JP2004093803A - Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having good electrophotographic properties which ensure no occurrence of image defects and little potential variation also in the case of an electrophotographic photoreceptor having an intermediate layer, in which an electrostatic latent image is formed on the surface with a semiconductor laser and to provide a process cartridge with the electrophotographic photoreceptor and an electrophotographic apparatus. <P>SOLUTION: The electrophotographic photoreceptor has an intermediate layer and a photosensitive layer in this order on a support, wherein the photosensitive layer contains a charge generating material and a charge transport material, and in the electrophotographic photoreceptor in which an electrostatic latent image is formed on the surface with a semiconductor laser, the intermediate layer contains an electron transport material and has a volume resistivity of ≥1×10<SP>12</SP>Ωcm in an environment at 30°C and 80% RH, and the ratio (Rz/λ) of the ten-point average roughness (Rz) of the photosensitive layer side surface of the support to the wavelength (λ) of the semiconductor laser is 0.6-2.5. <P>COPYRIGHT: (C)2004,JPO

Description

【００３３】
（式（１）中、Ｒ^１１は、置換または無置換のアルキル基、または、置換または無置換のアリール基を示す。Ｒ^１２〜Ｒ^１５は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、カルボン酸エステル基、置換基を有してもよいアルキル基、または、置換または無置換のアルコキシ基を示す。Ａ^１１は、置換または無置換のシクロアルキレン基、置換または無置換のアリーレン基、下記式（１０１）で示される構造を有する２価の基、または、下記式（１０２）で示される構造を有する２価の基を示す。
【００３４】
【外２】

【００３５】
【外３】

【００３６】
（式（１０１）、（１０２）中、Ｒ^１０１１〜Ｒ^１０１４、Ｒ^１０２１、Ｒ^１０２２は、それぞれ独立に、水素原子、置換または無置換のアルキル基、または、置換または無置換のアリール基を示し、ｎは、０または１を示す。）
【００３７】
上記表現のアルキル基としては、メチル基、エチル基、イソプロピル基、ｔ−ブチル基、ヘキシル基、オクチル基などが挙げられ、アリール基としては、フェニレン基、ナフチル基、アントリル基などが挙げられ、ハロゲン原子としては、塩素原子、フッ素原子などが挙げられ、カルボン酸エステル基としては、カルボキシエチル基、カルボキシｔ−ブチル基などが挙げられ、アルコキシ基としては、メトキシ基、エトキシ基、ｔ−ブトキシ基などが挙げられ、シクロアルキレン基としては、シクロペンチル基、シクロヘキシル基、シクロヘプチル基などが挙げられ、アリーレン基としては、エチレニル基、ブチレニル基、ヘキセニル基などが挙げられる。
【００３８】
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、ｔ−ブチル基などのアルキル基や、カルボキシメチル基、カルボキシエチル基、カルボキシブチル基などのカルボキシアルキル基や、ニトロ基および−ＣＦ３基などが挙げられる。
【００３９】
上記式（１）で示される構造を有するナフタレンアミジンイミド化合物の好適な化合物例を以下に挙げる。
【００４０】
【外４】

【００４１】
【外５】

【００４２】
【外６】

【００４３】
【外７】

【００４４】
【外８】

【００４５】
【外９】

【００４６】
【外１０】

【００４７】
【外１１】

【００４８】
【外１２】

【００４９】
【外１３】

【００５０】
【外１４】

【００５１】
【外１５】

【００５２】
これらの中でも、（１−１）、（１−３５）が特に好ましい。
【００５３】
また、中間層に含有される有機電子輸送物質しては、下記式（２）で示される構造を有するペリレンアミジンイミド化合物も好ましい。
【００５４】
【外１６】

【００５５】
（式（２）中、Ｒ^２１は、炭素数７〜４１の２級アルキル基、または、下記式（２０１）で示される構造を有する基であり、
【外１７】

【００５６】
（式（２０１）中、Ｒ^２０１１〜Ｒ^２０１５は、それぞれ独立に、水素原子、または、炭素数３〜８の分枝状アルキル基を示す。ただし、Ｒ^２０１１〜Ｒ^２０１５のうち水素原子は２つ以上であり、かつ、総てが水素原子であることはない。）
Ａ^２１は、置換または無置換の炭素数５〜７のシクロアルキレン基、置換または無置換のフェニレン基、置換または無置換のナフチレン基、置換または無置換のピリジレン基、ナフチレン基より高次である置換または無置換の２価の融合芳香族炭素環基、ピリジレン基より高次である置換または無置換の２価の融合芳香族複素環式基、下記式（２０２）で示される構造を有する２価の基、
【００５７】
【外１８】

【００５８】
下記式（２０３）で示される構造を有する２価の基、
【外１９】

【００５９】
（式（２０３）中、Ｒ^２０３１、Ｒ^２０３２は、それぞれ独立に、置換または無置換の炭素数１〜４のアルキル基、置換または無置換のフェニル基、または、置換または無置換の４−トリル基を示す。）
【００６０】
または、下記式（２０４）で示される構造を有する２価の基を示す。
【外２０】

【００６１】
（式（２０４）中、Ｒ^２０４１、Ｒ^２０４２は、それぞれ独立に、置換または無置換の炭素数１〜４のアルキル基、置換または無置換のフェニル基、または、置換または無置換の４−トリル基を示す。）
Ｒ^２２〜Ｒ^２９は、それぞれ独立に、水素原子、アルキル基、アリール基、ヘテロアリール基、ハロゲン原子、シアノ基、ニトロ基、−ＯＲ^２０５１、−ＣＯＲ^２０５１、−ＣＯＯＲ^２０５１、−ＯＣＯＲ^２０５１、−ＣＯＮＲ^２０５１Ｒ^２０５２、−ＯＣＯＮＲ^２０５１Ｒ^２０５２、−ＮＲ^２０５１Ｒ^２０５２、−ＮＲ^２０５１ＣＯＲ^２０５２、−ＮＲ^２０５１ＣＯＯＲ^２０５２、−ＮＲ^２０５１ＳＯ_２Ｒ^２０５２、−ＳＯ_２Ｒ^２０５１、−ＳＯ_３Ｒ^２０５１、−ＳＯ_２ＮＲ^２０５１Ｒ^２０５２、または、−Ｎ＝Ｎ−Ｒ^２０５１を示す。ただし、Ｒ^２０５１、Ｒ^２０５２は、それぞれ独立に、置換または無置換の炭素数１〜４のアルキル基、置換または無置換のフェニル基、または、置換または無置換の４−トリル基を示す。）
【００６２】
上記表現の炭素数７〜４１の２級アルキル基としては、６−ドデカニル基、５−トリデカニル基などが挙げられ、炭素数３〜８の分枝状アルキル基としては、イソプロピル基、ｔ−ブチル基、イソオクチル基などが挙げられ、炭素数５〜７のシクロアルキレン基としては、シクロヘキシル基、シクロペンチル基などが挙げられ、ナフチレン基より高次である２価の融合芳香族炭素環基としては、フェナントリル基、アントリル基などが挙げられ、ピリジレン基より高次である２価の融合芳香族複素環式基としては、キノリレニル基、ナフチリジレニル基などが挙げられ、炭素数１〜４のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基などが挙げられる。
【００６３】
また、上記表現のアルキル基としては、メチル基、エチル基、ｔ−ブチル基などが挙げられ、アリール基としては、フェニル基などが挙げられ、ヘテロアリール基としては、ピリジル基、ピラジル基などが挙げられ、ハロゲン原子としては、塩素原子、フッ素原子などが挙げられる。
【００６４】
上記各基が有してもよい置換基としては、メチル基、エチル基などのアルキル基、−ＣＦ_３基などのハロゲン化アルキル基、ニトロ基などが挙げられる。特に、上記式（２）のＲ^２１、Ａ^２１が有してもよい置換基としては、塩素原子、フッ素原子などのハロゲン原子、メチル基、エチル基、ｔ−ブチル基などのアルキル基、シアノ基またはニトロ基が特に好ましい。
【００６５】
上記式（２）で示される構造を有するペリレンアミジンイミド化合物の好適な化合物例を以下に挙げる。
【００６６】
【外２１】

【００６７】
【外２２】

【００６８】
【外２３】

【００６９】
【外２４】

【００７０】
【外２５】

【００７１】
【外２６】

【００７２】
【外２７】

【００７３】
【外２８】

【００７４】
【外２９】

【００７５】
【外３０】

【００７６】
【外３１】

【００７７】
【外３２】

【００７８】
これらの中でも、（２−１）、（２−１０）、（２−２５）、（２−４０）が特に好ましい。
【００７９】
また、中間層に含有される有機電子輸送物質しては、下記式（３）で示される構造を有するキノン系化合物、下記式（４）で示される構造を有するキノン系化合物、下記式（５）で示される構造を有するキノン系化合物、下記式（６）で示される構造を有するサルフォン系化合物、下記式（７）で示される構造を有するサルフォン系化合物、下記式（８）で示される構造を有するフルオレン系化合物、下記式（９）で示される構造を有するフルオレン系化合物、下記式（１０）で示される構造を有するフルオレン系化合物、下記式（１１）で示される構造を有するフルオレン系化合物、下記式（１２）で示される構造を有するスチリル系化合物が好ましい。
【００８０】
また、下記式（１３）で示される構造を有するアゾ系化合物、下記式（１４）で示される構造を有するベンズアンスロン系アゾ顔料、および、下記式（１５）で示される構造を有するペリレン系誘導体顔料などの有機顔料も好ましい。
【００８１】
【外３３】

