The scanning exposure light L forms an electrostatic latent image corresponding to target image information on the surface of the electrophotographic photosensitive member 31.
[0179]
Reference numeral 38 denotes fixing means such as a heat fixing system. The transfer material P, which is fed to the transfer contact portion b between the electrophotographic photosensitive member 31 and the transfer roller 37 and receives the transfer of the toner image on the electrophotographic photosensitive member 31 side, is transferred from the surface of the electrophotographic photosensitive member 31. The toner image is separated and introduced into the fixing unit 38, and the toner image is fixed and discharged as an image formed product (print / copy) to the outside of the apparatus. S 3 is a power source that applies a transfer bias to the transfer roller 37.
[0180]
Reference numeral 39 denotes a process cartridge. In this embodiment, the electrophotographic photosensitive member, the charging unit and the developing unit are integrally supported. The process cartridge 39 is detachably attached to the main body of the electrophotographic apparatus by guide means such as a rail 40 provided in the electrophotographic apparatus.
[0181]
The electrophotographic photosensitive member of the present invention can be used not only for electrophotographic copying machines but also for a wide range of electrophotographic applications such as laser beam printers, CRT printers, LED printers, FAX, liquid crystal printers, and laser plate making. It is.
[0182]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to the following examples. In the examples, “parts” and “%” indicate parts by mass and% by mass, respectively.
[0183]
( Reference Example 1)
By coating a 5 mass% methanol solution of polyamide resin (trade name: Amilan CM8000, manufactured by Toray Industries, Inc.) on an aluminum cylinder of φ30 mm × 261 mm as a conductive support by a dip coating method, the film thickness is obtained by drying. A binding layer having a thickness of 0.5 μm was formed.
[0184]
Next, 3.5 parts of hydroxygallium phthalocyanine crystals having strong peaks at 7.4 ° and 28.2 ° of the Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα and polyvinyl butyral resin (trade name) : 1 part of ESREC BX-1, Sekisui Chemical Co., Ltd.) is added to 120 parts of cyclohexanone, dispersed in a sand mill using φ1 mm glass beads for 3 hours, and further diluted with 120 parts of ethyl acetate to generate charge. A layer coating solution was prepared. The charge generation layer coating solution was dip coated on the binder layer and dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.15 μm.
[0185]
FIG. 4 shows a powder X-ray diffraction pattern of the hydroxygallium phthalocyanine crystal. The powder X-ray diffraction was measured using CuKα rays under the following conditions.
[0186]
Measuring instrument used: Fully automatic X-ray diffractometer MXP18, manufactured by Mac Science
X-ray tube: Cu
Tube voltage: 50 kV
Tube current: 300mA
Scan method: 2θ / θ scan Scan speed: 2 deg. / Min
Sampling interval: 0.020 deg.
Start angle (2θ): 5 deg.
Stop angle (2θ): 40 deg.
Divergence slit: 0.5 deg.
Scattering slit: 0.5 deg.
Receiving slit: 0.3 deg.
Next, 10 parts of a compound represented by the following formula as a charge transporting substance and 10 parts of bisphenol Z-type polycarbonate (trade name: Iupilon Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a binder resin were used. A charge transport layer coating solution was prepared by dissolving in 100 parts and 60 parts of tetrahydrofuran (THF).
[0187]
[Outside 30]

[0188]
This coating solution was applied onto the charge generation layer and dried with hot air at 105 ° C. for 1 hour to form a charge transport layer having a thickness of 20 μm.
[0189]
Next, 20 parts of antimony-doped tin oxide ultrafine particles surface-treated with a compound represented by the following formula (treatment amount: 7%),
[Outside 31]

