JP4418599B2 - Electrophotographic photosensitive member, process cartridge having the electrophotographic photosensitive member, and electrophotographic apparatus - Google Patents

Description

（一般式（１）中、Ｒ_１は水素原子、置換基を有してもよいアルキル基または置換基を有してもよいアリール基を示し、Ｒ_２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ール基またはＡｒ−Ｎ＝Ｎ−基を示す（Ａｒは置換基を有してもよい芳香族炭化水素環基、置換基を有してもよい複素環基、複数の芳香族炭化水素環が結合した基または複数の複素環が結合した基（芳香族炭化水素環あるいは複素環が結合基を介して結合したものも含む。）を示す。）。）
【００１４】
また、本発明は、上記電子写真感光体と、帯電手段、現像手段及びクリー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とを一体に支持し、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ートリッジである。
【００１５】
また、本発明は、上記電子写真感光体、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である。
【００１６】
【発明の実施の形態】
本発明に用いられるレゾルシナレーン化合物は下記一般式（１）で表される。一般式（１）
【００１７】
【化４】

一般式（１）中、Ｒ_１は水素原子、置換基を有してもよいアルキル基または置換基を有してもよいアリール基を示し、Ｒ_２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ール基またはＡｒ−Ｎ＝Ｎ−基を示す。Ａｒは置換基を有してもよい芳香族炭化水素環基、置換基を有してもよい複素環基、複数の芳香族炭化水素環が結合した基または複数の複素環が結合した基（芳香族炭化水素環あるいは複素環が結合基を介して結合したものも含む。）を示す。
【００１８】
上記表現のアルキル基としてはメチル、エチル、プロピル、ヘキシル、ウンデシル及びトリデシルなどの基が挙げられ、アリール基としてはフェニル及びナフチルなどの基が挙げられ、芳香族炭化水素環としてはベンゼン、ナフタレン、フルオレン、フェナンスレン、アンスラセン、フルオランテン及びピレンなどが挙げられ、複素環としてはフラン、チオフェン、ピリジン、インドール、ベンゾチアゾール、カルバゾール、ベンゾカルバゾール、アクリドン、ジベンゾチオフェン、ベンゾオキサゾール、ベンゾトリアゾール、オキサチアゾール、チアゾール、フェナジン、シンノリン及びベンゾシンノリンなどが挙げられ、更に、複数の芳香族炭化水素環あるいは複数の複素環を結合したものとしては、トリフェニルアミン、ジフェニルアミン、Ｎ−メチルジフェニルアミン、ビフェニル、ターフェニル、ビナフチル、フルオレノン、フェナンスレンキノン、アンスラキノン、ベンズアントロン、ジフェニルオキサゾール、フェニルベンズオキサゾール、ジフェニルメタン、ジフェニルスルホン、ジフェニルエーテル、ベンゾフェノン、スチルベン、ジスチリルベンゼン、テトラフェニル−ｐ−フェニレンジアミン及びテトラフェニルベンジジンなどが挙げられる。
【００１９】
上記表現の置換基としては、メチル、エチル、プロピル及びブチルなどのアルキル基、フェニル、ビフェニル及びナフチルなどのアリール基、メトキシ及びエトキシなどのアルコキシ基、ジメチルアミノ及びジエチルアミノなどのアルキルアミノ基、フェニルアミノ及びジフェニルアミノなどのアリールアミノ基、フッ素、塩素、臭素及びヨウ素などのハロゲン原子、ヒドロキシ基、ニトロ基、シアノ基、トリフルオロメチルなどのハロメチル基などが挙げられる。
【００２０】
次に、本発明において用いられるレゾルシナレーン化合物の例を掲げるが、本発明は、これ等に限定されるものではない。
【００２１】
基本骨格
【００２２】
【化５】

【００２３】
【表１】

【００２４】
【表２】

【００２５】
一般式（１）で表されるレゾルシナレーン化合物は、公知例（例えばJ.Am.Chem.Soc.,Vol.111,No.14,1989 p 5397-5404）に記載のように、レゾルシノール誘導体と各種アルデヒド化合物を硫酸及び塩酸などの酸を用いて脱水縮合することにより合成できる。更に、Ｒ₂にアゾ基を導入する方法は、Ｒ₂が水素のレゾルシナレーン化合物とジアゾ化合物誘導体とのアゾ化カップリング反応により合成できる（文献例：CHEMISTRY LETTERS, pp.1219-1222, 1990）。
【００２６】
以下、「％」及び「部」は、それぞれ「質量％」及び「質量部」を意味する。
【００２７】
合成例１〈例示化合物１５の合成〉
窒素雰囲気下、冷却管を付けたナスフラスコにレゾルシノール２５．６部、ドデシルアルデヒド４２．３部及びエタノール２３０部を加え、その中へ濃塩酸３７部を加え、７０℃で１０時間処理した後、冷却後ろ取し、得られた結晶を熱水で充分洗浄し、乾燥した後、メタノールで再結晶して、白色結晶の例示化合物１５を１７．３部得た。
【００２８】
以下に得られた化合物の ^１ Ｈ−ＮＭＲ及びＩＲのデータを示す。
【００２９】
^１ Ｈ−ＮＭＲ（ＣＤＣＬ３，４０℃）δ
０．９１（ｔ，１２Ｈ）、１．３０（ｂｒｓ，６４Ｈ）、１．４１（ｂｒｓ，８Ｈ）、２．２４（ｂｒｓ，８Ｈ）、４．３３（ｔ，４Ｈ）、６．１５（ｓ，４Ｈ）、７．２４（ｓ，４Ｈ）、９．２７、９．３７、９．５５、９．６２（ｅａｃｈｂｒｓ，４Ｈ）
ＩＲ（ＫＢｒ） ３５４８、３４９２、２９２４、２８５２、１６１８、１５０８、１４６５、１４３２、１３０２、１１９６、１１６７、９０３、８３７ｃｍ^−１
【００３０】
合成例２〈例示化合物１の合成〉
窒素雰囲気下、例示化合物１５ ４．４部をＤＭＦ３６０部に溶解させた溶液を０℃まで冷却した後、下記化合物
【００３１】
【化６】