【００８２】
【外３４】

【００８３】
【外３５】

【００８４】
上記物質に代表されるようなこれら電子輸送物質は、製膜性を有する結着樹脂に分散した状態で使用されるのが一般的である。
【００８５】
本発明においては、中間層が電子搬送性を有しており、中間層の抵抗を下げた状態で使用する必要がないため、結着樹脂として抵抗の低い樹脂を使用する必要は必ずしもなく、抵抗の高い樹脂でも使用することができる。
【００８６】
本発明の電子写真感光体の中間層に使用される結着樹脂としては、メラミン樹脂、ウレタン樹脂およびフェノール樹脂などの熱硬化性樹脂や、ポリアミド、ポリエステル、ポリカーボネート、ポリスチレン、ポリメタクリル酸エステルおよびポリアリレートなどの熱可塑性樹脂が挙げられる。熱可塑性樹脂の中でも、有機溶剤可溶型熱可塑性樹脂が残留電位などの電位特性の点で好ましい。
【００８７】
また、結着樹脂に電子輸送物質を分散した状態の中間層ではなく、電子輸送性樹脂を使用した中間層であってもよい。
【００８８】
電子輸送性樹脂としては、例えば下記式（１６）で示される繰り返し構造単位を有するイミド樹脂が挙げられる。
【外３６】

【００８９】
上記式（１６）中、Ｒ^１６１〜Ｒ^１６４は、それぞれ独立に、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ルコキシアルキル基、置換または無置換のアラルキル基、または、シアノ基を示す。）
Ａ^１６１は、下記式（１６−１）または（１６−２）で示される構造を有する２価の基であることが好ましい。
−Ａｒ^１６１１−　　　（１６−１）
−Ａｒ^１６２１−Ｘ^１６２１−Ａｒ^１６２２−　　　（１６−２）
上記式（１６−１）中のＡｒ^１６１１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。
【００９０】
上記式（１６−２）中のＡｒ^１６２１、Ａｒ^１６２２は、それぞれ独立に、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し、Ｘ^１６２１は、酸素原子、硫黄原子、置換または無置換のアルキレン基、カルボニル基、または、スルホニル基を表す。
【００９１】
上記２価の芳香族炭化水素環基としては、フェニレン基、ビフェニレン基、ナフチレン基などが挙げられ、２価の芳香族複素環基としては、ピリジンジイル基、チオフェンジイル基などが挙げられ、アルキレン基としては、メチレン基、エチレン基、プロピレン基、イソプロピレン基などが挙げられる。
【００９２】
また、これらの基が有してもよい置換基としては、メチル基、エチル基、プロピル基などのアルキル基や、フッ素原子、塩素原子、臭素原子などのハロゲン原子や、トリフルオロメチル基などのハロメチル基や、メトキシ基、エトキシ基、プロポキシ基などのアルコキシ基や、ジメチルアミノ基、ジエチルアミノ基などのアルキルアミノ基や、アセチル基、ベンゾイル基などのアシル基や、シアノ基などが挙げられる。
【００９３】
これらに相当する構造としては、例えば以下の基が挙げられる。
【００９４】
【表１】

【００９５】
上記式（１６）で示される繰り返し構造単位（イミド構造）は、電子輸送能を有しており、その効果により負帯電型積層感光体や負帯電型単層感光体の場合、感光層中で発生した電子を本発明の中間層を経由して支持体側に速やかに注入、移動させることができ、その結果として感光層や中間層の界面またはバルク内における電子の滞留が減少し、繰り返し使用による電位の安定化や環境変動に対する電位の安定化に効果が認められる。特に、繰り返し使用時の電位安定性に関しては、既に特許３０８３０４９号に記載されている。
【００９６】
しかしながら、例えば、高速度の電子写真プロセスなどの過酷な条件下での電位の安定化には、中間層の電子注入や電子輸送効果をさらに高める必要がある。電子注入や電子輸送効果をさらに高める手段としては、芳香環を増加してイミド構造の共役性を高める方法もあるが、溶解性や成膜性など実用性に乏しくなる。
【００９７】
本発明におけるポリイミド樹脂は１種類の構造のみで用いるだけでなく２種類以上のものの混合系や２種類以上の共重合系で使用することも可能である。
【００９８】
中間層の膜厚は、０．３〜５μｍが好ましい。
【００９９】
従来、イオン電導性の樹脂を使用して比較的抵抗の低い中間層を使用してきた場合などには、高温高湿下においてさらに抵抗が低下し、中間層が電荷阻止層としての役割を果たさなくなることがほとんどであった。
【０１００】
本発明においては、電子輸送物質の効果によって、中間層の高温高湿下における体積抵抗率を１×１０^１２Ω・ｃｍ以上になるような結着材料を選択することができるため、高湿下における使用でも電荷阻止層としての機能を失うことがない。
【０１０１】
次に、本発明の電子写真感光体の感光層について説明する。
【０１０２】
本発明の感光層の構成は、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、および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を有する積層型に大別される。
【０１０３】
まず、積層型の感光層を有する電子写真感光体について説明する。
【０１０４】
積層型の感光層の構成としては、支持体上に電荷発生層および電荷輸送層をこの順に積層したもの（順層型）と、逆に電荷輸送層および電荷発生層の順に積層したもの（逆層型）がある。電子写真特性の面からは順層型が好ましい。
【０１０５】
電荷発生層は、スーダンレッドおよびダイアンブルーなどのアゾ顔料や、ピレン、キノンおよびアントアントロンなどのキノン顔料や、キノシアニン顔料や、ペリレン顔料や、インディゴおよびチオインディゴなどのインディゴ顔料や、オキシチタニウムフタロシアニン、ガリウムフタロシアニン、シリコーンフタロシアニンなどのフタロシアニン顔料などの電荷発生物質を、ポリビニルブチラール、ポリスチレンおよびポリ酢酸ビニルおよびアクリル樹脂などの結着樹脂に分散した分散液を塗布し、乾燥するか、上記顔料を真空蒸着することによって形成する。
【０１０６】
電荷発生物質としては、上に挙げたものの中でも、高感度であるという非常に好ましい特性を有しているが高湿環境下において微小な黒点が多数生じ、地カブリに近い画像になる黒点カブリの現象が起こりやすく、使用状態に制約が生じる事も有り下地を選ぶ傾向にあったフタロシアニン顔料については好適であり、さらには、ヒドロキシガリウムフタロシアニンおよびクロロガリウムフタロシアニンなどのガリウムフタロシアニンや、オキシチタニウムフタロシアニンがより好ましい。
【０１０７】
電荷発生層の膜厚は、好ましくは５μｍ以下、より好ましくは０．０１〜３μｍである。
【０１０８】
電荷輸送層は、主鎖または側鎖にビフェニレン、アントラセン、ピレンおよびフェナントレンなどの構造を有する多環芳香族化合物や、インドール、カルバゾール、オキサジアゾールおよびピラゾリンなどの含窒素環化合物や、ヒドラゾン化合物およびスチリル化合物などの電荷輸送物質を、成膜性を有する結着樹脂に溶解した溶液を塗布し、乾燥することによって形成する。
【０１０９】
成膜性を有する結着樹脂としては、ポリエステル、ポリカーボネート、ポリスチレン、ポリメタクリル酸エステルおよびポリアリレートなどが挙げられる。
【０１１０】
電荷輸送層の膜厚は、好ましくは５〜４０μｍ、より好ましくは８〜３０μｍである。
【０１１１】
単層型の感光層は、上記電荷発生物質および上記電荷輸送物質を上記結着樹脂に分散および溶解した溶液を塗布し、乾燥することによって形成する。
【０１１２】
感光層の膜厚は、好ましくは５〜４０μｍ、より好ましくは１０〜３０μｍである。
【０１１３】
本発明の電子写真感光体の感光層は、上に挙げたような電子輸送物質を含有することが好ましい。
【０１１４】
感光層に電子輸送物質を添加することによって、感光層と中間層の界面における感光層から中間層への電子の移動が円滑に行われると考えられる。
【０１１５】
したがって、感光層に電子輸送物質を添加する場合には中間層と界面で接触している層に添加することが好ましい。例えば、支持体側から中間層、電荷発生層、電荷輸送層の順に積層した場合は、電荷発生層に電子輸送物質を添加することが好ましい。
【０１１６】
感光層に添加する電子輸送物質は、中間層に使用した電子輸送物質と同一の物質であることが層間の電荷の受け渡しが円滑に行われるという点でより好ましい。
【０１１７】
また、本発明においては、感光層上に感光層を保護することを目的として保護層を設けてもよい。
【０１１８】
保護層を構成する材料としては、ポリエステル、ポリアクリレート、ポリエチレン、ポリスチレン、ポリブタジエン、ポリカーボネート、ポリアミド、ポリプロピレン、ポリイミド、ポリアミドイミド、ポリサルホン、ポリアクリルエーテル、ポリアセタール、フェノール、アクリル、シリコーン、エポキシ、ユリア、アリル、アルキッド、ブチラール、フェノキシ、ホスファゼン、アクリル変性エポキシ、アクリル変性ウレタンおよびアクリル変性ポリエステル樹脂などが挙げられる。
【０１１９】
保護層の膜厚は、０．２〜１０μｍであることが好ましい。
【０１２０】
以上の各層には、クリーニング性や耐摩耗性などの改善のために、ポリ四フッ化エチレン、ポリフッ化ビニリデン、フッ素系グラフトポリマー、シリコーン系グラフトポリマー、フッ素系ブロックポリマー、シリコーン系ブロックポリマーおよびシリコーン系オイルなどの潤滑剤を含有させてもよい。
【０１２１】
さらに、耐候性を向上させる目的で、酸化防止剤などの添加物を加えてもよい。
【０１２２】
また、保護層には、抵抗制御の目的で、導電性酸化スズおよび導電性酸化チタニウムなどの導電性粉体を分散してもよい。
【０１２３】
図１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有する電子写真装置の概略構成の１例を示す。
【０１２４】
図において、１はドラム状の本発明の電子写真感光体であり、軸２を中心に矢印方向に所定の周速度で回転駆動される。
【０１２５】
電子写真感光体１は、回転過程において、（一次）帯電手段３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）からの露光光４を受ける。こうして電子写真感光体１の周面に静電潜像が順次形成されていく。
【０１２６】
形成された静電潜像は、次いで現像手段５によりトナー現像され、現像されたトナー現像像は、不図示の給紙部から電子写真感光体１と転写手段６との間に電子写真感光体１の回転と同期取り出されて給紙された転写材７に、転写手段６により順次転写されていく。
【０１２７】
像転写を受けた転写材７は、電子写真感光体面から分離されて定着手段８へ導入されて像定着を受けることにより複写物（コピー）として装置外へプリントアウトされる。
【０１２８】
像転写後の電子写真感光体１の表面は、クリーニング手段９によって転写残りトナーの除去を受けて清浄面化され、さらに前露光手段（不図示）からの前露光光１０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。
【０１２９】
帯電手段３は、コロナ放電を利用したスコロトロン帯電器やコロトロン帯電器でもよく、ローラ形状、ブレード形状、ブラシ形状など公知の形態が使用される接触型帯電器（接触帯電手段）を用いてもよい。接触型帯電器の部材の材料としては、導電性を付与した弾性体が一般的である。
【０１３０】
接触帯電部材に印加される電圧としては、直流電圧のみでもよく、直流電圧に交流電圧を重畳した振動電圧でもよい。
【０１３１】
ここでいう振動電圧とは、時間とともに周期的に電圧値が変化する電圧であり、交流電圧は、直流電圧のみ印加時における電子写真感光体の帯電開始電圧の２倍以上のピーク間電圧を有することが好ましい。
【０１３２】
接触帯電手段を用いる場合は、前露光は必ずしも必要ではない。
【０１３３】
本発明においては、上述の電子写真感光体１、帯電手段３、現像手段５およびクリーニング手段９などの構成要素のうち、複数のものを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。
【０１３４】
例えば、帯電手段３、現像手段５およびクリーニング手段９の少なくとも１つを電子写真感光体１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１２などの案内手段を用いて装置本体に着脱自在なプロセスカートリッジ１１とすることができる。
【０１３５】
また、露光光４は、電子写真装置が複写機やプリンターである場合には、原稿からの反射光や透過光、あるいは、センサーで原稿を読取り、信号化し、この信号にしたがって行われるレーザービームの走査、ＬＥＤアレイの駆動および液晶シャッターアレイの駆動などにより照射される光である。
【０１３６】
【実施例】
以下、実施例にしたがって、本発明をより一層詳細に説明する。
【０１３７】
（実施例１）
ＪＩＳ規格のＡ３００３材のアルミニウム合金をポートホール押し出し加工によりシリンダー状に加工したものを用意し、このシリンダーの外表面をダイヤモンドバイトにより鏡面切削し、外径２９．９２ｍｍ、内径２８．５ｍｍ、長さ２６０．５ｍｍ、外表面の十点平均表面粗さＲｚの値を０．１μｍとし、さらにこの支持体を、２０μｍ径の球状アルミナビーズと水を用いて液体ホーニング法により、アルミナビーズと水の混合したものをシリンダーの表面に吐出することにより表面を粗面加工し、表面のＲｚの値が０．４８μｍである電子写真感光体用支持体とした。
【０１３８】
この支持体上に、下記式（１７‐１）および（１７‐２）で示される構造を有する２種類の材料の混合物１０質量部に、Ｎ−メチル−２−ピロリドンとシクロヘキサノンの混合比１：２の混合溶剤９０質量部を加えた溶液を、浸漬塗布により塗工した後に、１５０℃の温度で３０分間乾燥し、下記式（２‐３）で示される繰り返し構造単位を有するイミド樹脂を含有する膜厚１μｍの中間層を形成した。
【０１３９】
【外３７】

