JP3774673B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

【００１１】
式中、Ｒ₁は水素原子、置換基を有してもよいアルキル基又はアリール基を示し、Ｒ₂は水素原子、置換基を有してもよいアルキル基、アリール基又はＡｒ−Ｎ＝Ｎ−基を示し、Ａｒは同一又は異なって、置換基を有してもよい芳香族炭化水素環、置換基を有してもよい複素環又は置換基を有してもよい複数の芳香族炭化水素環あるいは置換基を有してもよい複数の複素環を結合したものの１価の基を示す。
【００１２】
本発明において、アルキル基としてはメチル基、エチル基、プロピル基、ヘキシル基、ウンデシル基及びトリデシル基等が挙げられ、アリール基としてはフェニル基及びナフチル基等が挙げられ、芳香族炭化水素環としてはベンゼン基、ナフタレン基、フルオレン基、フェナンスレン基、アンスラセン基、フルオランテン基及びピレン基等が挙げられ、複素環としてはフラン基、チオフェン基、ピリジン基、インドール基、ベンゾチアゾール基、カルバゾール基、ベンゾカルバゾール基、アクリドン基、ジベンゾチオフェン基、ベンゾオキサゾール基、ベンゾトリアゾール基、オキサチアゾール基、チアゾール基、フェナジン基、シンノリン基及びベンゾシンノリン基等が挙げられ、複数の芳香族炭化水素環あるいは複素環を結合したものとしては、ビフェニル基、ターフェニル基、ビナフチル基、フルオレノン基、フェナンスレンキノン基、アンスラキノン基、ベンズアンスロン基、ジフェニルオキサゾール基及びフェニルベンズオキサゾール基等が挙げられる。
【００１３】
置換基としては、メチル基、エチル基、プロピル基及びブチル基等のアルキル基、フェニル基、ビフェニル基及びナフチル基等のアリール基、メトキシ基及びエトキシ基等のアルコキシ基、ジメチルアミノ基及びジエチルアミノ基等のジアルキルアミノ基、フェニルアミノ基及びジフェニルアミノ基等のアリールアミノ基、フッ素原子、塩素原子及び臭素原子等のハロゲン原子、ヒドロキシ基、ニトロ基、シアノ基及びハロメチル基等が挙げられる。
【００１４】
【発明の実施の形態】
以下に、本発明の実施の形態を詳細に示す。
【００１５】
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下記に示すが、本発明においては、これらの化合物に限定されるものではない。
【００１６】
【表１】

【００１７】
【表２】

【００１８】
【表３】

【００１９】
式（１）で示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 ｐ５３９７−５４０４）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等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カプリング反応により合成できる（文献例：ＣＨＥＭＩＳＴＲＹ ＬＥＴＴＥＲＳ，ｐｐ．１２１９−１２２２，１９９０）。
【００２０】
次に、レゾルシナレーン化合物の合成例を説明する。ここで示す「％」及び「部」は、それぞれ「質量％」及び「質量部」を意味する。
【００２１】
＜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時間処理した後で、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。得られた化合物の¹Ｈ−ＮＭＲ及びＩＲのデータを下記に示す。
【００２２】
¹Ｈ−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）
【００２３】
ＩＲ（ＫＢｒ）ｃｍ^-1
＝３５４８、３４９２、２９２４、２８５２、１６１８、１５０８、１４６５、１４３２、１３０２、１１９６、１１６７、９０３、８３７
【００２４】
＜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Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）３６０部に溶解させた溶液を０℃まで冷却した後、下記に示される化合物５．６部
【００２５】
【化４】