[0190]
Disperse 30 parts of antimony-doped tin oxide fine particles and 150 parts of ethanol treated with methyl hydrogen silicone oil (trade name: KF99, manufactured by Shin-Etsu Chemical Co., Ltd.) over 66 hours in a sand mill apparatus. Further, 20 parts of polytetrafluoroethylene fine particles (average particle size 0.18 μm) were added and dispersed for 2 hours. Then, 30 parts of a resol type thermosetting phenol resin (trade name: PL-4804, manufactured by Gunei Chemical Industry Co., Ltd., containing an amine compound) was dissolved as a resin component to obtain a protective layer coating solution.
[0191]
This coating solution was dip-coated on the charge transport layer and dried with hot air at 145 ° C. for 1 hour to form a protective layer.
[0192]
The film thickness of this protective layer was 3 μm when measured using an instantaneous multi-photometry system MCPD-2000 (manufactured by Otsuka Electronics Co., Ltd.) based on light interference. Moreover, the dispersibility of the coating liquid for protective layers was favorable, and when the surface of the protective layer was observed visually, it was uniform without unevenness.
[0193]
Vsl (0.2) and Vsl (0.5) of the obtained electrophotographic photosensitive member were measured using a drum testing machine (manufactured by Gentec Corporation). The measurement environment was 23 ° C./5% RH, and the surface of the electrophotographic photosensitive member was charged to −700 V and irradiated with white light having a light quantity of 10 lux · sec. A potential measurement probe is installed at 90 ° and 224.5 ° positions from the position irradiated with white light, and Vsl (0.2) is set at the potential probe at the 90 ° position, and the potential measurement probe at the 224.5 ° position. Vsl (0.5) was measured with this method.
[0194]
In addition, the electrophotographic photosensitive member obtained as described above is mounted on a modified machine of an electrophotographic apparatus (trade name: Laser Jet 4000, manufactured by Hewlett-Packard Co.) which is the same electrophotographic system as that of the first embodiment. The image was evaluated. The main modification is the configuration of the system according to the second embodiment.
[0195]
The charged particles M used had a volume resistance of 1 Ω · cm and an initial loading amount of 5 mg / cm ² . The voltage applied from the power source S1 to the charging member was only a DC voltage of -700V.
[0196]
Under the above conditions, the initial dark potential (Vd) was measured under a normal temperature and low humidity environment (23 ° C./5% RH), and the image was visually evaluated. Further, as an endurance test, the images obtained after image formation of 5000 images under a normal temperature and low humidity environment (23 ° C./5% RH) and under a high temperature high humidity environment (32 ° C./85% RH) were visually evaluated. A character image with a printing rate of 6% is used during endurance, and during evaluation, the first 1/3 rotation of the photoconductor is solid black, and the remaining 1200 dpi is surrounded by 1 dot white. A halftone image is used.
[0197]
The results are shown in Table 1.
[0198]
( Reference Example 2)
The electrophotographic photosensitive member was evaluated in the same manner as in Reference Example 1 except that the electrophotographic apparatus was used without modification to the configuration of Embodiment 2. The results are shown in Table 1.
[0199]
( Reference Examples 3 and 4)
Resole-type phenol resin (trade name: PL-4804) was resol-type phenol resin PL-4852 (manufactured by Gunei Chemical Industry Co., Ltd., containing amine compound) ( Reference Example 3) and PL-5294 (Gunei Chemical Industry ( An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Reference Example 1 except that the product was changed to “made by alkali metal-containing” ( Reference Example 4). The results are shown in Table 1.
[0201]
( Reference Examples 5 and 6 )
Resol type phenol resin (trade name: PL-4804) is changed to bisphenol A type epoxy resin (trade name: R309: manufactured by Mitsui Petrochemical Co., Ltd.), the solvent is changed from ethanol to tetrahydrofuran, and the coating method is changed from the dip coating method. An electrophotographic photosensitive member was prepared in the same manner as in Reference Example 1 except that a protective layer was formed instead of the spray coating method, and evaluated in the same manner as in Reference Example 1 ( Reference Example 5 ) and Reference Example 2 ( Reference Example 6 ). did. The results are shown in Table 1.
[0202]
( Reference Examples 7 and 8 )
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 5 and Reference Example 6 except that the amount of bisphenol A type epoxy resin used was changed from 30 parts to 40 parts. The results are shown in Table 1.
[0203]
( Reference Examples 9 and 10 )
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Reference Examples 7 and 8 except that the thickness of the protective layer was changed from 3 μm to 5 μm. The results are shown in Table 1.
[0204]
( Reference Examples 11 and 12 )
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Reference Example 7 and Reference Example 8 except that the thickness of the protective layer was changed from 3 μm to 5.5 μm. The results are shown in Table 1.
[0205]
(Comparative Examples 1 and 2)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 7 and Reference Example 8 except that the bisphenol A type epoxy resin was changed from 40 parts to 50 parts and the thickness of the protective layer was changed from 3 μm to 6.5 μm. did. The results are shown in Table 1.
[0206]
(Comparative Examples 3 and 4)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 5 and Reference Example 6 except that bisphenol A type epoxy resin was changed from 30 parts to 55 parts. The results are shown in Table 1.
[0207]
(Comparative Examples 5 and 6)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Reference Example 5 and Reference Example 6 except that the bisphenol A type epoxy resin was changed from 30 parts to 10 parts. The results are shown in Table 1.
[0208]
(Example 1 )
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Reference Example 2 except that no tin oxide particles were added and instead 30 parts of a charge transport material represented by the following formula was added to form a protective layer. The results are shown in Table 1.
[0209]
[Outside 32]