５．６部とピリジン６０部を加え、そのままの温度で６時間攪拌した後、水１５００部に注下し、析出物をろ取した。得られた結晶を２％塩酸次いで水で充分洗浄し、乾燥した後、テトラヒドロフランで再結晶して、赤色結晶の例示化合物１を５部得た。
【００３２】
以下に得られた化合物のＩＲのデータを示す。
【００３３】
ＩＲ（ＫＢｒ） ３１０１、２９２５、１５４２、１４９１、１３４２ｃｍ^-1
【００３４】
本発明における電荷発生材料として用いられるアゾ顔料としてはビスアゾ、トリスアゾ及びテトラキスアゾなど、いかなるアゾ顔料でも使用できるが、中でも特開昭５９−３１９６２号公報及び特開平１−１８３６６３号公報に開示されているベンズアンスロン系アゾ顔料が優れた感度特性を有しており好ましい。
【００３５】
また、フタロシアニン顔料としては、無金属フタロシアニン及び軸配位子を有してもよい金属フタロシアニンなど、いかなるフタロシアニンでも使用でき、置換基を有してもよいが、特にオキシチタニウムフタロシアニン及びガリウムフタロシアニンが好ましい。更に、いかなる結晶形でもよいが、その中でもＣｕＫα特性Ｘ線回折におけるブラッグ角２θの７．４°±０．２°及び２８．２°±０．２°に強いピークを有する結晶形のヒドロキシガリウムフタロシアニン、ＣｕＫα特性Ｘ線回折におけるブラッグ角２θ±０．２°の７．４°、１６．６°、２５．５°及び２８．３°に強いピークを有する結晶形のクロロガリウムフタロシアニン、ＣｕＫα特性Ｘ線回折におけるブラッグ角２θの２７．２°±０．２°に強いピークを有する結晶形のオキシチタニウムフタロシアニンが優れた感度特性を有し好ましい。更には、ＣｕＫα特性Ｘ線回折におけるブラッグ角２θの７．４°±０．２°及び２８．２°±０．２°に強いピークを有する結晶形のヒドロキシガリウムフタロシアニン、ＣｕＫα特性Ｘ線回折におけるブラッグ角２θの２７．２°±０．２°に強いピークを有する結晶形のオキシチタニウムフタロシアニンが好ましい。また、その中でも特に、ＣｕＫα特性Ｘ線回折におけるブラッグ角２θ±０．２°の７．３°、２４．９°及び２８．１°に強いピークを有する結晶形のヒドロキシガリウムフタロシアニン、ＣｕＫα特性Ｘ線回折におけるブラッグ角２θ±０．２°の７．５°、９．９°、１６．３°、１８．６°、２５．１°及び２８．３°に強いピークを有する結晶形のヒドロキシガリウムフタロシアニン、ＣｕＫα特性Ｘ線回折におけるブラッグ角２θ±０．２°の９．０°、１４．２°、２３．９°及び２７．１°に強いピークを有する結晶形のオキシチタニウムフタロシアニン、ＣｕＫα特性Ｘ線回折におけるブラッグ角２θ±０．２°の９．５°、９．７°、１１．７°、１５．０°、２３．５°、２４．１°及び２７．３°に強いピークを有する結晶形のオキシチタニウムフタロシアニンが好ましい。
【００３６】
本発明における電子写真感光体の層構成は、導電性支持体上に一般式（１）で表されレゾルシナレーン化合物と電荷発生材料及び電荷輸送材料を同時に含有する単一層からなる感光層を有する層構成と、導電性支持体上にレゾルシナレーン化合物と電荷発生材料を含有する電荷発生層と電荷輸送材料を含有する電荷輸送層を積層する感光層を有する層構成がある。なお、電荷発生層と電荷輸送層の積層関係は逆であってもよい。
【００３７】
導電性支持体としては、導電性を有するものであればよく、アルミニウム及びステンレスなどの金属、あるいは導電層を設けた金属、プラスチック及び紙などが挙げられ、形状としては円筒状またはフィルム状などが挙げられる。
【００３８】
導電性支持体と感光層の間にはバリヤー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ール、ポリエチレンオキシド、エチルセルロース、メチルセルロース、カゼイン、ポリアミド、にかわ及びゼラチンなどが用いられる。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。その膜厚は０．２〜３．０μｍであることが好ましい。
【００３９】
更に、支持体と下引き層との間に、支持体のムラや欠陥の被覆あるいは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、カーボンブラック、金属粒子及び金属酸化物などの導電性粉体を、バインダー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であることが好ましく、１０〜３０μｍであることがより好ましい。
【００４０】
単一層からなる感光層を形成する場合、レゾルシナレーン化合物と電荷発生材料と電荷輸送材料を適当なバインダー樹脂溶液中に混合して、この混合液を導電性支持体上に塗布し、乾燥して形成する。
【００４１】
積層構造からなる感光層を形成する場合、電荷発生層は、レゾルシナレーン化合物と電荷発生材料を適当なバインダー樹脂溶液と共に分散し、この分散液を塗布し、乾燥して形成する方法が挙げられる。
【００４２】
電荷輸送層は、主として電荷輸送材料とバインダー樹脂とを溶剤中に溶解させた塗料を塗布し、乾燥して形成する。電荷輸送材料としては各種のトリアリールアミン系化合物、ヒドラゾン系化合物、スチルベン系化合物、ピラゾリン系化合物、オキサゾール系化合物、チアゾール系化合物及びトリアリルメタン系化合物などが挙げられる。
【００４３】
各層に用いるバインダー樹脂としては、例えばポリエステル、アクリル樹脂、ポリビニルカルバゾール、フェノキシ樹脂、ポリカーボネート、ポリビニルブチラール、ポリスチレン、ポリビニルアセテート、ポリサルホン、ポリアリレート、塩化ビニリデン、アクリロニトリル共重合体及びポリビニルベンザールなどが挙げられる。
【００４４】
感光層の塗布方法としては、ディッピング法、スプレーコーティング法、スピンナーコーティング法、ビードコーティング法、ブレードコーティング法及びビームコーティング法などが挙げられる。
【００４５】
感光層が単一層の場合、膜厚は５〜４０μｍであることが好ましく、１０〜３０μｍであることがより好ましく、積層構造の場合、電荷発生層の膜厚は０．０５〜１０μｍであることが好ましく、０．１〜５μｍであることがより好ましく、電荷輸送層の膜厚は５〜４０μｍであることが好ましく、１０〜３０μｍであることがより好ましい。
【００４６】
積層構造の場合、レゾルシナレーン化合物の含有量は電荷発生層に対して０．０１〜１０質量％であることが好ましく、０．１〜５質量％であることがより好ましい。電荷発生材料の含有量は電荷発生層に対して３０〜９０質量％であることが好ましく、５０〜８０質量％であることがより好ましい。電荷輸送材料の含有量は電荷輸送層に対して２０〜８０質量％であることが好ましく、３０〜７０質量％であることがより好ましい。
【００４７】
感光層が単一層の場合、レゾルシナレーン化合物の含有量は感光層に対して０．０１〜５質量％であることが好ましい。電荷発生材料の含有量は感光層に対して３〜３０質量％であることが好ましい。電荷輸送層の含有量は感光層に対して３０〜７０質量％であることが好ましい。
【００４８】
感光層上には、必要に応じて保護層を設けてもよい。保護層はポリビニルブチラール、ポリエステル、ポリカーボネート（ポリカーボネートＺ及び変性ポリカーボネートなど）、ポリアミド、ポリイミド、ポリアリレート、ポリウレタン、スチレン−ブタジエンコポリマー、スチレン−アクリル酸コポリマー及びスチレン−アクリロニトリルコポリマーなどの樹脂を適当な有機溶剤によって溶解し、感光層の上に塗布し、乾燥して形成できる。保護層の膜厚は０．０５〜２０μｍであることが好ましい。また、保護層中に導電性粒子や紫外線吸収剤などを含有させてもよい。導電性粒子としては、例えば酸化錫粒子などの金属酸化物が好ましい。
【００４９】
次に、本発明の電子写真感光体を用いた電子写真装置について説明する。
【００５０】
図１において、１は本発明のドラム型電子写真感光体であり軸１ａを中心に矢印方向に所定の周速度で回転駆動される。該感光体１はその回転過程で帯電手段２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、次いで露光部３にて不図示の露光手段により像露光Ｌ（スリット露光あるいはレーザービーム走査露光など）を受ける。これにより感光体周面に露光像に対応した静電潜像が順次形成されていく。その静電潜像は、次いで現像手段４でトナー現像され、そのトナー像がコロナ転写手段５により不図示の給紙部から感光体１と転写手段５との間に感光体１の回転と同期取りされて給送された記録材９の面に順次転写されていく。像転写を受けた記録材９は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て複写物（コピー）として機外へプリントアウトされる。像転写後の感光体１の表面はクリーニング手段６により転写残りトナーの除去を受けて清浄面化され、前露光手段７により除電処理がされて繰り返して像形成に使用される。
【００５１】
また、図２に示す装置では、少なくとも感光体１、帯電手段２及び現像手段４を容器２０に納めてプロセスカートリッジとし、このプロセスカートリッジを電子写真装置本体のレールなどの案内手段１２を用いて着脱自在に構成している。クリーニング手段６は容器２０内に配置しても配置しなくてもよい。
【００５２】
また、図３及び図４に示すように、帯電手段として接触帯電部材１０を用い、電圧印加された接触帯電部材１０を感光体１に接触させることにより感光体１の帯電を行ってもよい（この帯電方法を、以下接触帯電という）。図３及び図４に示す装置では、感光体１上のトナー像も接触帯電部材２３で記録材９に転写される。即ち、電圧が印加された接触帯電部材２３を記録材９に接触させることにより感光体１上のトナー像を記録材９に転写させる。
【００５３】
更に、図４に示す装置では、少なくとも感光体１及び接触帯電部材１０を第１の容器２１に納めて第１のプロセスカートリッジとし、少なくとも現像手段４を第２の容器２２に納めて第２のプロセスカートリッジとし、これら第１のプロセスカートリッジと、第２のプロセスカートリッジとを着脱自在に構成している。クリーニング手段６は容器２１内に配置しても配置しなくてもよい。
【００５４】
像露光Ｌは、電子写真装置を複写機やプリンターとして使用する場合には、原稿からの反射光や透過光を用いる、あるいは、原稿を読み取り信号化に従って、この信号によりレーザービームの走査、発光ダイオードアレイの駆動、または液晶シャッターアレイの駆動などを行うことにより行われる。
【００５５】
【実施例】
［実施例１］
１０％の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体５０部、レゾール型フェノール樹脂２５部、メチルセロソルブ２０部、メタノール５部及びシリコーンオイル（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部を直径１ｍｍのガラスビーズを用いたサンドミル装置で２時間分散して導電層用塗料を調製した。
【００５６】
アルミニウムシリンダー（φ３０ｍｍ×２６０．５ｍｍ）上に、上記塗料をディッピング法により塗布し、１４０℃で３０分間乾燥させて、膜厚が２０μｍの導電層を形成した。
【００５７】
この上に６−６６−６１０−１２四元系ポリアミド共重合体樹脂５部をメタノール７０部とブタノール２５部の混合溶媒に溶解した溶液をディッピング法により塗布し、乾燥して、膜厚が１μｍの下引き層を設けた。
【００５８】
次に、ＣｕＫα特性Ｘ線回折におけるブラッグ角２θ±０．２°の７．５°、９．９°、１６．３°、１８．６°、２５．１°及び２８．３°に強いピークを有する結晶形のヒドロキシガリウムフタロシアニン１０部、前記例示化合物（１）０．１部及びポリビニルブチラール樹脂（商品名：エスレックＢＸ−１、積水化学工業社製）５部をシクロヘキサノン２５０部に添加し、直径１ｍｍのガラスビーズを用いたサンドミルで１時間分散し、これに２５０部の酢酸エチルを加えて希釈し、これを下引き層上に塗布した後、１００℃で１０分間乾燥して、膜厚が０．１６μｍの電荷発生層を形成した。
【００５９】
次に、下記構造式
【００６０】
【化７】