（１７−１）
【０１４０】
【外３８】

（１７−２）
【０１４１】
【外３９】

（１７‐３）
（ｌ、ｍおよびｎは正の整数を表わす。）
【０１４２】
次に、この中間層上にヒドロキシガリウムフタロシアニン顔料６質量部、ポリビニルブチラール樹脂（商品名：ＢＸ−１、積水化学工業株式会社製）３質量部およびシクロヘキサノン４０質量部からなる混合液をサンドミルで１０時間分散した後テトラヒドロフラン６０質量部を加えて電荷発生層用の分散液を調合し、上記中間層上に浸漬塗布し、さらに１００℃で１０分間乾燥して膜厚０．１μの電荷発生層を形成した。
【０１４３】
次に、下記式（３）で示されるトリアリールアミン化合物５０質量部およびビスフェノールＺ型ポリカーボネート樹脂５０質量部を、モノクロロベンゼン４００質量部に溶解した溶液を、上記電荷発生層上に浸漬塗布し、１１０℃の雰囲気中で１時間加熱乾燥して膜厚１７μｍの電荷輸送層を形成し、電子写真感光体を作製した。
【０１４４】
【外４０】

（１８）
【０１４５】
（実施例２〜５）
実施例１において液体ホーニング時の吐出圧を変化させることにより表面の十点平均粗さＲｚの値が０．６μｍ、１．０μｍ、１．５μｍ、２．０μｍのシリンダー支持体を作製し、これらの表面に実施例１と同様の中間層、感光層を形成した。
【０１４６】
これらを表面粗さが小さいものから順に実施例２、３、４、５とする。
【０１４７】
（比較例１および２）
実施例１において、ホーニング時の吐出圧を変化させて支持体の表面粗さＲｚの値を０．４μｍ、２．１μｍとした以外は、実施例１と同様である電子写真感光体を作製した。
【０１４８】
これらを順に比較例１、２とした。
【０１４９】
（実施例６〜１１）
実施例３において、中間層の膜厚を０．２μｍ、０．３μｍ、０．６μｍ、２．０μｍ、３．０μｍ、５．０μｍとしたものを、順に実施例６〜１１とした。
【０１５０】
（比較例３、４）
実施例３において、中間層の膜厚を０．１μｍ、６．０μｍとしたものを、順に比較例３、４とした。
【０１５１】
（実施例１２〜１６）
実施例１〜５において、支持体上にフェノール樹脂４部、化合物例（１−１）２部、メトキシプロパノール５０部、ベンジルアルコール５０部、メタノール１０部からなる中間層塗料を調整して塗布し、１４５℃で２０分間乾燥して膜厚１．０μｍの中間層を形成した。
【０１５２】
この中間層上に実施例１〜５と同様に感光層を形成して電子写真感光体とした。
【０１５３】
これらを順に実施例１２〜１６とした。
【０１５４】
（実施例１７〜２９）
実施例１４において、中間層に使用する電子輸送物質として、化合物（１−１）のかわりに、それぞれ（１−３）、（１−１０）、（１−１９）、（１−２６）、（１−３５）、（１−４８）、（２−１）、（２−１０）、（２−２５）、（２−４０）、（３）、（７）、（１１）を用いて中間層を形成したものを、順に実施例１７〜２９とした。
【０１５５】
（比較例５〜９）
実施例１〜５において、それぞれ中間層としてポリイミド樹脂のかわりにアルコール可溶性のポリアミド樹脂をメタノールとブタノールに３：１の混合溶媒に溶解したものを浸漬法により支持体上に塗布して１００℃の温度で１０分間乾燥して１．０μｍの膜厚とした以外は、実施例１〜５と同様にしたものを、順に比較例５〜９とした。
【０１５６】
（比較例１０〜２３）
実施例１４および１７〜２９において、中間層のバフェノール樹脂をアルコール可溶性ポリアミド樹脂に変更したものを、順に比較例１０〜２３とした。
【０１５７】
このようにして作製した実施例１〜２９および比較例１〜２３の各電子写真感光体を、市販のレーザービームプリンター（商品名：ＬａｓｅｒＪｅｔ　４０００，日本ヒューレット・パッカード（株）社製）の改造機（レーザー光量および帯電電位可変）に取り付け、暗部電位（ＶＤ）が−７００Ｖになるように帯電し、これに発光波長λが８００ｎｍのレーザー光を照射して明部電位（ＶＬ）が−１５０Ｖになるのに必要な光量を測定し感度とした。
【０１５８】
電子写真感光体の表面電位は、評価機から、現像用カートリッジを抜き取り、そこに電位測定装置を挿入し測定を行った。電位測定装置は、現像用カートリッジの現像位置に電位測定プローブを配置することで構成されており、電子写真感光体に対する電位測定プローブの位置は、ドラム軸方向の中央とした。
【０１５９】
測定はすべて、２５℃、相対湿度が５０％となる環境で評価を行い、電子写真感光体は、測定の２４時間前から、測定環境に放置したものを用いた。
【０１６０】
さらに、１μＪ／ｃｍ^２の光量を照射した場合の電位を残留電位Ｖｒとして測定した。
【０１６１】
また、この電子写真感光体を３０℃、８０％Ｒｈの環境下に２４時間以上放置した状態で、同様に明部電位を測定した。同時にベタ白画像を出した。
【０１６２】
さらに、常温常湿環境において繰り返し画像出し耐久試験を５０００枚行った後の、暗部電位および明部電位の初期との変動量ΔＶＤおよびΔＶＬを測定した。
【０１６３】
さらに、この電子写真感光体の中間層と同様の層（体積抵抗率評価用）を作製し、それを３０℃、８０％Ｒｈの環境下で２４時間放置した状態で、クシ型電極を使用して１０Ｖの電圧を引加して体積抵抗率を測定した。
【０１６４】
評価結果を表２、３に示す。
【０１６５】
【表２】