[0210]
(Example 2 )
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the resol type phenolic resin (trade name PL-4852) was changed to a curable siloxane resin KP-854 (manufactured by Shin-Etsu Chemical Co., Ltd.). The results are shown in Table 1.
[0211]
(Example 3 )
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2 except that the thickness of the protective layer was changed from 3 μm to 5.5 μm. The results are shown in Table 1.
[0212]
(Comparative Example 7)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2 except that the amount of the curable siloxane resin used was changed from 30 parts to 40 parts and the thickness of the protective layer was changed from 3 μm to 6.5 μm. The results are shown in Table 1.
[0213]
(Comparative Example 8)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2 except that the amount of charge transport material added was changed from 30 parts to 70 parts. The results are shown in Table 1.
[0214]
(Comparative Example 9)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2 except that the amount of the charge transport material added was changed from 30 parts to 10 parts and the thickness of the protective layer was changed from 3 μm to 6.5 μm. The results are shown in Table 1.
[0215]
(Comparative Example 10)
The charge generation material has strong peaks at 7.6 °, 10.2 °, 25.3 ° and 28.6 ° of the Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of the hydroxygallium phthalocyanine crystal CuKα. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 3 except that oxytitanium phthalocyanine crystals were used. The results are shown in Table 1.
[0216]
( Reference Example 13 )
The electrophotographic photosensitive member was evaluated in the same manner as in Reference Example 5 except that the voltage applied to the charging roller was changed from only DC to a voltage obtained by superimposing an AC voltage having a peak-to-peak voltage of 500 V on a DC voltage of −700 V. The results are shown in Table 1.
[0217]
(Comparative Example 11)
The electrophotographic photosensitive member was evaluated in the same manner as in Comparative Example 2 except that the voltage applied to the charging roller was changed from only DC to a voltage obtained by superimposing an AC voltage having a peak-to-peak voltage of 500 V on a DC voltage of −700 V. The results are shown in Table 1.
[0218]
(Comparative Example 12)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2 except that the amount of the curable siloxane resin used was changed from 30 parts to 45 parts and the thickness of the protective layer was changed from 3 μm to 2 μm. The results are shown in Table 1.
[0219]
[Table 1]

[0220]
[Table 2]

[0221]
【The invention's effect】
As described above, according to the present invention, there is almost no positive ghost or negative ghost due to endurance of repeated use, and there is no image blur, and an electrophotographic photosensitive member capable of stably obtaining a high-quality image, the electron It has become possible to provide a process cartridge and an electrophotographic apparatus having a photographic photoreceptor.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of a layer structure of an electrophotographic photosensitive member according to the present invention.
FIG. 2 is a diagram showing a schematic configuration of Embodiment 1 which is an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member according to the present invention.
FIG. 3 is a diagram showing an example of a schematic configuration of Embodiment 2 which is an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member according to the present invention.
FIG. 4 is a characteristic X-ray diffraction pattern of CuKα of hydroxygallium phthalocyanine used in an example of the present invention.