で表される電荷輸送材料１０部及びポリカーボネート樹脂（商品名：ユーピロンＺ−２００、三菱ガス化学工業社製）１０部をモノクロルベンゼン７０部に溶解した溶液を調製し、電荷発生層上にディッピング法により塗布した。これを１１０℃で１時間乾燥して、膜厚が２５μｍの電荷輸送層を形成し、電子写真感光体を作成した。
【００６１】
［実施例２］
例示化合物（１）の添加量を０．５部に代えた他は実施例１と全く同様にして実施例２の感光体を作成した。
【００６２】
［実施例３］
例示化合物（１）を例示化合物（２）に代えた他は実施例１と全く同様にして実施例３の感光体を作成した。
【００６３】
［実施例４］
例示化合物（２）の添加量を０．５部に代えた他は実施例３と全く同様にして実施例４の感光体を作成した。
【００６４】
［実施例５］
例示化合物（１）を例示化合物（３）に代えた他は実施例１と全く同様にして実施例５の感光体を作成した。
【００６５】
［実施例６］
例示化合物（１）を例示化合物（１５）に代えた他は実施例１と全く同様にして実施例６の感光体を作成した。
【００６６】
［実施例７］
ＣｕＫα特性Ｘ線回折におけるブラッグ角２θ±０．２°の７．５°、９．９°、１６．３°、１８．６°、２５．１°及び２８．３°に強いピークを有する結晶形のヒドロキシガリウムフタロシアニンをＣｕＫα特性Ｘ線回折におけるブラッグ角２θ±０．２°の９．０°、１４．２°、２３．９°及び２７．１°に強いピークを有する結晶形のオキシチタニウムフタロシアニンに代えた他は、実施例１と全く同様にして実施例７の感光体を作成した。
【００６７】
［実施例８］
実施例１と同様に電荷発生層を形成した。次に、下記構造式
【００６８】
【化８】