【０１６６】
【表３】

【０１６７】
次に、実施例１〜１６および比較例１〜９に関して画像を出した際の干渉縞および画像ゴーストについて調べたところ、表４に示すようになった。
【０１６８】
ゴースト評価は５ｍｍ×５ｍｍ角の黒い正方形（■）および５ｍｍ径の黒丸（●）がある画像を印刷した後に続けてハーフトーン画像を印刷し、このハーフトーン画像に黒い正方形、および黒丸の画像の残像が重なって印刷されていないかどうかを比較することによって行った。
【０１６９】
【表４】

【０１７０】
以上の結果から分かるように、実施例においては、電位安定性、画像共に良好な感光体が得られているが、比較例においては、感度、残留電位、電位安定性あるいは画像特性において何らかの不具合が発生していることが分かる。
【０１７１】
（実施例３０〜３５）
実施例１において支持体をホーニング加工する際の吐出圧を変更して、シリンダー支持体の外径表面の十点平均粗さＲｚの値を０．２４μｍ、０．３μｍ、０．６μｍ、０．８μｍ、１．０μｍとしたものを用意した。
【０１７２】
これらの支持体上に、下記式（１９）で示される繰り返し構造単位を有するポリイミド樹脂を実施例１と同様の方法で１μｍの厚さに形成して中間層とした。
【０１７３】
【外４１】

（１９）
ｎは正の整数。
【０１７４】
さらに、この上に実施例１と同様の感光層を形成したものを表面粗さの小さいものから、順に実施例３０〜３４とした。
【０１７５】
（実施例３６〜３８）
実施例３２において、中間層の膜厚を０．３μｍ、０．６μｍ、３．０μｍ、５．０μｍとしたものを、順に実施例３５〜３８とした。
【０１７６】
（比較例２４〜２８）
実施例３０において、アルミニウム支持体の外径表面粗さＲｚの値を０．２μｍ、１．１μｍとしたものを、順に比較例２４、２５とする。
【０１７７】
また、実施例３２において、中間層の厚さを０．１μｍ、６．０μｍとしたものを、順に比較例２６、２７とした。
【０１７８】
さらに、実施例３２において、中間層を比較例５と同様に膜厚１．０μｍのアルコール可溶性ポリアミドとしたものを比較例２８とした。
【０１７９】
次に、市販のレーザービームプリンター（商品名：ＬａｓｅｒＪｅｔ　４０００，日本ヒューレット・パッカード（株）社製）の改造機（レーザー光量および帯電電位可変）に市販の発光波長λが４００ｎｍである半導体ダイオードレーザー（日亜化学株式会社製）を取り付けた評価機を使用して実施例３０〜３９および比較例２４〜２８を評価した。
【０１８０】
評価結果を表５、６に示す。
【０１８１】
【表５】

【０１８２】
【表６】

【０１８３】
以上の評価より、実施例では、良好な特性の電子写真感光体が得られたが、比較例の電子写真感光体には、いずれかの項目において不都合が発生していることが分かる。
【０１８４】
【発明の効果】
以上説明したように、本発明によれば、半導体レーザーによって表面に静電潜像が形成される、中間層を有する電子写真感光体においても、画像欠陥が発生せず、電位変動の少ない良好な電子写真特性を有する電子写真感光体、該電子写真感光体を有するプロセスカートリッジおよび電子写真装置を提供することができる。
【図面の簡単な説明】
【図１】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有する電子写真装置の概略構成の１例である。
【符号の説明】
１　電子写真感光体
２　軸
３　帯電手段
４　露光光
５　現像手段
６　転写手段
７　転写材
８　定着手段
９　クリーニング手段
１０　前露光光
１１　プロセスカートリッジ
１２　レール[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electrophotographic photoreceptor, a process cartridge having the electrophotographic photoreceptor, and an electrophotographic apparatus. More specifically, the present invention has an intermediate layer and a photosensitive layer on a support in this order, and the photosensitive layer comprises a charge generating substance and a charge. An electrophotographic photosensitive member containing a transport material and having an electrostatic latent image formed on a surface thereof by a semiconductor laser; and an electrophotographic photosensitive member having the electrophotographic photosensitive member, wherein the electrostatic latent image is formed on the surface of the electrophotographic photosensitive member by the semiconductor laser. A process cartridge detachable from an electrophotographic apparatus main body having an exposure unit for forming an image, and an electron having an exposure unit for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member by the electrophotographic photosensitive member and a semiconductor laser Related to photographic equipment.
[0002]
[Prior art]
The photosensitive layer on the support of the organic electrophotographic photoreceptor using an organic photoconductive substance includes a charge generation layer containing a charge generation substance such as an azo pigment or a phthalocyanine pigment, and a hydrazone compound or a triarylamine compound. There are a laminated photosensitive layer having a charge transporting layer containing a hole transporting substance such as a stilbene compound, and a single-layered photosensitive layer containing these charge generating substance and a hole transporting substance in the same layer.
[0003]
However, simply providing these photosensitive layers on the support may cause peeling of the photosensitive layer or defects on the surface of the support (shape defects such as scratches, material defects such as impurities) may be directly reflected in the image. In many cases, problems such as black dot image defects and white spots occur.
[0004]
In order to solve these problems, many electrophotographic photosensitive members have a layer called an intermediate layer provided between the photosensitive layer and the support.
[0005]
Many of the intermediate layers are provided with an insulating organic polymer in the form of a thin film or provided with an insulating oxide film such as alumite. Or the space charge accumulated at the interface between the intermediate layer and the photosensitive layer causes fatigue of the electrophotographic photosensitive member such as an increase in residual potential.
[0006]
As a method for preventing these, a method of dispersing inorganic conductive particles in an intermediate layer, a method of using an ion conductive polymer, and the like are known.
[0007]
Titanium oxide or tin oxide is used as the inorganic conductive particles, but there are problems in the preparation of the dispersion and the stability of the solution, and also image defects due to poor dispersion.
[0008]
In the case of an intermediate layer containing an ion conductive polymer such as a soluble polyamide, instability of characteristics due to the environment becomes a problem.
[0009]
In recent years, methods that use a single-wavelength light source to perform exposure, such as laser printers and digital copiers, have become the dominant part of electrophotography. And interference fringes caused by factors such as uneven film thickness of the electrophotographic photosensitive member.
[0010]
That is, when the surface roughness of the support is less than a certain level, for example, when used in an electrophotographic apparatus using coherent light of a single wavelength by a semiconductor laser as exposure light, interference occurs. Since image defects called fringes occur, the surface roughness of the support must be a certain level or more.
[0011]
Therefore, in order to eliminate this problem, some means is required as an electrophotographic photosensitive member.
[0012]
Methods that have been performed so far include, for example, a method of cutting the surface of a support to prevent it by giving a certain surface roughness, a method of dry blasting the surface of the support, and a method of liquid honing A method such as a method of forming a conductive film that diffuses light on the surface has been adopted.
[0013]
In a usual electrophotographic photoreceptor, the roughening of this surface is combined with the provision of an intermediate layer thereon.
[0014]
When both are combined, in a conventional resistance control type intermediate layer in which conductive particles are dispersed in a binder resin, when provided on the surface of a support having a roughened surface, a thin portion is formed due to unevenness of the support. Although a thick part is formed, the withstand voltage is low in a thin part when charged, and image defects are likely to occur. Therefore, the entire film thickness must be increased, so that the residual potential increases and the image ghost increases. Was causing the outbreak.
[0015]
Even if the surface roughness of the support is reduced, the withstand voltage of the material used for the intermediate layer itself is low, and if the thickness of the intermediate layer is reduced, image defects occur. The thickness could not be reduced below.
[0016]
[Problems to be solved by the invention]
An object of the present invention is to solve the above problems and form an electrostatic latent image on the surface by a semiconductor laser. An object of the present invention is to provide an electrophotographic photosensitive member having electrophotographic characteristics.
[0017]
Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having such an electrophotographic photosensitive member.
[0018]
[Means for Solving the Problems]
The present inventors have conducted intensive studies and as a result, have found that a compound containing an electron transporting substance (electron transporting substance) has a volume resistivity of 1 × in a high temperature and high humidity environment (30 ° C., 80% RH). 10 ¹² An intermediate layer of Ω · cm or more is provided, and the ratio of the ten-point average roughness (Rz) of the surface of the support on the photosensitive layer side to the wavelength (λ) of the semiconductor laser used for image exposure (exposure) is further determined. It has been found that an electrophotographic photosensitive member having a value (Rz / λ) of 0.6 or more and 2.5 or less can solve the above problem.
[0019]
That is, the present invention is an electrophotographic photosensitive member having an intermediate layer and a photosensitive layer on a support in this order, and the photosensitive layer contains a charge generating substance and a charge transporting substance. In an electrophotographic photosensitive member on which a latent image is formed,
The intermediate layer contains an electron transport material,
The volume resistivity of the intermediate layer under an environment of 30 ° C. and 80% RH is 1 × 10 ¹² Ωcm or more,
The ratio (Rz / λ) of the ten-point average roughness (Rz) of the surface of the support on the photosensitive layer side to the wavelength (λ) of the semiconductor laser is 0.6 or more and 2.5 or less. An electrophotographic photosensitive member characterized by the following:
[0020]
Further, the present invention integrally supports an electrophotographic photosensitive member and at least one unit selected from the group consisting of a charging unit, a developing unit, a transfer unit and a cleaning unit, and is detachably attached to an electrophotographic apparatus main body. In the process cartridge,
The electrophotographic photoconductor is the electrophotographic photoconductor,
The process cartridge is characterized in that the electrophotographic apparatus is an electrophotographic apparatus having an exposure unit for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member by a semiconductor laser.
[0021]
Further, the present invention provides an electrophotographic apparatus having an electrophotographic photosensitive member, a charging unit, an exposing unit, a developing unit and a transferring unit.
The electrophotographic photoconductor is the electrophotographic photoconductor,
An electrophotographic apparatus, wherein the exposing means is means for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member by a semiconductor laser.
[0022]
Depending on the spectral sensitivity of the charge-generating substance, when the wavelength of the semiconductor laser is long, compared to when the wavelength is short, the binder resin in the photosensitive layer is not changed until the light reaches the charge-generating substance even at the same exposure dose. It is considered that the amount of light reaching the charge generating substance is large and the amount of generated carriers is relatively large because the attenuation due to such factors is small.
[0023]
Since both the photosensitive layer and the intermediate layer are mainly composed of resin components, there is an extremely thin region where both materials are mixed at the interface between them, and the transfer of electrons is performed relatively smoothly. However, since the interface between the intermediate layer and the support is relatively clear, the surface of the support needs to be roughened to increase the surface area so that electrons can be easily transferred.
[0024]
Conversely, when the wavelength of the semiconductor laser is short, a support having a small surface roughness can be used.
[0025]
The intermediate layer of the electrophotographic photoreceptor of the present invention has a higher resistance than the intermediate layer of the conventional electrophotographic photoreceptor, and thus has a higher withstand voltage per unit film thickness. It can be thinner than a layer, and can reduce defects such as ghosts, residual potential, and potential fluctuations during endurance caused by using a thick film in the past. It has become possible to provide a photoreceptor.
[0026]
When the surface roughness of the support becomes smoother than the above specified value, the contact area between the support surface and the intermediate layer becomes small, so that the electron transporting substance is in a molecular state or a fine particle state in the intermediate layer. When the particles are dispersed, the number of contact points between these materials and the support decreases, and the electrons generated in the charge generation layer hardly pass through the support, and the electrons easily remain. Further, when used in an electrophotographic apparatus using coherent light from a semiconductor laser as exposure light, image defects called so-called interference fringes occur.
[0027]
Therefore, the surface roughness of the support on the photosensitive layer side satisfies the above specified value, that is, the ratio of the ten-point average roughness (Rz) of the surface of the support on the photosensitive layer side to the wavelength (λ) of the semiconductor laser. The value (Rz / λ) needs to be 0.6 or more and 2.5 or less.
[0028]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the configuration of the electrophotographic photosensitive member of the present invention will be described.
[0029]
The support used in the electrophotographic photoreceptor of the present invention may have any conductivity, for example, aluminum, nickel, copper, gold, a metal or alloy such as iron, polyester, polycarbonate, polyimide, glass, etc. A thin film of a conductive material such as indium oxide, tin oxide, or a metal such as aluminum, silver, or gold formed on an insulative support, or a cylindrical support such as aluminum or resin. Examples thereof include those in which the surface roughness is adjusted, such as those in which a film in which fine particles are dispersed in a binder resin is provided.
[0030]
Examples of the method of roughening the surface of the support such as aluminum and resin include a method of cutting the surface of the support to give a certain surface roughness, and a method of dry blasting the surface of the support. Processing, liquid honing, polishing using a grindstone to polish the surface, centerless polishing, a method combining centerless polishing and electrolytic polishing, rough surface by etching the support surface with acid or alkali And a method of forming a conductive film on the surface that diffusely reflects light.
[0031]
The electrophotographic photoreceptor of the present invention has an intermediate layer containing an electron transport substance on a support.
[0032]
As the organic electron transporting substance contained in the intermediate layer, a naphthalene amidine imide compound having a structure represented by the following formula (1) is preferable.
[Outside 1]