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。得られた化合物のＩＲのデータを下記に示す。
【００２６】
ＩＲ（ＫＢｒ）ｃｍ^-1
＝３１０１、２９２５、１５４２、１４９１、１３４２
【００２７】
本発明の電子写真感光体の層構成は、導電性支持体上に前記式（１）で示されるレゾルシナレーン化合物を含有する中間層を有し、該中間層上に電荷発生材料と電荷輸送材料を含有する感光層を有する層構成である。また、感光層上には必要に応じて保護層を設けてもよい。
【００２８】
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、ステンレス及びニッケル等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等が挙げられ、形状としては円筒状及びフィルム状等が挙げられる。
【００２９】
中間層は、導電性支持体上の欠陥の被覆、感光層の接着性付与、干渉縞の防止、感光層の電気的破壊に対する保護、導電性支持体から感光層へのホール注入の阻止等を目的に導電性支持体と感光層の間に設けられる。
【００３０】
中間層は、前記式（１）で示されるレゾルシナレーン化合物及び結着樹脂からなり、これらを溶剤に溶解又は分散して塗布液を作製し、塗工により薄層が設けられる。用いられる結着樹脂は特に限定されることはなく、例えば、フェノール樹脂、エポキシ樹脂、ポリウレタン、ポリカーボネート、ポリアリレート、ポリエステル、ポリアミド、ポリイミド、ポリアミドイミド、ポリアミド酸、ポリエチレン、ポリスチレン、スチレン−アクリル共重合体、アクリル樹脂、ポリメタクリレート、ポリビニルアルコール、ポリビニルアセタール、ポリビニルブチラール、ポリビニルホルマール、ポリアクリロニトリル、ポリアクリルアミド、アクリロニトリル−ブタジエン共重合体、ポリ塩化ビニル、塩化ビニル−酢酸ビニル共重合体、セルロース、メラミン樹脂、アミロース、アミロペクチン、ポリスルホン、ポリエーテルスルホン又はシリコーン樹脂等が適宜用いられ、一種もしくは二種以上のものを混合して用いることができる。これらの中でも、フェノール樹脂、ポリウレタン、ポリアミド、ポリイミド、ポリアミドイミド、ポリアミド酸、ポリビニルアセタール、ポリビニルブチラール、エポキシ樹脂、アクリル樹脂、セルロース樹脂、メラミン樹脂及びポリエステル等が好ましい。
【００３１】
また、中間層の体積抵抗や誘電率等の調整を行うために、導電性物質を含有させてもよい。導電性物質としては、アルミニウム粉末及び銅粉末等の金属、酸化アルミニウム、酸化スズ、酸化インジウム、酸化チタン、酸化ジルコニウム、酸化亜鉛、酸化珪素、酸化タンタル、酸化モリブデン及び酸化タングステン等の金属酸化物、ジルコニウムテトラ−ｎ−ブトキサイド、チタニウムテトラ−ｎ−ブトキサイド、アルミニウムイソプロポキシド及びメチルメトキシシラン等の有機金属化合物及びカーボンブラック等が挙げられる。更に、それらの混合物等も用いることができる。
【００３２】
また、中間層が前記導電性物質の少なくとも１種を含有する第１中間層と、前記結着樹脂の少なくとも１種を含有する第２中間層の積層からなり、第１中間層と第２中間層の両層に前記式（１）で示されるレゾルシナレーン化合物を含有させてもよい。
【００３３】
中間層を積層にする場合は、第１中間層上に第２中間層を形成してもよいし、第２中間層上に第１中間層を形成してもよい。
【００３４】
前記式（１）で示されるレゾルシナレーン化合物の含有量は中間層に対して０．０１質量％〜１００質量％であり、より好ましくは０．１質量％〜５０質量％である。１００質量％の場合には塗工性や塗布液の安定性が悪くなり好ましくない。また、０．０１質量％より少ない場合には前記式（１）で示されるレゾルシナレーン化合物の含有量が低くなり過ぎ、その効果が期待できなくなる。また、前記式（１）で示されるレゾルシナレーン化合物は、一種もしくは二種以上のものを混合して用いることができる。
【００３５】
中間層に用いる塗布液は、前記式（１）で示されるレゾルシナレーン化合物と結着樹脂を適当な溶剤に溶解又は分散させて得ることができる。
【００３６】
用いられる溶剤は特に限定されることはなく、例えば、ベンゼン、トルエン、キシレン、テトラリン、クロロベンゼン、ジクロロメタン、クロロホルム、トリクロロエチレン、テトラクロロエチレン、四塩化炭素、酢酸メチル、酢酸エチル、酢酸プロピル、ギ酸メチル、ギ酸エチル、アセトン、メチルエチルケトン、シクロヘキサノン、ジエチルエーテル、ジプロピルエーテル、ジオキサン、メチラール、テトラヒドロフラン、メタノール、エタノール、イソプロピルアルコール、ブチルアルコール、メチルセロソルブ、メトキシプロパノール、ジメチルホルムアミド、ジメチルアセトアミド及びジメチルスルホキシド等の溶剤を用いることができる。
【００３７】
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等の塗布方法が挙げられ、膜厚は０．０１〜３０μｍ程度が好ましく、特には０．１〜２０μｍが好ましい。
【００３８】
感光層には大きく次の２種類がある。一方は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とを積層した積層型感光層であり、もう一方は電荷発生材料と電荷輸送材料とを同一層中に分散又は溶解させた単層型感光層である。なお、積層型において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が、電子写真特性的には電荷発生層の上に電荷輸送層を積層した方が好ましい。
【００３９】
電荷発生材料としては、アゾ顔料又はフタロシアニン顔料を用いることが好ましい。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等いかなるアゾ顔料でも使用できるが、中でも特開昭５９−３１９６２号公報や特開平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、またゴーストも発生し易いので本発明が有効に作用し好ましい。
【００４０】
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、軸配位子を有してもよい金属フタロシアニン等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優れた感度を有しており、ゴーストも発生し易いので本発明が有効に作用し好ましい。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特に優れた感度特性を有しており、ゴーストも発生し易いので本発明が有効に作用し好ましい。
【００４１】
電荷輸送材料としては、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、トリアリルメタン系化合物、エナミン系化合物及びブタジエン系化合物等が挙げられる。