で表される電荷輸送材料１０部及びポリカーボネート樹脂（商品名：ユーピロンＺ−４００、三菱ガス化学工業社製）１０部をモノクロロベンゼン１００部に溶解した溶液を調製し、電荷発生層上にディッピング法により塗布した。これを１５０℃で３０分間乾燥して、膜厚が１５μｍの電荷輸送層を形成して、電子写真感光体を作成した。
【００６９】
［実施例９］
実施例１と同様に電荷発生層を形成した。次に、下記構造式
【００７０】
【化９】

で表される電荷輸送材料７部、下記構造式
【００７１】
【化１０】

で表される電荷輸送材料３部及びポリカーボネート樹脂（商品名：ユーピロンＺ−２００、三菱ガス化学工業社製）１０部をモノクロロベンゼン７０部に溶解した溶液を調製し、電荷発生層上にディッピング法により塗布した。これを１１０℃で１時間乾燥して、膜厚が３２μｍの電荷輸送層を形成し電子写真感光体を作成した。
【００７２】
［比較例１］
例示化合物（１）を添加しなかった他は実施例１と全く同様にして比較例１の感光体を作成した。
【００７３】
［比較例２］
例示化合物（１）を添加しなかった他は実施例７と全く同様にして比較例２の感光体を作成した。
【００７４】
［比較例３］
例示化合物（１）に代えて下記構造式を有するビスアゾ顔料
【００７５】
【化１１】

３部を添加した他は実施例７と全く同様にして比較例３の感光体を作成した。
【００７６】
これら電子写真感光体を用いて明部電位測定及びゴースト画像評価を行った。評価はレーザービームプリンター（商品名：レーザージェット４０００：ヒューレットパッカード社製）を改造して使用した。まず、温度２３℃、５５％ＲＨ環境下での初期の明部電位の測定及びゴースト画像評価を行った後、同環境条件で１０００枚の通紙耐久試験を行い、耐久直後及び１５時間後での明部電位の測定及びゴースト画像の評価を行った。
【００７７】
次に、これらの感光体を評価機と共に、温度１５℃、１０％ＲＨの低温低湿（Ｌ／Ｌ）下で３日間放置した後、明部電位の測定及びゴースト画像の評価を行った。
【００７８】
前記通紙耐久の条件は１分間４枚プリントの間欠モードで耐久パターンは約０．５ｍｍ幅の線を縦１０ｍｍ置きに印字するモードで行った。
【００７９】
ゴースト画像評価方法は以下のようにした。
ゴースト画像は５ｍｍ角の黒四角パターンをドラム一周分任意の数だけ印字し、その後全面ハーフトーン画像（１ドット１スペースのドット密度の画像）、全面白画像または全面黒画像をそれぞれプリントした。ゴースト画像サンプルは、機械の現像ボリューム、Ｆ５（中心値）とＦ９（濃度薄い）で各サンプリングした。評価は目視で行い、ゴーストの程度で下記のようにランク付けした。
【００８０】
ランク１は「いずれのモードでもゴーストは全く見えない」
ランク２は「特定のモードでゴーストがうっすら見えるレベル」
ランク３は「いずれのモードでもゴーストがうっすら見えるレベル」
ランク４は「いずれのモードでもゴーストが見えるレベル」
以上の結果を表１にまとめた。
【００８１】
【表３】

【００８２】
【発明の効果】
以上説明してきたように、本発明によれば、高感度、特に半導体レーザー波長領域で高感度特性を維持しつつ画像欠陥の無い画像を供給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及び電子写真装置が提供される。
【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電子写真装置の概略構成を示す図である。
【図２】本発明の電子写真感光体を有するプロセスカートリッジを有する電子写真装置の概略構成を示す図である。
【図３】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を示す図である。
【図４】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を示す図である。
【符号の説明】
１ 電子写真感光体
１ａ 軸
２ 帯電手段
３ 露光部
４ 現像手段
５ 転写手段
６ クリーニング手段
７ 前露光手段
８ 定着手段
９ 記録材
１０、２３ 接触帯電部材
１２ 案内手段
２０、２１、２２ 容器
Ｌ 像露光[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotographic photoreceptor, a process cartridge having the electrophotographic photoreceptor, and an electrophotographic apparatus.
[0002]
[Prior art]
Inorganic photoconductive materials such as selenium, cadmium sulfide and zinc oxide have been conventionally used as photoconductive materials for electrophotographic photoreceptors. On the other hand, organic photoconductive materials such as polyvinylcarbazole, oxadiazole, azo pigments, and phthalocyanines have advantages such as pollution-free and high productivity compared to inorganic photoconductive materials, but their sensitivity is low and their practical application is difficult. Met. For this reason, several sensitization methods have been proposed, and the effective method is to use a function-separated type photoconductor in which a charge generation layer and a charge transport layer are laminated. It has become.
[0003]
On the other hand, in recent years, non-impact printers using electrophotographic technology have been widely used as terminal printers in place of conventional impact printers. These are laser beam printers mainly using laser light as a light source, and a semiconductor laser is used as the light source from the viewpoint of cost, size of the apparatus, and the like.
[0004]
At present, semiconductor lasers that are mainly used have an oscillation wavelength of 650 to 820 nm and have a long wavelength. Therefore, development of electrophotographic photosensitive members having sufficient sensitivity to light having these long wavelengths has been underway.
[0005]
Azo pigments and phthalocyanine pigments are extremely effective as charge generation materials having sensitivity up to such a long wavelength region. In particular, azo pigments are disclosed in Japanese Patent Application Laid-Open Nos. 59-31962 and 1-183663, and phthalocyanines are oxy pigments. Titanium phthalocyanine and gallium phthalocyanine have excellent sensitivity characteristics as compared with conventional phthalocyanine compounds, and thus far, JP-A-61-239248, JP-A-61-217050, JP-A-62-267094, JP-A-63. Various crystal forms are disclosed in JP-A Nos. 218768 / 64-17066, JP-A-5-098181, JP-A-5-263007, and JP-A-10-67946. Further, JP-A-7-128888 and JP-A-9-34149 disclose combinations with specific azo compounds in order to improve the problems of phthalocyanine compounds, while maintaining higher sensitivity characteristics. There has been a demand for a photoreceptor that provides an image free from image defects.
[0006]
[Problems to be solved by the invention]
An electrophotographic photoreceptor using an azo compound and phthalocyanine has excellent sensitivity characteristics as described above, but the generated photocarrier tends to remain in the photosensitive layer and easily causes potential fluctuation as a kind of memory. was there.
[0007]
Although not confirmed in principle, the electrons left in the charge generation layer are, for some reason, the interface between the charge generation layer and the charge transport layer, or the charge generation layer and the undercoat layer, or the undercoat layer and the conductive layer. It is considered that the barrier property of hole injection near the interface is increased or decreased.
[0008]
As a phenomenon that appears when it is actually used as an electrophotographic photosensitive member, when electrons remain at the interface between the charge transport layer and the charge generation layer, it appears as a decrease in the bright portion potential and the residual potential during continuous printing. For example, when used in a development process (so-called reversal development system) where the dark part potential part that is often used in printers is a non-development part and the bright part is a development part (so-called reverse development system) When the entire white image is taken at the time of the next printing, a so-called ghost phenomenon (hereinafter abbreviated as positive ghost) in which the previous print portion appears black appears remarkably.
[0009]
On the other hand, when electrons remain at the interface between the charge generation layer and the undercoat layer or between the undercoat layer and the conductive layer, it appears as an increase in the bright portion potential during printing. When used in a reversal development system, the sensitivity of the area exposed to light at the time of previous printing becomes slow, and if the entire black image is taken at the time of the next printing, a so-called ghost phenomenon (hereinafter abbreviated as “negative ghost”) occurs in which the previous printed part appears white Prominently appear.
[0010]
Of these phenomena, negative ghosts often appear at the beginning of printing and positive ghosts appear during continuous printing. This phenomenon is particularly significant in a photoreceptor using an undercoat layer as an adhesive layer for the charge generation layer, and the volume resistance to electrons of the charge generation layer and the undercoat layer increases under an environment such as low temperature and low humidity. There is a drawback that electrons are easily filled in the charge generation layer and further a ghost phenomenon is likely to occur.
[0011]
Accordingly, an object of the present invention is to provide an electrophotographic photosensitive member that supplies an image free from image defects while maintaining high sensitivity, particularly high sensitivity characteristics in a semiconductor laser wavelength region, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member. Is to provide.
[0012]
[Means for Solving the Problems]
  The present invention relates to a conductive support.And the conductive supportaboveBeen formedAn electrophotographic photosensitive member having a photosensitive layer, wherein the photosensitive layer contains a resorcinarene compound represented by the following general formula (1).
General formula (1)
[0013]
[Chemical Formula 3]

