JP3792909B2

JP3792909B2 - Electrophotographic photosensitive member, process cartridge having the electrophotographic photosensitive member, and electrophotographic apparatus

Info

Publication number: JP3792909B2
Application number: JP25334598A
Authority: JP
Inventors: 正人田中; 浩一中田
Original assignee: Canon Inc
Current assignee: Canon Inc
Priority date: 1998-08-25
Filing date: 1998-08-25
Publication date: 2006-07-05
Anticipated expiration: 2018-08-25
Also published as: JP2000066423A

Description

【０００１】
【発明の属する技術分野】
本発明は電子写真感光体並びに該電子写真感光体を備えたプロセスカ−トリッジ及び電子写真装置に関する。
【０００２】
【従来の技術】
有機光導電体を用いた電子写真感光体は、電荷輸送材料を含有する電荷輸送層と電荷発生材料を含有する電荷発生層を積層した機能分離方電子写真感光体の開発により、感度・耐久性において著しい改善がなされ実用化されるようになってきた。
【０００３】
一方、近年、複写機にレ−ザ−光による書き込み機能を持たせる等の目的で、可視域から赤外レ−ザ−波長域まで幅広い分光感度を有する感光体の開発が盛んである。こうした目的を達成する方法として、可視光域に感度を有する電荷発生材料と赤外域に感度を有する電荷発生材料を混合あるいは積層した電荷発生層を用いる方法が知られている。
【０００４】
また、端末用プリンタ−として電子写真技術を応用したプリンタ−が広く普及している。これ等は主としてレ−ザ−光を光源とするレ−ザ−ビ−ムプリンタ−であり、その光源としてはコスト、装置の大きさ等の点から半導体レ−ザ−が用いられる。現在、主として用いられている半導体レ−ザ−はその発振波長が７９０〜８２０ｎｍと長波長のため、これ等長波長の光に十分な感度を有する電子写真感光体の開発が進められており、感度、耐久性の改良のために電荷発生材料を混合あるいは積層した電荷発生層を用いる方法が知られている。
【０００５】
例えば、アゾ化合物とフタロシアニン化合物との組み合わせについては、特願平７−１７５２４１号公報に特定アゾ顔料とチタニルフタロシアニンを組み合わせる感光体、特開平７−１２８８８８号公報にアゾ化合物とガリウムフタロシアニンを組み合わせる感光体が開示されている。
【０００６】
しかしながら、こうした感光体においては、各々の電荷発生材料の特性が十分に発揮されなかったり、特に混合使用した場合、メモリ−特性の悪化に伴い耐久時の電位変動が大きくなるという欠点を有しており、ガリウムフタロシアニン化合物を用いた場合は、帯電能が悪く、ポチ、かぶりによる画像劣化が見られた。また、可視域及び赤外線緒感度自体も十分なものとは言えなかった。
【０００７】
【発明が解決しようとする課題】
本発明の目的は、従来の前記欠点を改善し、高感度、高画質で耐久時の電位変動の少ない電子写真感光体を提供することである。また該電子写真感光体を用いたプロセスカ−トリッジ並びに電子写真装置を提供することである。
【０００８】
【課題を解決するための手段】
本発明は、導電性支持体上に感光層を有する電子写真感光体において、該感光層が電荷発生層と電荷輸送層とを含み、該電荷発生層が、ヒドロキシガリウムフタロシアニンと下記一般式（１）で表わされるジスアゾ顔料とを混合状態で含有することを特徴とする電子写真感光体構成される。
一般式（１）
【外５】

式中、Ａ１はフェノ−ル性水酸基を有するカプラ−残基を表わし、Ｒ１及びＲ２は水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリ−ル基、置換基を有してもよいアラルキル基または置換基を有してもよい複素環基を表わし、Ｒ１、Ｒ２は共に窒素原子と結合して窒素原子を環内に含む環状アミノ基を形成してもよい。Ｘはベンゼン環と縮合して置換基を有してもよい多環芳香環または置換基を有してもよい複素環を形成するのに必要な残基を表わし、Ｚは酸素原子または硫黄原子を表わし、ｐは０または１の整数を表わす。
【０００９】
また、本発明は、前記本発明の電子写真感光体、及び帯電手段、現像手段及びクリ−ニング手段からなる群より選ばれる少なくとも一つの手段を一体に支持し、電子写真装置本体に着脱自在であることを特徴とするプロセスカ−トリッジから構成される。
【００１０】
また、本発明は、前記本発明の電子写真感光体、帯電手段、像露光手段、現像手段及び転写手段を有することを特徴とする電子写真装置から構成される。
【００１１】
【発明の実施の形態】
前記一般式（１）中、Ａ₁ 及びＡ₂ の好ましい例としては、下記一般式（４）〜（８）で表わされるカプラ−残基が挙げられる。
一般式（４）
【化６】