[0033]
(In the formula (1), R ¹¹ Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ¹² ~ R ^Fifteen Each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxylic acid ester group, an alkyl group which may have a substituent, or a substituted or unsubstituted alkoxy group. A ¹¹ Is a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group, a divalent group having a structure represented by the following formula (101), or a divalent group having a structure represented by the following formula (102) Represents a group.
[0034]
[Outside 2]

[0035]
[Outside 3]

[0036]
(In the formulas (101) and (102), R ¹⁰¹¹ ~ R ¹⁰¹⁴ , R ¹⁰²¹ , R ¹⁰²² Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and n represents 0 or 1. )
[0037]
Examples of the alkyl group in the above expression include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a hexyl group, and an octyl group.Examples of the aryl group include a phenylene group, a naphthyl group, and an anthryl group. Examples of the halogen atom include a chlorine atom and a fluorine atom. Examples of the carboxylate group include a carboxyethyl group and a carboxy t-butyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a t-butoxy group. And the like. Examples of the cycloalkylene group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, and examples of the arylene group include an ethylenyl group, a butenyl group, and a hexenyl group.
[0038]
Examples of the substituent which each of the above groups may have include an alkyl group such as a methyl group, an ethyl group and a t-butyl group; a carboxyalkyl group such as a carboxymethyl group, a carboxyethyl group and a carboxybutyl group; and a nitro group. And a -CF3 group.
[0039]
Preferred examples of the naphthalene amidine imide compound having the structure represented by the above formula (1) are shown below.
[0040]
[Outside 4]

[0041]
[Outside 5]

[0042]
[Outside 6]

[0043]
[Outside 7]

[0044]
[Outside 8]

[0045]
[Outside 9]

[0046]
[Outside 10]

[0047]
[Outside 11]

[0048]
[Outside 12]

[0049]
[Outside 13]

[0050]
[Outside 14]

[0051]
[Outside 15]

[0052]
Among these, (1-1) and (1-35) are particularly preferred.
[0053]
Further, as the organic electron transporting substance contained in the intermediate layer, a perylene amidine imide compound having a structure represented by the following formula (2) is also preferable.
[0054]
[Outside 16]

[0055]
(In the formula (2), R ²¹ Is a secondary alkyl group having 7 to 41 carbon atoms or a group having a structure represented by the following formula (201);
[Outside 17]

[0056]
(In the formula (201), R ²⁰¹¹ ~ R ²⁰¹⁵ Each independently represents a hydrogen atom or a branched alkyl group having 3 to 8 carbon atoms. Where R ²⁰¹¹ ~ R ²⁰¹⁵ Are two or more hydrogen atoms, and not all are hydrogen atoms. )
A ²¹ Is a substituted or unsubstituted cycloalkylene group having 5 to 7 carbon atoms, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted naphthylene group, Unsubstituted divalent fused aromatic carbocyclic group, substituted or unsubstituted divalent fused aromatic heterocyclic group higher in order than pyridylene group, divalent having a structure represented by the following formula (202) Group,
[0057]
[Outside 18]

[0058]
A divalent group having a structure represented by the following formula (203),
[Outside 19]

[0059]
(In the formula (203), R ²⁰³¹ , R ²⁰³² Each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 4-tolyl group. )
[0060]
Alternatively, a divalent group having a structure represented by the following formula (204) is shown.
[Outside 20]