(In the general formula (1), R₁Represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and R₂Represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an Ar—N═N— group (Ar is an aromatic hydrocarbon which may have a substituent) A ring group, a heterocyclic group which may have a substituent, a group to which a plurality of aromatic hydrocarbon rings are bonded, or a group to which a plurality of heterocyclic rings are bonded(Includes those in which an aromatic hydrocarbon ring or heterocyclic ring is bonded via a linking group.)Indicates. ). )
[0014]
  The present invention also provides the electrophotographic photoreceptor described above.When,At least one means selected from the group consisting of charging means, developing means and cleaning meansWhenIs a process cartridge characterized by being integrally supported and detachable from the main body of the electrophotographic apparatus.
[0015]
The present invention also provides an electrophotographic apparatus comprising the electrophotographic photosensitive member, a charging unit, an image exposing unit, a developing unit, and a transfer unit.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The resorcinarene compound used in the present invention is represented by the following general formula (1). General formula (1)
[0017]
[Formula 4]

In general formula (1), R₁Represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and R₂Represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an Ar—N═N— group. Ar is an aromatic hydrocarbon ring group that may have a substituent, a heterocyclic group that may have a substituent, a group in which a plurality of aromatic hydrocarbon rings are bonded, or a group in which a plurality of heterocyclic rings are bonded(Includes those in which an aromatic hydrocarbon ring or heterocyclic ring is bonded via a linking group.)Indicates.
[0018]
Examples of the alkyl group in the above expression include groups such as methyl, ethyl, propyl, hexyl, undecyl and tridecyl. Examples of the aryl group include groups such as phenyl and naphthyl. Examples of the aromatic hydrocarbon ring include benzene, naphthalene, Fluorene, phenanthrene, anthracene, fluoranthene, pyrene and the like, and examples of the heterocyclic ring include furan, thiophene, pyridine, indole, benzothiazole, carbazole, benzocarbazole, acridone, dibenzothiophene, benzoxazole, benzotriazole, oxathiazole, thiazole, Examples include phenazine, cinnoline, benzocinnoline, and the like, and those in which a plurality of aromatic hydrocarbon rings or a plurality of heterocycles are bonded include triphenylamine, diphenylamine. , N-methyldiphenylamine, biphenyl, terphenyl, binaphthyl, fluorenone, phenanthrenequinone, anthraquinone, benzanthrone, diphenyloxazole, phenylbenzoxazole, diphenylmethane, diphenylsulfone, diphenylether, benzophenone, stilbene, distyrylbenzene, tetra Examples include phenyl-p-phenylenediamine and tetraphenylbenzidine.
[0019]
Substituents in the above expressions include alkyl groups such as methyl, ethyl, propyl and butyl, aryl groups such as phenyl, biphenyl and naphthyl, alkoxy groups such as methoxy and ethoxy, alkylamino groups such as dimethylamino and diethylamino, phenylamino And arylamino groups such as diphenylamino, halogen atoms such as fluorine, chlorine, bromine and iodine, halomethyl groups such as hydroxy group, nitro group, cyano group and trifluoromethyl.
[0020]
Next, examples of the resorcinarene compound used in the present invention will be given, but the present invention is not limited to these.
[0021]
Basic skeleton
[0022]
[Chemical formula 5]

[0023]
[Table 1]

[0024]
[Table 2]