一般式（５）
【化７】

一般式（６）
【化８】

一般式（７）
【化９】

一般式（８）
【化１０】

【００１２】
一般式（１）、（４）、（５）及び（６）中、Ｘはベンゼン環と縮合して置換基を有してもよいナフタレン環、置換基を有してもよいアントラセン環、置換基を有してもよいカルバゾ−ル環、置換基を有してもよいベンズカルバゾ−ル環、置換基を有してもよいジベンゾフラン環等の多環芳香環または複素環を形成するのに必要な残基を表わす。
【００１３】
一般式（８）中、Ｙは置換基を有してもよい２価の芳香族炭化水素基ないしは窒素原子を環内に含む２価の複素環基を表わし、具体的には、ｏ−フェニレン、ｏ−ナフチレン、ペリナフチレン、１，２−アンスリレン、３，４−ピラゾ−ルジイル、２，３−ピリジンジイル、４，５−ピリジンジイル、６，７−インダゾ−ルジイル、６，７−キノリンジイル等の基が挙げられる。
【００１４】
一般式（１）、（４）及び（５）中、Ｒ₁ 及びＲ₂ は水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリ−ル基、置換基を有してもよいアラルキル基または置換基を有してもよい複素環基を表わし、Ｒ、Ｒ₂ は共に窒素原子と結合して窒素原子を環内に含む環状アミノ基を形成してもよい。
【００１５】
一般式（６）中、Ｒ₄ は水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリ−ル基、置換基を有してもよいアラルキル基または置換基を有してもよい複素環基を表わす。
【００１６】
一般式（７）中、Ｒ₅ は置換基を有してもよいアルキル基、置換基を有してもよいアリ−ル基、置換基を有してもよいアラルキル基または置換基を有してもよい複素環基を表わす。
【００１７】
前記表現のアルキル基としてはメチル、エチル、プロピル等の基、アリ−ル基としてはフェニル、ナフチル、アンスリル等の基、アラルキル基としてはベンジル、フェネチル等の基、複素環基としてはピリジル、チエニル、チアゾリル、カルバゾリル、ベンゾイミダゾリル、ベンゾチアゾリル等の基が挙げられ、窒素原子を環内に含む環状アミノ基としてはピロ−ル、ピロリン、ピロリジン、ピロリドン、インド−ル、インドリン、カルバゾ−ル、イミダゾ−ル、ピラゾ−ル、ピラゾリン、オキサジン、フェノキサジン等の基が挙げられる。
【００１８】
また、置換基としては、メチル、エチル、プロピル、ブチル等のアルキル基、メトキシ、エトキシ、プロポキシ等のアルコキシ基、フッ素原子、塩素原子、臭素原子等のハロゲン原子、ジメチルアミノ、ジエチルアミノ等のジアルキルアミノ基、フェニルカルバモイル基、ニトロ基、シアノ基、トリフルオロメチル等のハロメチル基等が挙げられる。
【００１９】
一般式（４）中、Ｚは酸素原子または硫黄原子を表わし、ｐは０または１の整数を表わす。
【００２０】
表１〜５に一般式（１）で表わされるジスアゾ顔料の代表例を列挙するが、該顔料はこれ等に限定されるものではない。
【００２１】
【表１】

【表２】

【表３】

【表４】

【表５】

【００２２】
一般式（１）で表わされるジスアゾ顔料は、相当するジアミンを常法によりテトラゾ化し、アルカリの存在下、カプラ−と水系でカップリングするか、または前記ジアミンのテトラゾニウム塩をホウフッ化塩あるいは塩化亜鉛複塩等の形で一旦単離した後、適当な溶剤、例えばＮ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド等の溶剤中で酢酸ソ−ダ、トリエチルアミン、Ｎ−メチルモルホリン等の塩基の存在下、前記カプラ−とカップリングすることにより容易に合成できる。
【００２３】
次に、本発明において用いられるヒドロキシガリウムフタロシアニン（以下、ＨＯＧａＰｃと称す）の一般式を示す。
【化１１】