[0061]
(In the formula (204), R ²⁰⁴¹ , R ²⁰⁴² Each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 4-tolyl group. )
R ²² ~ R ²⁹ Is independently a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a halogen atom, a cyano group, a nitro group, -OR ²⁰⁵¹ , -COR ²⁰⁵¹ , -COOR ²⁰⁵¹ , -OCOR ²⁰⁵¹ , -CONR ²⁰⁵¹ R ²⁰⁵² , -OCONR ²⁰⁵¹ R ²⁰⁵² , -NR ²⁰⁵¹ R ²⁰⁵² , -NR ²⁰⁵¹ COR ²⁰⁵² , -NR ²⁰⁵¹ COOR ²⁰⁵² , -NR ²⁰⁵¹ SO ₂ R ²⁰⁵² , -SO ₂ R ²⁰⁵¹ , -SO ₃ R ²⁰⁵¹ , -SO ₂ NR ²⁰⁵¹ R ²⁰⁵² Or -N = NR ²⁰⁵¹ Is shown. Where R ²⁰⁵¹ , R ²⁰⁵² Each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 4-tolyl group. )
[0062]
Examples of the secondary alkyl group having 7 to 41 carbon atoms in the above expression include a 6-dodecanyl group and a 5-tridecanyl group. Examples of the branched alkyl group having 3 to 8 carbon atoms include an isopropyl group and a t-butyl group. Group, isooctyl group, and the like.Examples of the cycloalkylene group having 5 to 7 carbon atoms include a cyclohexyl group and a cyclopentyl group.Examples of the divalent fused aromatic carbocyclic group having a higher order than a naphthylene group include: Phenanthryl group, anthryl group and the like, as examples of divalent fused aromatic heterocyclic group higher than pyridylene group, quinolylenyl group, naphthyridylenyl group and the like, as an alkyl group having 1 to 4 carbon atoms , A methyl group, an ethyl group, a propyl group, a butyl group and the like.
[0063]
Examples of the alkyl group in the above expression include a methyl group, an ethyl group, a t-butyl group and the like, examples of the aryl group include a phenyl group, and examples of the heteroaryl group include a pyridyl group and a pyrazyl group. Examples of the halogen atom include a chlorine atom and a fluorine atom.
[0064]
Examples of the substituent which each of the above groups may have include an alkyl group such as a methyl group and an ethyl group; ₃ Groups, such as a halogenated alkyl group and a nitro group. In particular, R in the above formula (2) ²¹ , A ²¹ As a substituent which may have, a halogen atom such as a chlorine atom and a fluorine atom, an alkyl group such as a methyl group, an ethyl group and a t-butyl group, a cyano group and a nitro group are particularly preferable.
[0065]
Preferred examples of the perylene amidine imide compound having the structure represented by the above formula (2) are shown below.
[0066]
[Outside 21]

[0067]
[Outside 22]

[0068]
[Outside 23]

[0069]
[Outside 24]

[0070]
[Outside 25]

[0071]
[Outside 26]

[0072]
[Outside 27]

[0073]
[Outside 28]

[0074]
[Outside 29]

[0075]
[Outside 30]

[0076]
[Outside 31]

[0077]
[Outside 32]

[0078]
Among these, (2-1), (2-10), (2-25) and (2-40) are particularly preferred.
[0079]
Examples of the organic electron transporting substance contained in the intermediate layer include a quinone compound having a structure represented by the following formula (3), a quinone compound having a structure represented by the following formula (4), and a quinone compound having a structure represented by the following formula (4). ), A sulfone compound having a structure represented by the following formula (6), a sulfone compound having a structure represented by the following formula (7), and a structure represented by the following formula (8): A fluorene-based compound having a structure represented by the following formula (9), a fluorene-based compound having a structure represented by the following formula (10), and a fluorene-based compound having a structure represented by the following formula (11) And a styryl compound having a structure represented by the following formula (12).
[0080]
Further, an azo compound having a structure represented by the following formula (13), a benzanthrone-based azo pigment having a structure represented by the following formula (14), and a perylene-based derivative having a structure represented by the following formula (15) Organic pigments such as pigments are also preferred.
[0081]
[Outside 33]

[0082]
[Outside 34]

[0083]
[Outside 35]

[0084]
These electron transporting substances such as the above substances are generally used in a state of being dispersed in a binder resin having film forming properties.
[0085]
In the present invention, since the intermediate layer has an electron-transporting property and it is not necessary to use the intermediate layer in a state where the resistance is lowered, it is not necessary to use a resin having a low resistance as the binder resin. Resin can be used.
[0086]
Examples of the binder resin used in the intermediate layer of the electrophotographic photoreceptor of the present invention include thermosetting resins such as melamine resin, urethane resin and phenol resin, polyamide, polyester, polycarbonate, polystyrene, polymethacrylate and polymethacrylate. A thermoplastic resin such as arylate is exemplified. Among the thermoplastic resins, an organic solvent-soluble thermoplastic resin is preferable in terms of potential characteristics such as residual potential.
[0087]
Further, the intermediate layer may be an intermediate layer using an electron transporting resin, instead of the intermediate layer in which the electron transporting substance is dispersed in the binder resin.
[0088]
Examples of the electron transporting resin include an imide resin having a repeating structural unit represented by the following formula (16).
[Outside 36]

[0089]
In the above formula (16), R ¹⁶¹ ~ R ¹⁶⁴ Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted aralkyl group, or a cyano group. )
A ¹⁶¹ Is preferably a divalent group having a structure represented by the following formula (16-1) or (16-2).
-Ar ¹⁶¹¹ -(16-1)
-Ar ¹⁶²¹ -X ¹⁶²¹ -Ar ¹⁶²² -(16-2)
Ar in the above formula (16-1) ¹⁶¹¹ Represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group or a substituted or unsubstituted divalent aromatic heterocyclic group.
[0090]
Ar in the above formula (16-2) ¹⁶²¹ , Ar ¹⁶²² Each independently represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group or a substituted or unsubstituted divalent aromatic heterocyclic group; ¹⁶²¹ Represents an oxygen atom, a sulfur atom, a substituted or unsubstituted alkylene group, a carbonyl group, or a sulfonyl group.
[0091]
Examples of the divalent aromatic hydrocarbon ring group include a phenylene group, a biphenylene group, and a naphthylene group. Examples of the divalent aromatic heterocyclic group include a pyridinediyl group and a thiophendiyl group. Examples of the group include a methylene group, an ethylene group, a propylene group, and an isopropylene group.
[0092]
Examples of the substituent which these groups may have include alkyl groups such as methyl group, ethyl group and propyl group, halogen atoms such as fluorine atom, chlorine atom and bromine atom, and trifluoromethyl group and the like. Examples thereof include an alkoxy group such as a halomethyl group, a methoxy group, an ethoxy group, and a propoxy group; an alkylamino group such as a dimethylamino group and a diethylamino group; an acyl group such as an acetyl group and a benzoyl group; and a cyano group.
[0093]
The structures corresponding to these include, for example, the following groups.
[0094]
[Table 1]