Claims (7)

An electrophotographic photosensitive member having a conductive support, a photosensitive layer and a protective layer in this order, wherein the protective layer is in contact with the photosensitive layer;
The electrophotographic photosensitive member is charged with -700 V on the surface of the electrophotographic photosensitive member in an environment of 23 ° C./5% RH and irradiated with white light having a light quantity of 10 lux · sec. When the surface potential Vsl (0.2) of the electrophotographic photosensitive member of the above satisfies the following formula (1) and 0.5 seconds have elapsed after irradiation of the Vsl (0.2) and white light: The difference from the surface potential Vsl (0.5) of the photoconductor satisfies the following formula (2):
20 (V) ≦ | Vsl (0.2) | ≦ 80 (V) (1)
10 (V) ≦ | Vsl (0.2) −Vsl (0.5) | ≦ 30 (V) (2),
The protective layer includes a binder resin and a charge transport material, the binder resin is a cured product of a phenol resin, and the charge transport material is a compound represented by the following structural formulas (2) to (7). An electrophotographic photosensitive member characterized in that:
[Outside 1]

(In formula (2), R ²¹ , R ²² and R ²³ each independently represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. The benzene rings of α, β and γ are Each independently substituted with a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group A, b, d, m and n each independently represents 0 or 1.
[Outside 2]

(In the formula (3), R ³¹ , R ³² and R ³³ each independently represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Independently, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group as a substituent E, f and g each independently represent 0 or 1. p, q and r are each independently 0 or 1, but all of them may be 0 at the same time. Z ³¹ and Z ³² are each independently a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted group. Aromatic heterocyclic group Or they may form a ring together.)
[Outside 3]

(In the formula (4), R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ζ, η, θ and The benzene ring of i is independently a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic group It may have a heterocyclic group as a substituent, h, i, j, k, s, t and u each independently represent 0 or 1. Z ⁴¹ and Z ⁴² each independently represent a halogen atom. An atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group, or a ring together May be made.)
[Outside 4]

(In formula (5), R ⁵¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. R ⁵² represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Ar ⁵¹ and Ar ⁵² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted phenyl group. A hydrocarbon ring group or a substituted or unsubstituted aromatic heterocyclic group, Ar ⁵³ represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group, or a substituted or unsubstituted divalent aromatic group. And v and w each independently represent 0 or 1. However, when v = 0, w = 0, and the benzene rings of κ and λ each independently represent a halogen atom. Atom, substituted or unsubstituted al Group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group or a substituted or unsubstituted aromatic heterocyclic group which may have a substituent.)
[Outside 5]

(In Formula (6), R ⁶¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁶¹ and Ar ⁶² are each independently a substituted or unsubstituted alkyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group, x represents 0 or 1. A benzene ring of μ and ν Each independently represents a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group. It may have as a substituent, and the benzene rings of μ and ν may form a ring jointly via a substituent.)
[Outside 6]

(In Formula (7), R ⁷¹ and R ⁷² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁷¹ represents a substituted or unsubstituted alkyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group, and y and z each independently represent 0 or 1. The benzene rings of ξ, π, ρ and σ are each independently a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aromatic hydrocarbon ring group, or a substituted Alternatively, it may have an unsubstituted aromatic heterocyclic group as a substituent, and the ξ and π benzene rings and the ρ and σ benzene rings each independently form a ring through a substituent. You can do it.)   The electrophotographic photosensitive member according to claim 1, wherein | Vsl (0.2) | is 20 (V) or more and 70 (V) or less.   The electrophotographic photosensitive member according to claim 2, wherein | Vsl (0.2) | is 20 (V) or more and 60 (V) or less.   The electrophotographic photosensitive member according to claim 1, wherein the protective layer has a thickness of 1 to 5.5 μm.   The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer contains hydroxygallium phthalocyanine as a charge generating substance. An electrophotographic photosensitive member according to any one of claims 1 to 5 the charging unit, at least one means selected from the group consisting of the developing means and cleaning means supported integrally, a detachable to a main body of an electrophotographic apparatus A process cartridge characterized by being. The electrophotographic photosensitive member according to any one of claims 1 to 5, a charging means, an exposure means, the electrophotographic apparatus, characterized by comprising a developing means and transfer means.

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