[0025]
Resorcinolene compounds represented by the general formula (1) can be prepared from resorcinol derivatives and various compounds as described in known examples (for example, J. Am. Chem. Soc., Vol. 111, No. 14, 1989 p 5397-5404). The aldehyde compound can be synthesized by dehydration condensation using an acid such as sulfuric acid and hydrochloric acid. In addition, R₂The method of introducing an azo group into R₂Can be synthesized by an azotation coupling reaction between a resorcinarene compound of hydrogen and a diazo compound derivative (example: CHEMISTRY LETTERS, pp.1219-1222, 1990).
[0026]
Hereinafter, “%” and “part” mean “% by mass” and “part by mass”, respectively.
[0027]
Synthesis Example 1 <Synthesis of Exemplary Compound 15>
Under a nitrogen atmosphere, 25.6 parts of resorcinol, 42.3 parts of dodecyl aldehyde, and 230 parts of ethanol were added to an eggplant flask equipped with a condenser, and 37 parts of concentrated hydrochloric acid was added thereto, followed by treatment at 70 ° C. for 10 hours. After cooling, the resulting crystals were sufficiently washed with hot water, dried, and recrystallized from methanol to obtain 17.3 parts of Exemplified Compound 15 as white crystals.
[0028]
  Of the compound obtained below ¹ 1 shows H-NMR and IR data.
[0029]
¹ H-NMR (CDCL3, 40 ° C) δ
  0.91 (t, 12H), 1.30 (brs, 64H), 1.41 (brs, 8H), 2.24 (brs, 8H), 4.33 (t, 4H), 6.15 (s) , 4H), 7.24 (s, 4H), 9.27, 9.37, 9.55, 9.62 (eachbrrs, 4H)
  IR (KBr) 3548, 3492, 2924, 2852, 1618, 1508, 1465, 1432, 1302, 1196, 1167, 903, 837 cm^-1
[0030]
Synthesis Example 2 <Synthesis of Exemplary Compound 1>
In a nitrogen atmosphere, a solution prepared by dissolving 4.4 parts of Exemplified Compound 15 in 360 parts of DMF was cooled to 0 ° C.
[0031]
[Chemical 6]

5.6 parts and 60 parts of pyridine were added and stirred at the same temperature for 6 hours, and then poured into 1500 parts of water, and the precipitate was collected by filtration. The obtained crystals were sufficiently washed with 2% hydrochloric acid and then with water, dried, and recrystallized with tetrahydrofuran to obtain 5 parts of Exemplified Compound 1 as red crystals.
[0032]
The IR data of the obtained compound are shown below.
[0033]
IR (KBr) 3101, 2925, 1542, 1491, 1342cm^-1
[0034]
As the azo pigment used as the charge generation material in the present invention, any azo pigment such as bisazo, trisazo, and tetrakisazo can be used, and among others, disclosed in JP-A-59-31962 and JP-A-1-183663. Preferred benzanthrone azo pigments have excellent sensitivity characteristics.
[0035]
Further, as the phthalocyanine pigment, any phthalocyanine such as metal-free phthalocyanine and metal phthalocyanine which may have an axial ligand may be used and may have a substituent, but oxytitanium phthalocyanine and gallium phthalocyanine are particularly preferable. . In addition, any crystalline form may be used, among which crystalline hydroxygallium having strong peaks at 7.4 ° ± 0.2 ° and 28.2 ° ± 0.2 ° of the Bragg angle 2θ in CuKα characteristic X-ray diffraction. Phthalocyanine, CuKα Characteristic Crystalline chlorogallium phthalocyanine having a strong peak at 7.4 °, 16.6 °, 25.5 ° and 28.3 ° with a Bragg angle 2θ ± 0.2 ° in X-ray diffraction, CuKα property Crystalline oxytitanium phthalocyanine having a strong peak at 27.2 ° ± 0.2 ° with a Bragg angle 2θ in X-ray diffraction has excellent sensitivity characteristics and is preferable. Furthermore, the crystalline form of hydroxygallium phthalocyanine having strong peaks at 7.4 ° ± 0.2 ° and 28.2 ° ± 0.2 ° of the Bragg angle 2θ in CuKα characteristic X-ray diffraction, in CuKα characteristic X-ray diffraction, A crystalline form of oxytitanium phthalocyanine having a strong peak at a Bragg angle 2θ of 27.2 ° ± 0.2 ° is preferred. Among them, in particular, crystalline hydroxygallium phthalocyanine having strong peaks at 7.3 °, 24.9 °, and 28.1 ° with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction, CuKα characteristic X Crystalline hydroxy with strong peaks at 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° with a Bragg angle 2θ ± 0.2 ° in line diffraction Gallium phthalocyanine, crystalline form of oxytitanium phthalocyanine, CuKα having strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction Strong at 9.5 °, 9.7 °, 11.7 °, 15.0 °, 23.5 °, 24.1 ° and 27.3 ° with Bragg angle 2θ ± 0.2 ° in characteristic X-ray diffraction Crystalline oxytitani with a peak Beam phthalocyanine is preferable.
[0036]
The layer structure of the electrophotographic photoreceptor in the present invention is a layer structure having a photosensitive layer composed of a single layer, which is represented by the general formula (1) and contains a resorcinarene compound, a charge generation material and a charge transport material simultaneously on a conductive support. And a photosensitive layer in which a charge generating layer containing a resorcinarene compound and a charge generating material and a charge transporting layer containing a charge transporting material are laminated on a conductive support. The stacking relationship between the charge generation layer and the charge transport layer may be reversed.
[0037]
As the conductive support, any conductive support may be used, and examples thereof include metals such as aluminum and stainless steel, metals provided with a conductive layer, plastics, paper, and the like. Can be mentioned.
[0038]
An undercoat layer having a barrier function and an adhesive function may 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. The film thickness is preferably 0.2 to 3.0 μm.
[0039]
Furthermore, it is preferable to provide a conductive layer between the support and the undercoat layer for the purpose of covering unevenness or defects on the support or preventing interference fringes. 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 preferably 5 to 40 μm, and more preferably 10 to 30 μm.
[0040]
When forming a photosensitive layer consisting of a single layer, the resorcinarene compound, charge generation material and charge transport material are mixed in an appropriate binder resin solution, and this mixture is applied onto a conductive support and dried. To do.
[0041]
In the case of forming a photosensitive layer having a laminated structure, the charge generation layer may be formed by dispersing a resorcinarene compound and a charge generation material together with an appropriate binder resin solution, applying the dispersion, and drying.
[0042]
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 include various triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, and triallylmethane compounds.
[0043]
Examples of the binder resin used for each layer include polyester, acrylic resin, polyvinyl carbazole, phenoxy resin, polycarbonate, polyvinyl butyral, polystyrene, polyvinyl acetate, polysulfone, polyarylate, vinylidene chloride, acrylonitrile copolymer, and polyvinyl benzal. .
[0044]
Examples of the photosensitive layer coating method include a dipping method, a spray coating method, a spinner coating method, a bead coating method, a blade coating method, and a beam coating method.
[0045]
When the photosensitive layer is a single layer, the film thickness is preferably 5 to 40 μm, more preferably 10 to 30 μm. In the case of a laminated structure, the charge generation layer has a film thickness of 0.05 to 10 μm. The thickness of the charge transport layer is preferably 5 to 40 μm, and more preferably 10 to 30 μm.
[0046]
In the case of a laminated structure, the content of the resorcinarene compound is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass with respect to the charge generation layer. The content of the charge generation material is preferably 30 to 90% by mass and more preferably 50 to 80% by mass with respect to the charge generation layer. The content of the charge transport material is preferably 20 to 80% by mass and more preferably 30 to 70% by mass with respect to the charge transport layer.
[0047]
When the photosensitive layer is a single layer, the content of the resorcinarene compound is preferably 0.01 to 5% by mass with respect to the photosensitive layer. The content of the charge generating material is preferably 3 to 30% by mass with respect to the photosensitive layer. The content of the charge transport layer is preferably 30 to 70% by mass with respect to the photosensitive layer.
[0048]
A protective layer may be provided on the photosensitive layer as necessary. The protective layer is made of a resin such as polyvinyl butyral, polyester, polycarbonate (such as polycarbonate Z and modified polycarbonate), polyamide, polyimide, polyarylate, polyurethane, styrene-butadiene copolymer, styrene-acrylic acid copolymer and styrene-acrylonitrile copolymer. It can be dissolved by coating, coated on the photosensitive layer, and dried. The thickness of the protective layer is preferably 0.05 to 20 μm. Moreover, you may contain electroconductive particle, a ultraviolet absorber, etc. in a protective layer. As the conductive particles, metal oxides such as tin oxide particles are preferable.
[0049]
Next, an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention will be described.
[0050]
In FIG. 1, reference numeral 1 denotes a drum-type electrophotographic photosensitive member of the present invention, which is rotationally driven in a direction of an arrow about a shaft 1a at a predetermined peripheral speed. The photosensitive member 1 is uniformly charged at a predetermined positive or negative potential on its peripheral surface by the charging means 2 during the rotation process, and then the image exposure L (slit exposure or laser beam) is performed by the exposure means (not shown) in the exposure unit 3. Scanning exposure). As a result, electrostatic latent images corresponding to the exposure image are sequentially formed on the peripheral surface of the photosensitive member. The electrostatic latent image is then developed with toner by the developing unit 4, and the toner image is synchronized with the rotation of the photoconductor 1 between the photoconductor 1 and the transfer unit 5 from a paper feeding unit (not shown) by the corona transfer unit 5. It is sequentially transferred onto the surface of the recording material 9 taken and fed. The recording material 9 that has received the image transfer is separated from the surface of the photosensitive member, introduced into the fixing means 8, and subjected to image fixing, and printed out as a copy (copy). After the image transfer, the surface of the photoreceptor 1 is cleaned by the transfer unit 6 after removal of the transfer residual toner, is subjected to charge removal processing by the pre-exposure unit 7 and repeatedly used for image formation.
[0051]
  In the apparatus shown in FIG. 2, at least the photosensitive member 1, the charging unit 2, and the developing unit 4 are housed in a container 20 to form a process cartridge.Electronic photographyDevice bookbodyIt is configured to be detachable using guide means 12 such as a rail. The cleaning means 6 may or may not be disposed in the container 20.
[0052]
Further, as shown in FIGS. 3 and 4, the contact charging member 10 may be used as a charging unit, and the photosensitive member 1 may be charged by bringing the contact charging member 10 to which voltage is applied into contact with the photosensitive member 1 ( This charging method is hereinafter referred to as contact charging). In the apparatus shown in FIGS. 3 and 4, the toner image on the photoreceptor 1 is also transferred to the recording material 9 by the contact charging member 23. That is, the toner image on the photoreceptor 1 is transferred to the recording material 9 by bringing the contact charging member 23 to which a voltage is applied into contact with the recording material 9.
[0053]
Further, in the apparatus shown in FIG. 4, at least the photosensitive member 1 and the contact charging member 10 are housed in a first container 21 to form a first process cartridge, and at least the developing means 4 is housed in a second container 22 to form a second container. The process cartridge is configured such that the first process cartridge and the second process cartridge are detachable. The cleaning means 6 may or may not be disposed in the container 21.
[0054]
When the electrophotographic apparatus is used as a copying machine or a printer, the image exposure L uses reflected light or transmitted light from the original, or scans the original with a laser beam by using this signal as a read signal, and a light emitting diode. This is done by driving the array or driving the liquid crystal shutter array.
[0055]
【Example】
[Example 1]
50 parts of titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of resol type phenol resin, 20 parts of methyl cellosolve, 5 parts of methanol and silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average A conductive layer coating material was prepared by dispersing 0.002 part of molecular weight 3000) for 2 hours in a sand mill using glass beads having a diameter of 1 mm.
[0056]
The paint was applied on an aluminum cylinder (φ30 mm × 260.5 mm) by dipping and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.
[0057]
A solution prepared by dissolving 5 parts of 6-66-610-12 quaternary polyamide copolymer resin in a mixed solvent of 70 parts of methanol and 25 parts of butanol was applied by a dipping method and dried to obtain a film thickness of 1 μm. An undercoat layer was provided.
[0058]
Next, strong peaks at 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction 10 parts of a crystalline form of hydroxygallium phthalocyanine having the above, 0.1 part of the exemplified compound (1) and 5 parts of polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) are added to 250 parts of cyclohexanone, Disperse with a sand mill using glass beads with a diameter of 1 mm for 1 hour, add 250 parts of ethyl acetate to this, dilute, apply this onto the undercoat layer, and then dry at 100 ° C. for 10 minutes to obtain a film thickness. A charge generation layer having a thickness of 0.16 μm was formed.
[0059]
Next, the following structural formula
[0060]
[Chemical 7]