式中、Ｘ₁ 、Ｘ₂ 、Ｘ₃ 及びＸ₄ は、ＣｌまたはＢｒを表わし、ｎ，ｍ，ｋ及びｊは０〜４の整数である。
【００２４】
本発明においては、いかなる結晶形のＨＯＧａＰｃも使用できるが、ＣｕＫαのＸ線回折におけるブラッグ角２θ±０．２°が７．４°、２８．２°に強いピ−クを有する結晶のＨＯＧａＰｃが高感度で、本発明において有効に作用し特に好ましい。
【００２５】
本発明によれば可視光域に高い感度を示す前記一般式（１）で表わされるジスアゾ顔料と赤外レ−ザ−域の高い感度を示すＨＯＧａＰｃを共に電荷発生物質として含有することから、可視光域から赤外域の光に対して効率よく電荷を発生することができる。
【００２６】
本発明において、ＨＯＧａＰｃと前記特定のジスアゾ顔料の含有比は好ましくは２０／１〜１／２０、更に好ましくは１０／１〜１／５に設定される。
【００２７】
感光層を形成するに当たって、電荷発生材料を混合する場合は、各材料を上記範囲の比率で適当な結着樹脂と溶剤に分散するか、あるいは個々に分散した液を所定の比率になるように混合する。個々に分散する場合、結着樹脂や溶剤はそれぞれ異なっても差し支えない。積層する場合は個々に分散した液を、含まれる材料の量が所定の比率になるような膜厚で各々塗布する。
【００２８】
ここで用いられる結着樹脂としては、例えば、ポリエステル、アクリル樹脂、ポリビニルカルバゾ−ル、フェノキシ樹脂、ポリカ−ボネ−ト、ポリビニルブチラ−ル、ポリビニルベンザ−ル、ポリスチレン、ポリビニルアセテ−ト、ポリスルホン、ポリアリレ−ト、塩化ビニリデン・アクリロニトリル共重合体等が主として挙げられる。
【００２９】
本発明の電子写真感光体の構成は、電荷発生層と電荷輸送層との積層型、あるいは電荷発生材料と電荷輸送材料とが混在する単層型の両者が適用される。更に積層型の場合、積層の順序が２通りあるが、そのうち、支持体側から電荷発生層、電荷輸送層の順で積層する構成が一般的である。その構成を例にとって電子写真感光体の態様を説明する。
【００３０】
導電性支持体としては導電性を有するものであれば良く、アルミニウム、ステンレス等の金属あるいは導電層を設けた金属、プラスチック、紙等が挙げられ、形状としては円筒状またはフィルム状等が挙げられる。
【００３１】
また、導電性支持体と感光層との間に、バリヤ−機能と接着機能を持つ下引き層を設けることもできる。下引き層の材料としてはポリビニルアルコ−ル、ポリエチレンオキシド、エチルセルロ−ス、メチルセルロ−ス、カゼイン、ポリアミド、にかわ、ゼラチン等が用いられる。これ等は、適当な溶剤に溶解して導電性支持体上に塗布される。
【００３２】
更に、支持体と下引き層との間に、支持体のむらや欠陥の被覆及び画像入力がレ−ザ−光の場合には散乱による干渉縞防止を目的とした導電層を設けることが好適である。これはカ−ボンブラック、金属粒子、金属酸化物等の導電性粉体を結着樹脂中に分散して形成することができる。導電層の膜厚は５〜４０μｍ、好ましくは１０〜３０μｍが適当である。
【００３３】
電荷輸送層は、主として電荷輸送材料と結着樹脂とを溶剤中に溶解させた塗料を塗工乾燥して形成する。用いられる電荷輸送材料としては、各種のトリアリ−ルアミン系化合物、ヒドラゾン系化合物、スチルベンゼン系化合物、ピラゾリン系化合物、オキサゾ−ル系化合物、チアゾ−ル系化合物、トリアリルメタン系化合物等が挙げられる。結着樹脂としては電荷発生層に用いたと同様の樹脂を用いることができる。
【００３４】
これ等の感光層の塗布方法としては、浸漬コ−ティング法、スプレ−コ−ティング法、スピンナ−コ−ティング法、ビ−ドコ−ティング法、ブレ−ドコ−ティング法、ビ−ムコ−ティング法等の方法を用いることができる。
【００３５】
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−ザ−ビ−ムプリンタ−、ＣＲＴプリンタ−、ＬＥＤプリンタ−、液晶プリンタ−、レ−ザ−製版等電子写真応用分野にも広く利用することができる。
【００３６】
次に、本発明のプロセスカ−トリッジ並びに電子写真装置について説明する。図５に本発明の電子写真感光体を有するプロセスカ−トリッジを有する電子写真装置の概略構成を示す。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。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−ザ−ビ−ム走査露光等の像露光手段（不図示）からの画像露光光４を受ける。こうして感光体１の周面に静電潜像が順次形成されていく。
【００３７】
形成された静電潜像は、次いで現像手段５によりトナ−現像され、現像されたトナ−現像像は、不図示の給紙部から感光体１と転写手段６との間に感光体１の回転と同期取りされて給送された転写材７に、転写手段６により順次転写されていく。像転写を受けた転写材７は感光体面から分離されて像定着手段８へ導入されて像定着を受けることにより複写物（コピ−）として装置外へプリントアウトされる。像転写後の感光体１の表面は、クリ−ニング手段９によって転写残りトナ−の除去を受けて清浄面化され、更に前露光手段（不図示）からの前露光光１０により除電処理がされた後、繰り返し画像形成に使用される。なお、一次帯電手段３が帯電ロ−ラ−等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。
【００３８】
本発明においては、上述の感光体１、一次帯電手段３、現像手段５及びクリ−ニング手段９等の構成要素のうち、複数のものをプロセスカ−トリッジとして一体に結合して構成し、このプロセスカ−トリッジを複写機やレ−ザ−ビ−ムプリンタ−等の電子写真装置本体に対して着脱可能に構成してもよい。例えば一次帯電手段３、現像手段５及びクリ−ニング手段９の少なくとも１つを感光体１と共に一体に支持してカ−トリッジ化し、装置本体のレ−ル１２等の案内手段を用いて装置本体に着脱可能なプロセスカ−トリッジ１１とすることができる。また、画像露光光４は、電子写真装置が複写機やプリンタ−である場合には、原稿からの反射光や透過光を用いる、あるいは、センサ−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−ザ−ビ−ムの走査、ＬＥＤアレイの駆動及び液晶シャッタ−アレイの駆動等により照射される光である。
【００３９】
次に本発明において用いるＨＯＧａＰｃの製造例を挙げる。
製造例１
ｏ−フタロジニトリル７３ｇ、三塩化ガリウム２５ｇ、α−クロルナフタレン４００ｍｌを窒素雰囲気下、２００℃で４時間反応させた後、１３０℃で生成物をろ過した。得られた生成物をＮ，Ｎ−ジメチルホルムアミドを用いて１３０℃で１時間分散洗浄した後、ろ過し、メタノ−ルで洗浄後乾燥し、クロロガリウムフタロシアニンを４５ｇ得た。この化合物の元素分析値を示す。

【００４０】
ここで得られたクロロガリウムフタロシアニン１５ｇを１０℃の濃硫酸４５０ｇに溶解させ、氷水２３００ｇ中に撹拌下に滴下して再析出させてろ過した。２％アンモニア水で分散洗浄後、イオン交換水で十分に水洗した後、ろ別、乾燥して低結晶性のＨＯＧａＰｃを１３ｇ得た。
【００４１】
製造例２
製造例１で得られたＨＯＧａＰｃを１０ｇ、Ｎ，Ｎージメチルホルムアミド３００ｇを１ｍｍφのガラスビ−ズ４５０ｇと共にミリング処理を室温（２２℃）下、６時間行った。この分散液により固形分を取り出し、メタノ−ル、次いで水で十分に洗浄、乾燥してＨＯＧａＰｃを９．２ｇ得た。このＨＯＧａＰｃのＸ線回折における回折角２θ±０．２°は７．４°、２８．２°に強いピ−クを有していた（図１）。この化合物の元素分析値を示す。

【００４２】
製造例３
製造例１で得られたＨＯＧａＰｃを１０ｇ、テトラヒドロフラン３００ｇを１ｍｍφのガラスビ−ズ４５０ｇと共にミリング処理を室温（２２℃）下、２０時間行った。この分散液により固形分を取り出し、メタノ−ル、次いで水で十分に洗浄、乾燥してＨＯＧａＰｃを９．２ｇ得た。このＨＯＧａＰｃのＸ線回折における回折角２θ±０．２°は７．４°、２８．２°に強いピ−クを有していた（図２）。この化合物の元素分析値を示す。