【００４２】
積層型からなる感光層を形成する場合、電荷発生層は、顔料と適当な溶剤及び結着樹脂を共に溶解又は分散させ、この塗布液を中間層上に塗布し乾燥して形成する方法が挙げられる。電荷輸送層は、主として電荷輸送材料と結着樹脂を溶剤中に溶解させた塗布液を電荷発生層上に塗布し、乾燥して形成される。
【００４３】
単層型からなる感光層は、顔料と電荷輸送材料を適当な溶剤及び結着樹脂に分散させて、この塗布液を中間層上に塗布し、乾燥することによって形成される。
【００４４】
感光層用の塗布液作製時に用いられる溶剤や結着樹脂は中間層の塗布液作製時で挙げたものと同様なものを用いることができる。感光層の塗布方法についても中間層で挙げた方法と同様の方法が用いられる。
【００４５】
感光層が積層型の場合、電荷発生層の膜厚は０．０１〜１０μｍであることが好ましく、特に０．０５〜５μｍであることが好ましく、電荷輸送層の膜厚は５〜４０μｍであることが好ましく、特に１０〜３０μｍであることが好ましい。感光層が単層型の場合、膜厚は５〜４０μｍであることが好ましく、特に１０〜３０μｍであることが好ましい。
【００４６】
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や変性ポリカーボネート等）、ポリアミド、ポリイミド、ポリアリレート、ポリウレタン、フェノール、スチレン−ブタジエンコポリマー、エチレン−アクリル酸コポリマー又はスチレン−アクリロニトリルコポリマー等の樹脂を適当な有機溶剤によって溶解し、感光層の上に塗布乾燥して形成される。保護層の膜厚は０．０５〜２０μｍが好ましい。また、保護層中に導電性粒子や紫外線吸収剤等を含有させてもよい。導電性粒子としては、例えば酸化スズ粒子等の金属酸化物が好ましい。
【００４７】
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備えた電子写真装置の概略構成を示す。
【００４８】
図１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（プロセススピード）をもって回転駆動される。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又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等の露光手段（不図示）から出力される目的の画像情報の時系列電気デジタル画像信号に対応して強度変調された露光光４を受ける。こうして電子写真感光体１の周面に対し、目的の画像情報に対応した静電潜像が順次形成されていく。
【００４９】
形成された静電潜像は、次いで現像手段５内の荷電粒子（トナー）で正規現像又は反転現像により可転写粒子像（トナー像）として顕画化され、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の回転と同期して取り出されて給送された転写材７に、電子写真感光体１の表面に形成担持されているトナー像が転写手段６により順次転写されていく。この時、転写手段にはバイアス電源（不図示）からトナーの保有電荷とは逆極性のバイアス電圧が印加される。
【００５０】
トナー画像の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像定着手段８へ搬送されてトナー像の定着処理を受けることにより画像形成物（プリント、コピー）として装置外へプリントアウトされる。
【００５１】
トナー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等の付着物の除去を受けて清浄面化される。近年、クリーナレスシステムも研究され、転写残りトナーを直接、現像器等で回収することもできる。更に、前露光手段（不図示）からの前露光光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。なお、一次帯電手段３が帯電ローラー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。
【００５２】
本発明においては、上述の電子写真感光体１、一次帯電手段３、現像手段５及びクリーニング手段９等の構成要素のうち、複数のものを容器に納めてプロセスカートリッジとして一体に結合して構成し、このプロセスカートリッジを複写機やレーザービームプリンター等の電子写真装置本体に対して着脱自在に構成してもよい。例えば、一次帯電手段３、現像手段５及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、装置本体のレール等の案内手段１２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。
【００５３】
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、この信号に従って行われるレーザービームの走査、ＬＥＤアレイの駆動又は液晶シャッターアレイの駆動等により照射される光である。
【００５４】
本発明の電子写真感光体は、電子写真複写機に利用するのみならず、レーザービームプリンター、ＣＲＴプリンター、ＬＥＤプリンター、ＦＡＸ、液晶プリンター及びレーザー製版等の電子写真応用分野にも幅広く適用し得るものである。
【００５５】
【実施例】
以下に、具体的な実施例を挙げて本発明を更に詳細に説明する。ただし、本発明の実施の形態は、これらに限定されるものではない。なお、実施例中の「％」及び「部」は、それぞれ「質量％」及び「質量部」を意味する。
【００５６】
（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、例示化合物Ｎｏ．１ １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、第１中間層用塗布液を調製した。アルミニウムシリンダー（直径３０ｍｍ×長さ２６０．５ｍｍ）上に、この塗布液を浸漬塗布し、１４０℃で３０分間乾燥させ、膜厚が１５μｍの第１中間層を形成した。
【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／ブタノール２５部の混合溶媒に溶解した溶液を第１中間層上に浸漬塗布し、膜厚が１μｍの第２中間層を形成した。
【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部とポリビニルブチラール樹脂（商品名：エスレックＢＸ−１、積水化学工業社製）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装置で３時間分散し、これに２５０部の酢酸エチルを添加して希釈し、この塗布液を第２中間層上に浸漬塗布し、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、下記に示される電荷輸送材料１０部、
【００６０】
【化５】