A solution in which 10 parts of a charge transport material and 10 parts of a polycarbonate resin (trade name: Iupilon Z-200, manufactured by Mitsubishi Gas Chemical Industries, Ltd.) are dissolved in 70 parts of monochlorobenzene is prepared, and a dipping method is performed on the charge generation layer. Was applied. This was dried at 110 ° C. for 1 hour to form a charge transport layer having a thickness of 25 μm, and an electrophotographic photoreceptor was prepared.
[0061]
[Example 2]
A photoconductor of Example 2 was prepared in the same manner as in Example 1 except that the amount of Example Compound (1) added was changed to 0.5 part.
[0062]
[Example 3]
A photoconductor of Example 3 was prepared in the same manner as in Example 1, except that Exemplified Compound (1) was replaced with Exemplified Compound (2).
[0063]
[Example 4]
A photoconductor of Example 4 was prepared in the same manner as in Example 3 except that the amount of Example Compound (2) added was changed to 0.5 part.
[0064]
[Example 5]
A photoconductor of Example 5 was prepared in the same manner as in Example 1 except that the exemplified compound (1) was replaced with the exemplified compound (3).
[0065]
[Example 6]
A photoconductor of Example 6 was prepared in the same manner as in Example 1 except that the exemplified compound (1) was replaced with the exemplified compound (15).
[0066]
[Example 7]
Crystals having strong peaks at 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction Form of hydroxygallium phthalocyanine in crystalline form with strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° with Bragg angles 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction A photoconductor of Example 7 was prepared in the same manner as in Example 1 except that phthalocyanine was used.
[0067]
[Example 8]
A charge generation layer was formed in the same manner as in Example 1. Next, the following structural formula
[0068]
[Chemical 8]