【００４３】
製造例４
製造例１で得られたＨＯＧａＰｃを１０ｇ、Ｎ，Ｎージメチルアニリン３００ｇを１ｍｍφのガラスビ−ズ４５０ｇと共にミリング処理を室温（２２℃）下、６時間行った。この分散液により固形分を取り出し、メタノ−ル、次いで水で十分に洗浄、乾燥してＨＯＧａＰｃを９．２ｇ得た。このＨＯＧａＰｃのＸ線回折における回折角２θ±０．２°は７．６°、１６．４°、２５．０°、２６．５°に強いピ−クを有していた（図３）。
【００４４】
製造例５
製造例１で得られたＨＯＧａＰｃを１０ｇ、クロロホルム３００ｇを１ｍｍφのガラスビ−ズ４５０ｇと共にミリング処理を室温（２２℃）下、２４時間行った。この分散液により固形分を取り出し、メタノ−ル、次いで水で十分に洗浄、乾燥してＨＯＧａＰｃを９．２ｇ得た。このＨＯＧａＰｃのＸ線回折における回折角２θ±０．２°は６．９°、１６．５°、２６．７°に強いピ−クを有していた（図４）。
【００４５】
製造例６
特開昭６１−２３９２４８号公報（ＵＳＰ４，７２８，５９２）に開示されている製造例に従って、いわゆるα型といわれる結晶形のオキシチタニウムフタロシアニンを得た。
【００４６】
【実施例】
実施例１
１０％酸化アンチモンを含有する酸化スズで被覆した酸化チタン粉末５０部（重量部）、レゾ−ル型フェノ−ル樹脂２５部、メチルセロソルブ２０部、メタノ−ル５部及びシリコ−ンオイル（ポリジメチルシロキサンポリオキシアルキレン共重合体、平均分子量３０００）０．００２部を１ｍｍφのガラスビ−ズを用いたサンドミルで２時間分散して導電性塗料を調製した。
【００４７】
アルミニウムシリンダ−上に上記塗料を浸漬塗布し、１４０℃で３０分間乾燥させ、膜厚２０μｍの導電層を形成した。
【００４８】
この上に、６−６６−６１０−１２四元系ポリアミド共重合体５部をメタノ−ル７０部とブタノ−ル２５部の混合溶媒に溶解した溶液を浸漬塗布、乾燥して膜厚１μｍの下引き層を形成した。
【００４９】
次に、例示顔料８のジスアゾ顔料１部とテトラヒドロフラン５０部を１ｍｍφのガラスビ−ズを用いたサンドミルで６時間分散した後、その分散液に製造例２で得られたＨＯＧａＰｃ結晶７部とポリビニルブチラ−ル（商品名エスレックＢＸ−１、積水化学（株）製）４部をテトラヒドロフラン５０部に溶解した液を添加し、更に１時間分散した。これに１００部の酢酸ブチルを加えて、希釈した後回収して、これを下引き層上に浸漬塗布し、１００℃で１０分間乾燥して、膜厚０．３０μｍの電荷発生層を形成した。
【００５０】
次に、下記構造式の電荷輸送材料１０部
【化１２】

とビスフェノ−ルＺ型ポリカ−ボネ−ト１０部をモノクロルベンゼン６０部に溶解した溶液を調製し、電荷発生層上に浸漬塗布し、１１０℃で１時間乾燥して膜厚２５μｍの電荷輸送層を形成して電子写真感光体を作成した。
【００５１】
比較例１
実施例１において、例示顔料８に代えて下記構造式のジスアゾ顔料を用いたことの他は、実施例１と同様にして電子写真感光体を作成した。
【化１３】

【００５２】
比較例２
実施例１において用いたＨＯＧａＰｃに代えて前記製造例６で得たＴｉＯＰｃを用いたことの他は、実施例１と同様にして電子写真感光体を作成した。
【００５３】
比較例３
実施例１において、例示顔料８に代えて下記構造式のジスアゾ顔料を用いたことの他は、実施例１と同様にして電子写真感光体を作成した。
【化１４】

【００５４】
実施例１、比較例１、２及び３で作成した電子写真感光体を像露光光源としてハロゲンランプを用い、更に半導体レ−ザ−（波長７８５ｎｍ）によるイレ−ス露光手段を有する複写機（商品名ＮＰ−４８３５、キヤノン（株）製改造機）に装着し、電子写真特性を評価した。暗部電位を−６５０Ｖとした時に明部電位が１３０Ｖとなる光量、イレ−ス後電位が８０Ｖとなるレ−ザ−光量、更に１０００枚連続コピ−を行った時の表面電位の変化を測定し、結果を表６に示す。
【００５５】
【表６】

【００５６】
ここに示すように、実施例１で作成した電子写真感光体は可視光光源、赤外レ−ザ−光源共に高い感度を有していると同時に連続コピ−時の電位の安定性も十分であり、優れた特性を示す。一方、比較例の電子写真感光体においては、両光源での感度を満足しないと共に、メモリ−特性の劣化に起因する連続電位変化が大きい。
【００５７】
実施例２
実施例１において、ジスアゾ顔料とＨＯＧａＰｃとの比率を１対１とした他は、実施例１と同様にして電子写真感光体を作成した。
【００５８】
実施例３
実施例１において、ジスアゾ顔料として例示顔料２２を用い、ＨＯＧａＰｃとして製造例２で得られたＨＯＧａＰｃを用い、ジスアゾ顔料対ＨＯＧａＰｃの比率を５対１とした。また、電荷輸送材料として下記構造式のヒドラゾン化合物を用いた。その他は実施例１と同様にして電子写真感光体を作成した。
【化１５】

【００５９】
実施例４
実施例１において、製造例２で得られたＨＯＧａＰｃ結晶１部と例示顔料２３のジスアゾ顔料２部を用いた他は、実施例１と同様にして電子写真感光体を作成した。
【００６０】
実施例５
実施例１において、ＨＯＧａＰｃとして製造例３で得られたＨＯＧａＰｃを用いた他は、実施例１と同様にして電子写真感光体を作成した。
【００６１】
実施例６
実施例１において、ＨＯＧａＰｃとして製造例４で得られたＨＯＧａＰｃを用いた他は、実施例１と同様にして電子写真感光体を作成した。
【００６２】
実施例７
実施例１において、ＨＯＧａＰｃとして製造例５で得られたＨＯＧａＰｃを用いた他は、実施例１と同様にして電子写真感光体を作成した。
【００６３】
実施例８
実施例１において、電荷輸送材料として下記構造式のフルオレノン化合物を用いた他は、実施例１と同様にして電子写真感光体を作成した。
【化１６】