[0095]
The repeating structural unit (imide structure) represented by the above formula (16) has an electron-transporting ability, and due to its effect, in the case of a negatively charged laminated photoconductor or a negatively charged single-layered photoconductor, the photosensitive layer has The generated electrons can be quickly injected and transferred to the support side via the intermediate layer of the present invention, and as a result, the stagnation of electrons at the interface of the photosensitive layer or the intermediate layer or in the bulk is reduced. The effect is recognized in stabilizing the potential and stabilizing the potential against environmental fluctuations. In particular, the potential stability upon repeated use is already described in Japanese Patent No. 3083049.
[0096]
However, for example, in order to stabilize the potential under severe conditions such as a high-speed electrophotographic process, it is necessary to further enhance the electron injection and electron transport effects of the intermediate layer. As a means for further enhancing the electron injection or electron transport effect, there is a method of increasing the conjugation property of the imide structure by increasing the number of aromatic rings. However, the method has poor practicality such as solubility and film formability.
[0097]
The polyimide resin in the present invention can be used not only in one type of structure but also in a mixed system of two or more types or a copolymerized system of two or more types.
[0098]
The thickness of the intermediate layer is preferably 0.3 to 5 μm.
[0099]
Conventionally, when an intermediate layer having a relatively low resistance has been used using an ion conductive resin, the resistance further decreases under high temperature and high humidity, and the intermediate layer no longer serves as a charge blocking layer. Most of that was.
[0100]
In the present invention, the volume resistivity of the intermediate layer under high temperature and high humidity is 1 × 10 ¹² Since a binder material having a resistance of Ω · cm or more can be selected, the function as a charge blocking layer is not lost even when used under high humidity.
[0101]
Next, the photosensitive layer of the electrophotographic photosensitive member of the present invention will be described.
[0102]
The constitution of the photosensitive layer of the present invention is a single layer containing both a charge generating substance and a charge transporting substance in the same layer, and a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance. It is roughly divided into the laminated type having.
[0103]
First, an electrophotographic photosensitive member having a laminated photosensitive layer will be described.
[0104]
As the constitution of the laminated type photosensitive layer, a charge generation layer and a charge transport layer are laminated on a support in this order (normal layer type), and a charge transport layer and a charge generation layer are laminated in this order (reverse). Layer type). From the viewpoint of electrophotographic characteristics, a forward layer type is preferable.
[0105]
The charge generation layer is an azo pigment such as Sudan Red and Diane Blue, a quinone pigment such as pyrene, quinone and anthantrone, a quinocyanine pigment, a perylene pigment, an indigo pigment such as indigo and thioindigo, and an oxytitanium phthalocyanine. Gallium phthalocyanine, a charge-generating substance such as a phthalocyanine pigment such as silicone phthalocyanine is dispersed in a binder resin such as polyvinyl butyral, polystyrene and polyvinyl acetate and an acrylic resin, and then dried or vacuum-evaporated. It forms by doing.
[0106]
Among the charge-generating substances, among those listed above, they have very favorable characteristics of high sensitivity, but a large number of minute black spots are generated in a high-humidity environment, and black spot fog that becomes an image close to ground fog is generated. Phenomenon is likely to occur, it is suitable for the phthalocyanine pigments that tend to select the substrate because there may be restrictions on the use condition, furthermore, gallium phthalocyanine such as hydroxygallium phthalocyanine and chlorogallium phthalocyanine, and oxytitanium phthalocyanine are more preferable. preferable.
[0107]
The thickness of the charge generation layer is preferably 5 μm or less, more preferably 0.01 to 3 μm.
[0108]
The charge transport layer is a polycyclic aromatic compound having a structure such as biphenylene, anthracene, pyrene and phenanthrene in the main chain or side chain, a nitrogen-containing ring compound such as indole, carbazole, oxadiazole and pyrazoline, and a hydrazone compound. It is formed by applying a solution in which a charge transport material such as a styryl compound is dissolved in a binder resin having film forming properties, and drying the solution.
[0109]
Examples of the binder resin having a film forming property include polyester, polycarbonate, polystyrene, polymethacrylate, and polyarylate.
[0110]
The thickness of the charge transport layer is preferably 5 to 40 μm, more preferably 8 to 30 μm.
[0111]
The single-layer type photosensitive layer is formed by applying a solution in which the charge generation material and the charge transport material are dispersed and dissolved in the binder resin, and drying the solution.
[0112]
The thickness of the photosensitive layer is preferably 5 to 40 μm, more preferably 10 to 30 μm.
[0113]
The photosensitive layer of the electrophotographic photoreceptor of the present invention preferably contains the above-mentioned electron transporting substance.
[0114]
It is considered that the addition of the electron transporting substance to the photosensitive layer facilitates the transfer of electrons from the photosensitive layer to the intermediate layer at the interface between the photosensitive layer and the intermediate layer.
[0115]
Therefore, when the electron transporting substance is added to the photosensitive layer, it is preferable to add the electron transporting substance to the layer in contact with the intermediate layer at the interface. For example, when the intermediate layer, the charge generation layer, and the charge transport layer are laminated in this order from the support side, it is preferable to add an electron transport material to the charge generation layer.
[0116]
The electron transporting substance added to the photosensitive layer is more preferably the same as the electron transporting substance used for the intermediate layer, in that charge transfer between the layers is smoothly performed.
[0117]
In the present invention, a protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer.
[0118]
Examples of the material constituting the protective layer include polyester, polyacrylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, polyamideimide, polysulfone, polyacrylether, polyacetal, phenol, acrylic, silicone, epoxy, urea, and allyl. Alkyd, butyral, phenoxy, phosphazene, acrylic-modified epoxy, acrylic-modified urethane, and acrylic-modified polyester resin.
[0119]
The thickness of the protective layer is preferably from 0.2 to 10 μm.
[0120]
Each of the above layers includes polytetrafluoroethylene, polyvinylidene fluoride, a fluorine-based graft polymer, a silicone-based graft polymer, a fluorine-based block polymer, a silicone-based block polymer, and a silicone-based polymer to improve cleaning properties and abrasion resistance. A lubricant such as a system oil may be contained.
[0121]
Further, additives such as an antioxidant may be added for the purpose of improving weather resistance.
[0122]
Further, a conductive powder such as conductive tin oxide and conductive titanium oxide may be dispersed in the protective layer for the purpose of resistance control.
[0123]
FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.
[0124]
In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around an axis 2 in a direction of an arrow at a predetermined peripheral speed.
[0125]
In the rotation process, the electrophotographic photoreceptor 1 receives a uniform charge of a predetermined positive or negative potential on its peripheral surface by a (primary) charging unit 3, and then exposes an exposure unit (not shown) such as a slit exposure or a laser beam scanning exposure. ) Is received. Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1.
[0126]
The formed electrostatic latent image is then developed with toner by a developing unit 5, and the developed toner developed image is transferred between an electrophotographic photosensitive member 1 and a transfer unit 6 from a paper feeding unit (not shown). The image is sequentially transferred by the transfer unit 6 to the transfer material 7 taken out and fed in synchronization with the rotation of the first rotation.
[0127]
The transfer material 7 having undergone the image transfer is separated from the electrophotographic photosensitive member surface, introduced into the fixing means 8 and subjected to image fixing, thereby being printed out of the apparatus as a copy.
[0128]
The surface of the electrophotographic photoreceptor 1 after the image transfer is cleaned and cleaned by removing the untransferred toner by a cleaning unit 9 and further subjected to a static elimination process by a pre-exposure light 10 from a pre-exposure unit (not shown). , Is repeatedly used for image formation.
[0129]
The charging unit 3 may be a scorotron charger or corotron charger using corona discharge, or may be a contact-type charger (contact charging unit) using a known form such as a roller shape, a blade shape, or a brush shape. . As a material of a member of the contact type charger, an elastic body having conductivity is generally used.
[0130]
The voltage applied to the contact charging member may be a DC voltage alone or an oscillating voltage obtained by superimposing an AC voltage on a DC voltage.
[0131]
The oscillating voltage here is a voltage whose voltage value changes periodically with time, and the AC voltage has a peak-to-peak voltage that is twice or more the charging start voltage of the electrophotographic photosensitive member when only the DC voltage is applied. Is preferred.
[0132]
When contact charging means is used, pre-exposure is not always necessary.
[0133]
In the present invention, a plurality of components such as the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, and the cleaning unit 9 are integrally connected as a process cartridge. It may be configured to be detachable from the main body of an electrophotographic apparatus such as a copying machine or a laser beam printer.
[0134]
For example, at least one of the charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported with the electrophotographic photosensitive member 1 to form a cartridge, and is detachably attached to the apparatus main body by using a guide unit such as the rail 12 of the apparatus main body. Process cartridge 11.
[0135]
When the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is reflected light or transmitted light from the original, or the original is read by a sensor and converted into a signal. Light emitted by scanning, driving of an LED array, driving of a liquid crystal shutter array, and the like.
[0136]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples.
[0137]
(Example 1)
Prepare a JIS standard A3003 aluminum alloy processed into a cylinder by porthole extrusion, mirror cut the outer surface of this cylinder with a diamond bite, outer diameter 29.92 mm, inner diameter 28.5 mm, length 260.5 mm, the value of the ten-point average surface roughness Rz of the outer surface was set to 0.1 μm, and the support was further mixed with alumina beads and water by a liquid honing method using spherical alumina beads having a diameter of 20 μm and water. The resultant was discharged onto the surface of a cylinder to roughen the surface, thereby obtaining a support for an electrophotographic photosensitive member having a surface Rz value of 0.48 μm.
[0138]
On this support, 10 parts by mass of a mixture of two kinds of materials having the structures represented by the following formulas (17-1) and (17-2) was mixed with N-methyl-2-pyrrolidone and cyclohexanone at a mixing ratio of 1: The solution obtained by adding 90 parts by mass of the mixed solvent of No. 2 was applied by dip coating, dried at a temperature of 150 ° C. for 30 minutes, and contained an imide resin having a repeating structural unit represented by the following formula (2-3). An intermediate layer having a thickness of 1 μm was formed.
[0139]
[Outside 37]

(17-1)
[0140]
[Outside 38]

(17-2)
[0141]
[Outside 39]

(17-3)
(I, m and n represent a positive integer.)
[0142]
Next, a mixture of 6 parts by mass of a hydroxygallium phthalocyanine pigment, 3 parts by mass of a polyvinyl butyral resin (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 40 parts by mass of cyclohexanone was placed on the intermediate layer by a sand mill. After dispersion for an hour, 60 parts by mass of tetrahydrofuran is added to prepare a dispersion for the charge generation layer, dip-coated on the intermediate layer, and further dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.1 μm. Formed.
[0143]
Next, a solution obtained by dissolving 50 parts by mass of a triarylamine compound represented by the following formula (3) and 50 parts by mass of a bisphenol Z-type polycarbonate resin in 400 parts by mass of monochlorobenzene is dip-coated on the charge generation layer, The film was heated and dried in an atmosphere at 110 ° C. for 1 hour to form a charge transport layer having a thickness of 17 μm, thereby producing an electrophotographic photosensitive member.
[0144]
[Outside 40]