A solution in which 10 parts of a charge transporting material represented by the formula (1) and 10 parts of a polycarbonate resin (trade name: Iupilon Z-400, manufactured by Mitsubishi Gas Chemical Industries, Ltd.) are dissolved in 100 parts of monochlorobenzene is prepared, and a dipping method is performed on the charge generation layer. Was applied. This was dried at 150 ° C. for 30 minutes to form a charge transport layer having a thickness of 15 μm, and an electrophotographic photosensitive member was produced.
[0069]
[Example 9]
A charge generation layer was formed in the same manner as in Example 1. Next, the following structural formula
[0070]
[Chemical 9]

7 parts of charge transport material represented by the following structural formula
[0071]
[Chemical Formula 10]

A solution in which 3 parts of a charge transport material represented by the formula (1) and 10 parts of a polycarbonate resin (trade name: Iupilon Z-200, manufactured by Mitsubishi Gas Chemical Industries, Ltd.) are dissolved in 70 parts of monochlorobenzene is prepared, and a dipping method is performed on the charge generation layer. Was applied. This was dried at 110 ° C. for 1 hour to form a charge transport layer having a thickness of 32 μm, and an electrophotographic photosensitive member was prepared.
[0072]
[Comparative Example 1]
A photoconductor of Comparative Example 1 was prepared in the same manner as in Example 1 except that Example Compound (1) was not added.
[0073]
[Comparative Example 2]
A photoconductor of Comparative Example 2 was prepared in the same manner as in Example 7 except that Example Compound (1) was not added.
[0074]
[Comparative Example 3]
A bisazo pigment having the following structural formula instead of the exemplified compound (1)
[0075]
Embedded image

A photoconductor of Comparative Example 3 was prepared in the same manner as in Example 7 except that 3 parts were added.
[0076]
Using these electrophotographic photoreceptors, bright part potential measurement and ghost image evaluation were performed. The laser beam printer (trade name: Laserjet 4000: manufactured by Hewlett-Packard Company) was modified and used for evaluation. First, after measuring the initial bright part potential and evaluating the ghost image under a temperature of 23 ° C. and 55% RH, a 1,000 sheet passing durability test was performed under the same environmental conditions. The bright part potential was measured and the ghost image was evaluated.
[0077]
Next, these photoconductors were allowed to stand together with an evaluation machine under low temperature and low humidity (L / L) at a temperature of 15 ° C. and 10% RH for 3 days, and then the light potential was measured and the ghost image was evaluated.
[0078]
The conditions for endurance of the paper passing were intermittent mode of printing 4 sheets per minute, and the endurance pattern was a mode in which lines of about 0.5 mm width were printed every 10 mm in length.
[0079]
The ghost image evaluation method was as follows.
For the ghost image, a black square pattern of 5 mm square was printed in an arbitrary number for one round of the drum, and then an entire halftone image (an image having a dot density of one dot and one space), an entire white image, or an entire black image was printed. The ghost image samples were sampled at the machine development volume, F5 (center value) and F9 (light density). Evaluation was performed visually and ranked as follows according to the degree of ghost.
[0080]
Rank 1 is “No ghosts in any mode”
Rank 2 is “a level where you can see a ghost in a specific mode”
Rank 3 is “a level where you can see ghosts in any mode”
Rank 4 is “a level where you can see ghosts in any mode”
The above results are summarized in Table 1.
[0081]
[Table 3]

[0082]
【The invention's effect】
As described above, according to the present invention, an electrophotographic photosensitive member that supplies an image free from image defects while maintaining high sensitivity, particularly high sensitivity characteristics in a semiconductor laser wavelength region, and a process having the electrophotographic photosensitive member A cartridge and an electrophotographic apparatus are provided.
[Brief description of the drawings]
FIG. 1 is a diagram showing a schematic configuration of an electrophotographic apparatus having an electrophotographic photosensitive member of the present invention.
FIG. 2 is a diagram showing a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.
FIG. 3 is a diagram showing a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.
FIG. 4 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]
1 Electrophotographic photoreceptor
1a axis
2 Charging means
3 exposure part
4 Development means
5 Transfer means
6 Cleaning means
7 Pre-exposure means
8 Fixing means
9 Recording material
10, 23 Contact charging member
12 Guide means
20, 21, 22 container
L Image exposure

Claims (9)

An electrophotographic photosensitive member having a conductive support and a photosensitive layer formed on the conductive support, wherein the photosensitive layer contains a resorcinarene compound represented by the following general formula (1): Photoconductor.
General formula (1)

(In the general formula (1), R ₁ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ₂ has a hydrogen atom or a substituent. Represents an alkyl group, an aryl group which may have a substituent, or an Ar—N═N— group (Ar may have an aromatic hydrocarbon ring group which may have a substituent, or a substituent; A good heterocyclic group, a group in which a plurality of aromatic hydrocarbon rings are bonded, or a group in which a plurality of heterocyclic rings are bonded (including those in which an aromatic hydrocarbon ring or a heterocyclic ring is bonded through a bonding group) . ).) The electrophotographic photoreceptor according to claim 1, wherein the resorcinarene compound is a compound represented by the following general formula (2).
General formula (2)

(In the general formula (2), R ₁ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and Ar represents an aromatic which may have a substituent. A hydrocarbon ring group, a heterocyclic group which may have a substituent, a group in which a plurality of aromatic hydrocarbon rings are bonded, or a group in which a plurality of heterocyclic rings are bonded (an aromatic hydrocarbon ring or a heterocyclic ring is a bonding group) Including those bonded via a) .)   The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer contains a phthalocyanine pigment or an azo pigment as a charge generating material. The electrophotographic photosensitive member according to claim 3 , wherein the phthalocyanine pigment is oxytitanium phthalocyanine. The electrophotographic photosensitive member according to claim 3 , wherein the phthalocyanine pigment is gallium phthalocyanine. The electrophotographic photosensitive member according to claim 5 wherein the gallium phthalocyaninato two emissions is hydroxygallium phthalocyanine. It said photosensitive layer has a charge generation layer and a charge transport layer, the electrophotographic photosensitive member according to claim 1, the charge generation layer contains the Rezorushinaren compound represented by the general formula (1) . An electrophotographic photosensitive member according to claim 1, charging means, integrally supported and at least one means selected from the group consisting of the developing means and cleaning means, detachably mountable to an electrophotographic apparatus main body A process cartridge characterized by being.   An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an exposure unit, a developing unit, and a transfer unit.

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