【００６４】
実施例９
実施例１において、電荷輸送材料として下記構造式のベンジジン化合物を用いた他は、実施例１と同様にして電子写真感光体を作成した。
【化１７】

【００６５】
【表７】

【００６６】
また、ポチ、かぶりの目視検査による画像評価で、実施例の電子写真感光体は画像欠陥のない良好な画像が得られたが、比較例の電子写真感光体は画像欠陥が見られた。
【００６７】
【発明の効果】
本発明の電子写真感光体は、可視光から赤外光までの幅広い波長域において高い感度を有し、高画質で、なお、かつ耐久時に良好な電位安定性を維持するなどの顕著な効果を奏する。また、プロセスカ−トリッジ並びに電子写真装置においても同様に顕著な効果を奏する。
【図面の簡単な説明】
【図１】製造例２で製造したヒドロキシガリウムフタロシアニンのＸ線回折図
【図２】製造例３で製造したヒドロキシガリウムフタロシアニンのＸ線回折図
【図３】製造例４で製造したヒドロキシガリウムフタロシアニンのＸ線回折図
【図４】製造例５で製造したヒドロキシガリウムフタロシアニンのＸ線回折図
【図５】本発明の電子写真感光体を有するプロセスカ−トリッジを有する電子写真装置の概略構成を示す図。
【符号の説明】
１本発明の電子写真感光体
２軸
３一次帯電手段
４画像露光光
５現像手段
６転写手段
７転写材
８像定着手段
９クリ−ニング手段
１０前露光光
１１プロセスカ−トリッジ
１２レ−ル[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotographic photoreceptor, a process cartridge and an electrophotographic apparatus provided with the electrophotographic photoreceptor.
[0002]
[Prior art]
Electrophotographic photoconductors using organic photoconductors are sensitive and durable by developing a functionally separated electrophotographic photoconductor that has a charge transport layer containing a charge transport material and a charge generation layer containing a charge generation material. In recent years, there has been a significant improvement and practical application has been made.
[0003]
On the other hand, in recent years, a photoconductor having a wide spectral sensitivity from a visible range to an infrared laser wavelength range has been actively developed for the purpose of providing a copying machine with a laser beam writing function. As a method for achieving such an object, a method using a charge generation layer obtained by mixing or laminating a charge generation material having sensitivity in the visible light region and a charge generation material having sensitivity in the infrared region is known.
[0004]
Also, printers that apply electrophotographic technology are widely used as terminal printers. These are laser beam printers mainly using laser light as a light source, and a semiconductor laser is used as the light source in terms of cost, size of the apparatus, and the like. At present, the semiconductor laser mainly used has an oscillation wavelength of 790 to 820 nm and a long wavelength. Therefore, development of an electrophotographic photosensitive member having sufficient sensitivity to light of these long wavelengths has been promoted. In order to improve sensitivity and durability, a method using a charge generation layer in which charge generation materials are mixed or laminated is known.
[0005]
For example, for a combination of an azo compound and a phthalocyanine compound, a photoconductor in which a specific azo pigment and titanyl phthalocyanine are combined in Japanese Patent Application No. 7-175241, and a photoconductor in which an azo compound and gallium phthalocyanine are combined in Japanese Patent Application Laid-Open No. 7-128888. Is disclosed.
[0006]
However, such photoconductors have the disadvantage that the characteristics of each charge generating material are not sufficiently exhibited, and particularly when used in a mixed manner, the potential fluctuation during durability increases as the memory characteristics deteriorate. When the gallium phthalocyanine compound was used, the charging ability was poor, and image deterioration due to the spots and fogging was observed. Also, the visible range and infrared sensitivity itself were not sufficient.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide an electrophotographic photosensitive member that improves the above-mentioned drawbacks and has high sensitivity, high image quality, and little potential fluctuation during durability. Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus using the electrophotographic photosensitive member.
[0008]
[Means for Solving the Problems]
The present invention relates to an electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer includes a charge generation layer and a charge transport layer, and the charge generation layer includes hydroxygallium phthalocyanine and the following general formula (1): And a disazo pigment represented by the formula (1) in a mixed state .
General formula (1)
[Outside 5]

In the formula, A1 represents a coupler residue having a phenolic hydroxyl group, R1 and R2 are a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, An aralkyl group which may have a substituent or a heterocyclic group which may have a substituent, R1 and R2 are both bonded to a nitrogen atom to form a cyclic amino group containing the nitrogen atom in the ring. Also good. X represents a residue necessary for condensing with a benzene ring to form an optionally substituted polycyclic aromatic ring or an optionally substituted heterocyclic ring, and Z represents an oxygen atom or a sulfur atom. P represents an integer of 0 or 1.
[0009]
In addition, the present invention integrally supports at least one means selected from the group consisting of the electrophotographic photosensitive member of the present invention and a charging means, a developing means and a cleaning means, and is detachable from the main body of the electrophotographic apparatus. It is composed of a process cartridge characterized by being.
[0010]
The present invention also comprises an electrophotographic apparatus comprising the electrophotographic photosensitive member of the present invention, a charging unit, an image exposing unit, a developing unit, and a transfer unit.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
In the general formula (1), preferred examples of A ₁ and A ₂ include coupler residues represented by the following general formulas (4) to (8).
General formula (4)
[Chemical 6]

General formula (5)
[Chemical 7]

General formula (6)
[Chemical 8]

General formula (7)
[Chemical 9]

General formula (8)
[Chemical Formula 10]