(18)
[0145]
(Examples 2 to 5)
In Example 1, by changing the discharge pressure at the time of liquid honing, cylinder supports having values of ten-point average roughness Rz of the surface of 0.6 μm, 1.0 μm, 1.5 μm, and 2.0 μm were produced. An intermediate layer and a photosensitive layer similar to those in Example 1 were formed on the surface of Example 1.
[0146]
These are referred to as Examples 2, 3, 4, and 5 in ascending order of surface roughness.
[0147]
(Comparative Examples 1 and 2)
An electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the discharge pressure during honing was changed to set the surface roughness Rz of the support to 0.4 μm and 2.1 μm. .
[0148]
These were designated as Comparative Examples 1 and 2 in order.
[0149]
(Examples 6 to 11)
In Example 3, the thickness of the intermediate layer was set to 0.2 μm, 0.3 μm, 0.6 μm, 2.0 μm, 3.0 μm, and 5.0 μm, and these were designated as Examples 6 to 11, respectively.
[0150]
(Comparative Examples 3 and 4)
Comparative examples 3 and 4 in which the thickness of the intermediate layer was set to 0.1 μm and 6.0 μm in Example 3 were set in order.
[0151]
(Examples 12 to 16)
In Examples 1 to 5, an intermediate layer paint composed of 4 parts of a phenol resin, 2 parts of Compound Example (1-1), 50 parts of methoxypropanol, 50 parts of benzyl alcohol, and 10 parts of methanol was prepared and applied on a support. After drying at 145 ° C. for 20 minutes, an intermediate layer having a thickness of 1.0 μm was formed.
[0152]
A photosensitive layer was formed on this intermediate layer in the same manner as in Examples 1 to 5 to obtain an electrophotographic photosensitive member.
[0153]
These were named Examples 12 to 16 in order.
[0154]
(Examples 17 to 29)
In Example 14, as the electron transporting substance used for the intermediate layer, (1-3), (1-10), (1-19), (1-26), Using (1-35), (1-48), (2-1), (2-10), (2-25), (2-40), (3), (7), (11) Those having the intermediate layer formed thereon were Examples 17 to 29 in this order.
[0155]
(Comparative Examples 5 to 9)
In each of Examples 1 to 5, a solution obtained by dissolving an alcohol-soluble polyamide resin in a mixed solvent of methanol and butanol in a 3: 1 mixture of methanol and butanol instead of a polyimide resin as an intermediate layer was applied on a support by a dipping method, and then heated to 100 ° C. Comparative examples 5 to 9 were made in the same manner as in Examples 1 to 5 except that the film was dried at a temperature for 10 minutes to a thickness of 1.0 μm.
[0156]
(Comparative Examples 10 to 23)
In Examples 14 and 17 to 29, Comparative Examples 10 to 23 were made by changing the baphenol resin of the intermediate layer to an alcohol-soluble polyamide resin.
[0157]
Each of the electrophotographic photoreceptors of Examples 1 to 29 and Comparative Examples 1 to 23 manufactured in this manner was converted from a commercially available laser beam printer (trade name: LaserJet 4000, manufactured by Hewlett-Packard Japan Co., Ltd.). (Variable in the amount of laser light and charging potential), and charged so that the dark part potential (VD) becomes -700 V, and irradiate the laser light with an emission wavelength λ of 800 nm to make the bright part potential (VL) -150 V. The amount of light required for the measurement was measured and defined as sensitivity.
[0158]
The surface potential of the electrophotographic photoreceptor was measured by extracting the developing cartridge from the evaluator and inserting a potential measuring device therein. The potential measuring device is configured by disposing a potential measuring probe at a developing position of a developing cartridge, and the position of the potential measuring probe with respect to the electrophotographic photosensitive member is set at the center in the drum axis direction.
[0159]
All measurements were performed in an environment in which the temperature was 25 ° C. and the relative humidity was 50%. The electrophotographic photoreceptor used was left in the measurement environment 24 hours before the measurement.
[0160]
Further, 1 μJ / cm ² Was measured as the residual potential Vr.
[0161]
Further, the bright portion potential was measured in a state where the electrophotographic photoreceptor was left in an environment of 30 ° C. and 80% Rh for 24 hours or more. At the same time, a solid white image was produced.
[0162]
Further, the variation amounts ΔVD and ΔVL of the dark portion potential and the bright portion potential from the initial stage after 5,000 repeated image output durability tests were performed in a normal temperature and normal humidity environment.
[0163]
Further, a layer (for volume resistivity evaluation) similar to the intermediate layer of this electrophotographic photoreceptor was prepared, and left standing at 30 ° C. and 80% Rh for 24 hours, using a comb-shaped electrode. Then, a voltage of 10 V was applied to measure the volume resistivity.
[0164]
The evaluation results are shown in Tables 2 and 3.
[0165]
[Table 2]

[0166]
[Table 3]

[0167]
Next, when the interference fringes and the image ghosts when images were produced for Examples 1 to 16 and Comparative Examples 1 to 9 were examined, the results are as shown in Table 4.
[0168]
In the ghost evaluation, after printing an image having a black square (■) of 5 mm × 5 mm square and a black circle (●) of 5 mm diameter, a halftone image is continuously printed, and a black square and a black circle image are added to the halftone image. This was done by comparing whether the afterimages were printed on top of each other.
[0169]
[Table 4]

[0170]
As can be seen from the above results, in the example, a photosensitive member having good potential stability and good image was obtained, but in the comparative example, there was some problem in sensitivity, residual potential, potential stability or image characteristics. It can be seen that this has occurred.
[0171]
(Examples 30 to 35)
In Example 1, the discharge pressure at the time of honing the support was changed, and the values of the ten-point average roughness Rz of the outer diameter surface of the cylinder support were changed to 0.24 μm, 0.3 μm, 0.6 μm, and 0.1 μm. Thicknesses of 8 μm and 1.0 μm were prepared.
[0172]
On such a support, a polyimide resin having a repeating structural unit represented by the following formula (19) was formed to a thickness of 1 μm in the same manner as in Example 1 to form an intermediate layer.
[0173]
[Outside 41]

(19)
n is a positive integer.
[0174]
Further, a photosensitive layer similar to that of Example 1 was formed thereon, and Examples 30 to 34 were formed in ascending order of surface roughness.
[0175]
(Examples 36 to 38)
In Example 32, Examples 35 to 38 in which the thickness of the intermediate layer was 0.3 μm, 0.6 μm, 3.0 μm, and 5.0 μm were set in this order.
[0176]
(Comparative Examples 24-28)
In Example 30, Comparative Examples 24 and 25 in which the values of the outer diameter surface roughness Rz of the aluminum support were 0.2 μm and 1.1 μm, respectively, were used.
[0177]
In Example 32, Comparative Examples 26 and 27 in which the thickness of the intermediate layer was 0.1 μm and 6.0 μm, respectively, were used.
[0178]
Further, in Example 32, the intermediate layer was made of an alcohol-soluble polyamide having a film thickness of 1.0 μm in the same manner as in Comparative Example 5 to make Comparative Example 28.
[0179]
Then, a commercially available laser beam printer (trade name: LaserJet 4000, manufactured by Hewlett-Packard Japan Co., Ltd.) was modified (variable in laser light amount and charging potential) by a commercially available semiconductor diode laser having an emission wavelength λ of 400 nm. Examples 30 to 39 and Comparative Examples 24 to 28 were evaluated using an evaluator equipped with Nichia Corporation.
[0180]
Tables 5 and 6 show the evaluation results.
[0181]
[Table 5]

[0182]
[Table 6]

[0183]
From the above evaluations, it can be seen that the electrophotographic photosensitive member having good characteristics was obtained in the example, but the electrophotographic photosensitive member of the comparative example had inconvenience in any of the items.
[0184]
【The invention's effect】
As described above, according to the present invention, an electrostatic latent image is formed on the surface by a semiconductor laser. An electrophotographic photosensitive member having electrophotographic characteristics, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus can be provided.
[Brief description of the drawings]
FIG. 1 is an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member of the present invention.
[Explanation of symbols]
1. Electrophotographic photoreceptor
2 axes
3 Charging means
4 Exposure light
5 Developing means
6 transfer means
7 Transfer material
8 Fixing means
9 Cleaning means
10 Pre-exposure light
11 Process cartridge
12 rails

Claims (14)

An electrophotographic photosensitive member having an intermediate layer and a photosensitive layer in this order on a support, and the photosensitive layer contains a charge generating substance and a charge transporting substance. An electrostatic latent image is formed on the surface by a semiconductor laser. In electrophotographic photoreceptors,
The intermediate layer contains an electron transport material,
The volume resistivity of the intermediate layer under an environment of 30 ° C. and 80% RH is 1 × 10 ¹² Ω · cm or more;
The ratio (Rz / λ) of the ten-point average roughness (Rz) of the surface of the support on the photosensitive layer side to the wavelength (λ) of the semiconductor laser is 0.6 or more and 2.5 or less. An electrophotographic photosensitive member comprising: The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer contains an electron transporting substance. The photosensitive layer is a laminated photosensitive layer having a charge generation layer containing the charge generation substance and a charge transport layer containing the charge transport substance in order from the support side, and the charge generation layer contains the electron transport substance. The electrophotographic photosensitive member according to claim 2. 4. The electrophotographic photoreceptor according to claim 2, wherein the electron transporting substance contained in the intermediate layer and the electron transporting substance contained in the photosensitive layer are the same. The electrophotographic photoreceptor according to claim 1, wherein the intermediate layer has a thickness of 0.3 to 5 μm. The electrophotographic photosensitive member according to any one of claims 1 to 5, wherein the electron transporting substance contained in the intermediate layer is an organic pigment, and the intermediate layer is a layer in which the organic pigment is dispersed in a binder resin. body. The electrophotographic photoreceptor according to claim 6, wherein the binder resin contained in the intermediate layer is a thermosetting resin. The electrophotographic photosensitive member according to claim 6, wherein the binder resin contained in the intermediate layer is an organic solvent-soluble thermoplastic resin. The electrophotographic photosensitive member according to claim 1, wherein the electron transporting substance contained in the intermediate layer is an electron transporting resin, and the electron transporting resin is a binder resin of the intermediate layer. The electrophotographic photoreceptor according to claim 1, wherein the charge generating substance is a phthalocyanine pigment. The electrophotographic photoreceptor according to claim 10, wherein the phthalocyanine pigment is gallium phthalocyanine. The electrophotographic photosensitive member according to claim 10, wherein the phthalocyanine pigment is oxytitanium phthalocyanine. An electrophotographic photosensitive member and at least one unit selected from the group consisting of a charging unit, a developing unit, a transfer unit, and a cleaning unit are integrally supported, and the process cartridge is detachable from the electrophotographic apparatus main body.
The electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 1 to 12,
A process cartridge, wherein the electrophotographic apparatus is an electrophotographic apparatus having an exposure unit for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member by using a semiconductor laser. In an electrophotographic apparatus having an electrophotographic photosensitive member, a charging unit, an exposing unit, a developing unit, and a transferring unit,
The electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 1 to 12,
An electrophotographic apparatus, wherein the exposing means is means for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member using a semiconductor laser.

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