[0012]
In the general formulas (1), (4), (5) and (6), X is a naphthalene ring which may have a substituent by condensing with a benzene ring, an anthracene ring which may have a substituent, a substituted Necessary for forming a polycyclic aromatic ring or heterocyclic ring such as a carbazole ring which may have a group, a benzcarbazole ring which may have a substituent, a dibenzofuran ring which may have a substituent Represents a residue.
[0013]
In the general formula (8), Y represents a divalent aromatic hydrocarbon group which may have a substituent or a divalent heterocyclic group containing a nitrogen atom in the ring, specifically, o-phenylene. , O-naphthylene, perinaphthylene, 1,2-anthrylene, 3,4-pyrazoldiyl, 2,3-pyridinediyl, 4,5-pyridinediyl, 6,7-indazoldiyl, 6,7-quinolinediyl, etc. Groups.
[0014]
In general formulas (1), (4) and (5), R ₁ and R ₂ are a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an aralkyl group that may have a substituent or a heterocyclic group that may have a substituent, and R and R ₂ may be bonded to a nitrogen atom to form a cyclic amino group containing the nitrogen atom in the ring. Good.
[0015]
In general formula (6), R ₄ is a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group or a substituent which may have a substituent. Represents a heterocyclic group which may have
[0016]
In general formula (7), R ₅ has an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. Represents an optionally substituted heterocyclic group.
[0017]
The alkyl group in the above expression is a group such as methyl, ethyl or propyl, the aryl group is a group such as phenyl, naphthyl or anthryl, the aralkyl group is a group such as benzyl or phenethyl, and the heterocyclic group is pyridyl or thienyl. , Thiazolyl, carbazolyl, benzoimidazolyl, benzothiazolyl and the like, and cyclic amino groups containing a nitrogen atom in the ring include pyrrole, pyrroline, pyrrolidine, pyrrolidone, indol, indoline, carbazole, imidazole. , Pyrazole, pyrazoline, oxazine, phenoxazine and the like.
[0018]
Substituents include alkyl groups such as methyl, ethyl, propyl and butyl, alkoxy groups such as methoxy, ethoxy and propoxy, halogen atoms such as fluorine, chlorine and bromine, and dialkylamino such as dimethylamino and diethylamino. Group, phenylcarbamoyl group, nitro group, cyano group, halomethyl group such as trifluoromethyl, and the like.
[0019]
In the general formula (4), Z represents an oxygen atom or a sulfur atom, and p represents an integer of 0 or 1.
[0020]
In Tables 1 to 5, typical examples of the disazo pigment represented by the general formula (1) are listed, but the pigment is not limited thereto.
[0021]
[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[0022]
The disazo pigment represented by the general formula (1) is obtained by tetrazotizing a corresponding diamine by a conventional method and coupling with a coupler in an aqueous system in the presence of an alkali, or a tetrazonium salt of the diamine is a borofluoride salt or zinc chloride. Once isolated in the form of a double salt, etc., in the presence of a base such as soda acetate, triethylamine, N-methylmorpholine in a suitable solvent such as N, N-dimethylformamide, dimethylsulfoxide, etc. It can be easily synthesized by coupling with a coupler.
[0023]
Next, a general formula of hydroxygallium phthalocyanine (hereinafter referred to as HOGaPc) used in the present invention is shown.
Embedded image

In the formula, X ₁ , X ₂ , X ₃ and X ₄ represent Cl or Br, and n, m, k and j are integers of 0 to 4.
[0024]
In the present invention, any crystal form of HOGaPc can be used. However, the Bragg angle 2θ ± 0.2 ° in the X-ray diffraction of CuKα is 7.4 °, and the crystal HOGaPc has a strong peak at 28.2 °. It is particularly preferable because of its high sensitivity and effective action in the present invention.
[0025]
According to the present invention, both the disazo pigment represented by the general formula (1) exhibiting high sensitivity in the visible light region and the HOGaPc exhibiting high sensitivity in the infrared laser region are contained as the charge generation material. Charges can be generated efficiently with respect to light in the light range to the infrared range.
[0026]
In the present invention, the content ratio of HOGaPc and the specific disazo pigment is preferably set to 20/1 to 1/20, more preferably 10/1 to 1/5.
[0027]
When mixing the charge generating material in forming the photosensitive layer, each material is dispersed in an appropriate binder resin and solvent at a ratio within the above range, or the individually dispersed liquid is adjusted to a predetermined ratio. Mix. When dispersed individually, the binder resin and solvent may be different. When laminating, each of the individually dispersed liquids is applied in such a film thickness that the amount of the contained material becomes a predetermined ratio.
[0028]
Examples of the binder resin used here include polyester, acrylic resin, polyvinyl carbazole, phenoxy resin, polycarbonate, polyvinyl butyral, polyvinyl benzal, polystyrene, polyvinyl acetate, Mainly mentioned are polysulfone, polyarylate, vinylidene chloride / acrylonitrile copolymer and the like.
[0029]
The configuration of the electrophotographic photoreceptor of the present invention is applied to either a stacked type of a charge generation layer and a charge transport layer or a single layer type in which a charge generation material and a charge transport material are mixed. Furthermore, in the case of a laminated type, there are two kinds of order of lamination. Of these, a structure in which a charge generation layer and a charge transport layer are laminated in this order from the support side is common. An embodiment of the electrophotographic photosensitive member will be described by taking the configuration as an example.
[0030]
Any conductive support may be used as long as it has conductivity. Examples thereof include metals such as aluminum and stainless steel, metals provided with a conductive layer, plastics, paper, and the like, and examples of the shape include a cylindrical shape or a film shape. .
[0031]
Further, an undercoat layer having a barrier function and an adhesive function can be provided between the conductive support and the photosensitive layer. As the material for the undercoat layer, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, methyl cellulose, casein, polyamide, glue, gelatin and the like are used. These are dissolved in a suitable solvent and coated on the conductive support.
[0032]
Furthermore, it is preferable to provide a conductive layer between the support and the undercoat layer for the purpose of preventing interference fringes due to scattering when the support is coated with unevenness or defects and the image input is laser light. is there. This can be formed by dispersing conductive powder such as carbon black, metal particles, and metal oxide in a binder resin. The thickness of the conductive layer is 5 to 40 μm, preferably 10 to 30 μm.
[0033]
The charge transport layer is formed by applying and drying a paint in which a charge transport material and a binder resin are mainly dissolved in a solvent. Examples of the charge transport material used include various triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, triallylmethane compounds, and the like. . As the binder resin, the same resin as that used for the charge generation layer can be used.
[0034]
These photosensitive layer coating methods include immersion coating, spray coating, spinner coating, bead coating, blade coating, and beam coating. A method such as a method can be used.
[0035]
The electrophotographic photosensitive member of the present invention is used not only for electrophotographic copying machines but also for electrophotography such as laser beam printers, CRT printers, LED printers, liquid crystal printers, laser plate making, etc. It can be widely used in application fields.
[0036]
Next, the process cartridge and the electrophotographic apparatus of the present invention will be described. FIG. 5 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention. In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotated about a shaft 2 in the direction of an arrow at a predetermined peripheral speed. In the rotating process, the photosensitive member 1 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the primary charging unit 3, and then exposed to image exposure means (non-exposure means such as slit exposure and laser beam scanning exposure). The image exposure light 4 from the figure is received. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the photoreceptor 1.
[0037]
The formed electrostatic latent image is then toner developed by the developing means 5, and the developed toner developed image is transferred from the sheet feeding unit (not shown) between the photoreceptor 1 and the transfer means 6. The transfer means 6 sequentially transfers the transfer material 7 fed in synchronization with the rotation. The transfer material 7 that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means 8, and subjected to image fixing, thereby being printed out as a copy (copy). The surface of the photoreceptor 1 after the image transfer is cleaned by removing the transfer residual toner by the cleaning means 9, and is further subjected to charge removal processing by the pre-exposure light 10 from the pre-exposure means (not shown). And repeatedly used for image formation. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not necessarily required.
[0038]
In the present invention, a plurality of components such as the photosensitive member 1, the primary charging unit 3, the developing unit 5 and the cleaning unit 9 described above are integrally coupled as a process cartridge. The process cartridge may be configured to be attachable to and detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, at least one of the primary charging means 3, the developing means 5 and the cleaning means 9 is integrally supported together with the photosensitive member 1 to form a cartridge, and the apparatus main body is used using a guide means such as a rail 12 of the apparatus main body. The process cartridge 11 can be attached and detached. Further, when the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 uses reflected light or transmitted light from the original, or reads the original with a sensor and converts it into a signal, and the image exposure light 4 is processed according to this signal. The light is emitted by scanning the laser beam, driving the LED array, driving the liquid crystal shutter array, and the like.
[0039]
Next, production examples of HOGaPc used in the present invention will be given.
Production Example 1
After reacting 73 g of o-phthalodinitrile, 25 g of gallium trichloride and 400 ml of α-chloronaphthalene in a nitrogen atmosphere at 200 ° C. for 4 hours, the product was filtered at 130 ° C. The obtained product was dispersed and washed at 130 ° C. for 1 hour using N, N-dimethylformamide, filtered, washed with methanol and dried to obtain 45 g of chlorogallium phthalocyanine. The elemental analysis value of this compound is shown.

[0040]
15 g of the chlorogallium phthalocyanine obtained here was dissolved in 450 g of concentrated sulfuric acid at 10 ° C., dropped into 2300 g of ice water with stirring, reprecipitated and filtered. After being dispersed and washed with 2% aqueous ammonia and sufficiently washed with ion-exchanged water, it was filtered and dried to obtain 13 g of low crystalline HOGaPc.
[0041]
Production Example 2
Milling was performed at room temperature (22 ° C.) for 6 hours with 10 g of HOGaPc obtained in Production Example 1 and 300 g of N, N-dimethylformamide together with 450 g of 1 mmφ glass beads. Solids were taken out from this dispersion, washed thoroughly with methanol and then with water, and dried to obtain 9.2 g of HOGaPc. The diffraction angle 2θ ± 0.2 ° in X-ray diffraction of this HOGaPc had strong peaks at 7.4 ° and 28.2 ° (FIG. 1). The elemental analysis value of this compound is shown.

[0042]
Production Example 3
Milling was performed at room temperature (22 ° C.) for 20 hours with 10 g of HOGaPc obtained in Production Example 1 and 300 g of tetrahydrofuran together with 450 g of 1 mmφ glass beads. Solids were taken out from this dispersion, washed thoroughly with methanol and then with water, and dried to obtain 9.2 g of HOGaPc. The diffraction angle 2θ ± 0.2 ° in X-ray diffraction of this HOGaPc had strong peaks at 7.4 ° and 28.2 ° (FIG. 2). The elemental analysis value of this compound is shown.

[0043]
Production Example 4
Milling was performed for 6 hours at room temperature (22 ° C.) together with 10 g of HOGaPc obtained in Production Example 1, 300 g of N, N-dimethylaniline and 450 g of 1 mmφ glass beads. Solids were taken out from this dispersion, washed thoroughly with methanol and then with water, and dried to obtain 9.2 g of HOGaPc. The diffraction angle 2θ ± 0.2 ° in X-ray diffraction of this HOGaPc had strong peaks at 7.6 °, 16.4 °, 25.0 ° and 26.5 ° (FIG. 3).
[0044]
Production Example 5
Milling was performed at room temperature (22 ° C.) for 24 hours with 10 g of HOGaPc obtained in Production Example 1, 300 g of chloroform and 450 g of 1 mmφ glass beads. Solids were taken out from this dispersion, washed thoroughly with methanol and then with water, and dried to obtain 9.2 g of HOGaPc. The diffraction angle 2θ ± 0.2 ° in X-ray diffraction of this HOGaPc had strong peaks at 6.9 °, 16.5 °, and 26.7 ° (FIG. 4).
[0045]
Production Example 6
According to the production example disclosed in JP-A-61-239248 (USP 4,728,592), a crystalline form of oxytitanium phthalocyanine called so-called α-type was obtained.
[0046]
【Example】
Example 1
50 parts (parts by weight) of titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of resole phenol resin, 20 parts of methyl cellosolve, 5 parts of methanol and silicone oil (polydimethyl) A conductive paint was prepared by dispersing 0.002 part of siloxane polyoxyalkylene copolymer (average molecular weight 3000) in a sand mill using a glass bead of 1 mmφ for 2 hours.
[0047]
The paint was dip-coated on an aluminum cylinder and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.
[0048]
On top of this, a solution prepared by dissolving 5 parts of 6-66-610-12 quaternary polyamide copolymer in a mixed solvent of 70 parts of methanol and 25 parts of butanol was dip coated and dried to a film thickness of 1 μm. An undercoat layer was formed.
[0049]
Next, 1 part of the disazo pigment of Exemplified Pigment 8 and 50 parts of tetrahydrofuran were dispersed in a sand mill using 1 mmφ glass beads for 6 hours, and then 7 parts of the HOGaPc crystals obtained in Production Example 2 and polyvinyl butyrate were dispersed in the dispersion. A solution prepared by dissolving 4 parts of Lahr (trade name S-REC BX-1, manufactured by Sekisui Chemical Co., Ltd.) in 50 parts of tetrahydrofuran was added, and the mixture was further dispersed for 1 hour. 100 parts of butyl acetate was added to this, diluted and recovered, and this was dip-coated on the undercoat layer and dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.30 μm. .
[0050]
Next, 10 parts of a charge transport material having the following structural formula:

And a solution of 10 parts of bisphenol Z-type polycarbonate dissolved in 60 parts of monochlorobenzene, dip-coated on the charge generation layer, dried at 110 ° C. for 1 hour, and a charge transport layer having a thickness of 25 μm To form an electrophotographic photoreceptor.
[0051]
Comparative Example 1
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that a disazo pigment having the following structural formula was used instead of the exemplified pigment 8.
Embedded image

[0052]
Comparative Example 2
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that TiOPc obtained in Production Example 6 was used instead of HOGaPc used in Example 1.
[0053]
Comparative Example 3
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that a disazo pigment having the following structural formula was used instead of the exemplified pigment 8.
Embedded image

[0054]
A copying machine (product) using an electrophotographic photosensitive member produced in Example 1, Comparative Examples 1, 2 and 3 with a halogen lamp as an image exposure light source and further having an erase exposure means using a semiconductor laser (wavelength 785 nm) No. NP-4835, a modified machine manufactured by Canon Inc.) and the electrophotographic characteristics were evaluated. Measure the change in the surface potential when the dark part potential is -650V, the light quantity at which the bright part potential is 130V, the laser light quantity at which the post-erase potential is 80V, and 1000 copies continuously. The results are shown in Table 6.
[0055]
[Table 6]

[0056]
As shown here, the electrophotographic photosensitive member produced in Example 1 has high sensitivity for both the visible light source and the infrared laser light source, and at the same time, the potential stability during continuous copying is sufficient. Yes, showing excellent properties. On the other hand, in the electrophotographic photosensitive member of the comparative example, the sensitivity with both light sources is not satisfied, and the continuous potential change due to the deterioration of memory characteristics is large.
[0057]
Example 2
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the ratio of the disazo pigment to HOGaPc was 1: 1 in Example 1.
[0058]
Example 3
In Example 1, Example Pigment 22 was used as the disazo pigment, HOGaPc obtained in Production Example 2 was used as HOGaPc, and the ratio of the disazo pigment to HOGaPc was set to 5: 1. Further, a hydrazone compound having the following structural formula was used as the charge transport material. Otherwise, an electrophotographic photoreceptor was prepared in the same manner as in Example 1.
Embedded image

[0059]
Example 4
In Example 1, an electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that 1 part of the HOGaPc crystal obtained in Production Example 2 and 2 parts of the disazo pigment of Exemplified Pigment 23 were used.
[0060]
Example 5
In Example 1, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that HOGaPc obtained in Production Example 3 was used as HOGaPc.
[0061]
Example 6
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that HOGaPc obtained in Production Example 4 was used as HOGaPc.
[0062]
Example 7
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that HOGaPc obtained in Production Example 5 was used as HOGaPc.
[0063]
Example 8
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that a fluorenone compound having the following structural formula was used as the charge transport material.
Embedded image

[0064]
Example 9
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that a benzidine compound having the following structural formula was used as the charge transport material.
Embedded image

[0065]
[Table 7]

[0066]
In addition, as a result of image evaluation by visual inspection of poti and fog, the electrophotographic photosensitive member of the example obtained a good image without image defects, but the electrophotographic photosensitive member of the comparative example showed image defects.
[0067]
【The invention's effect】
The electrophotographic photosensitive member of the present invention has a high sensitivity in a wide wavelength range from visible light to infrared light, has a remarkable effect such as high image quality and maintaining good potential stability during durability. Play. In addition, the process cartridge and the electrophotographic apparatus have the same remarkable effect.
[Brief description of the drawings]
1 is an X-ray diffraction pattern of hydroxygallium phthalocyanine produced in Production Example 2. FIG. 2 is an X-ray diffraction pattern of hydroxygallium phthalocyanine produced in Production Example 3. FIG. X-ray diffractogram FIG. 4 is an X-ray diffractogram of hydroxygallium phthalocyanine produced in Production Example 5. FIG. 5 is a diagram showing a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention. .
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 of this invention Axis 3 Primary charging means 4 Image exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Image fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Rail

Claims

In an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the photosensitive layer includes a charge generation layer and a charge transport layer, and the charge generation layer is represented by hydroxygallium phthalocyanine and the following general formula (1). An electrophotographic photoreceptor comprising a disazo pigment in a mixed state .
General formula (1)
[Outside 1]

In the formula, A ₁ represents a coupler residue having a phenolic hydroxyl group, and R ₁ and R ₂ are a hydrogen atom, an alkyl group which may have a substituent, and an aryl which may have a substituent. Represents an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a heterocyclic group which may have a substituent, and R ₁ and R ₂ are both cyclic amino groups which are bonded to a nitrogen atom and contain a nitrogen atom in the ring. A group may be formed. X represents a residue necessary for condensing with a benzene ring to form an optionally substituted polycyclic aromatic ring or an optionally substituted heterocyclic ring, and Z represents an oxygen atom or a sulfur atom. P represents an integer of 0 or 1.

The electrophotographic photoreceptor according to claim 1, wherein the disazo pigment is a disazo pigment represented by the following general formula (2).
General formula (2)
[Outside 2]

In the general formula disazo pigment represented by (2), the general A ₁ is the following formula in the formula (3) the electrophotographic photosensitive member according to claim 2, wherein the disazo pigment represented by. General formula (3)
[Outside 3]

The electrophotographic photoreceptor according to claim 1, wherein the disazo pigment is a disazo pigment having the following structural formula.
[Outside 4]

The hydroxygallium phthalocyanine is a hydroxygallium phthalocyanine crystal having a strong peak at a Bragg angle 2θ ± 0.2 ° of 7.4 ° and 28.2 ° in X-ray diffraction of CuKα. The electrophotographic photosensitive member described.

The electrophotographic photosensitive member according to claim 1 and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means are integrally supported and detachable from the main body of the electrophotographic apparatus. Process cartridge.

An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposing unit, a developing unit, and a transferring unit.