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、電子写真感光体を作製した。
【００６１】
（実施例２）
実施例１において例示化合物Ｎｏ．１ １部を例示化合物Ｎｏ．２ １部に代えた以外は、実施例１と全く同様にして実施例２の電子写真感光体を作製した。
【００６２】
（実施例３）
実施例１において例示化合物Ｎｏ．１ １部を例示化合物Ｎｏ．３ ５部に代えた以外は、実施例１と全く同様にして実施例３の電子写真感光体を作製した。
【００６３】
（実施例４）
実施例３において第１中間層には例示化合物Ｎｏ．３ ５部を含有させたままの状態で、更に第２中間層に例示化合物Ｎｏ．１５ ０．５部を含有させた以外は、実施例３と全く同様にして実施例４の電子写真感光体を作製した。
【００６４】
（実施例５）
実施例４において第１中間層に例示化合物Ｎｏ．３を含有させなかった以外は、実施例４と全く同様にして実施例５の電子写真感光体を作製した。
【００６５】
（比較例１）
実施例１において第１中間層に例示化合物Ｎｏ．１を含有させなかった以外は、実施例１と全く同様にして比較例１の電子写真感光体を作製した。
【００６６】
（実施例６）
ポリアミド樹脂（商品名：アミランＣＭ−８０００、東レ社製）５部、例示化合物Ｎｏ．４ ０．５部をメタノール６０部／ブタノール３０部の混合溶媒に溶解して直径１ｍｍガラスビーズを用いたサンドミル装置で１時間分散して中間層用塗布液を調製した。この塗布液をアルミニウムシリンダー（直径３０ｍｍ×長さ２６０．５ｍｍ）上に浸漬塗布し、膜厚が０．３μｍの中間層を形成した。
【００６７】
次に、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１０部とポリビニルブチラール樹脂（商品名：エスレックＢＸ−１、積水化学工業社製）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装置で３時間分散し、これに２５０部の酢酸エチルを添加して希釈し、この塗布液を中間層上に浸漬塗布し、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。
【００６８】
次に、下記に示される電荷輸送材料１０部、
【００６９】
【化６】

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、電荷発生層上に浸漬塗布し、１１０℃で１時間乾燥して、膜厚が２５μｍの電荷輸送層を形成し、実施例６の電子写真感光体を作製した。
【００７０】
（比較例２）
実施例６において中間層に例示化合物Ｎｏ．４を含有させなかった以外は、実施例６と全く同様にして比較例２の電子写真感光体を作製した。
【００７１】
（実施例７）
ポリアミド樹脂（商品名：アミランＣＭ−４０００、東レ社製）７部、二酸化チタン粉末（商品名：タイペークＲ−６７０、石原産業社製）１５部、例示化合物Ｎｏ．１９ ０．５部をメタノール５０部／イソプロピルアルコール２０部のの混合溶媒に溶解して直径１ｍｍのガラスビーズを用いたサンドミル装置で１時間分散して中間層用塗布液を調製した。この塗布液をアルミニウムシリンダー（直径３０ｍｍ×長さ２６０．５ｍｍ）上に浸漬塗布し、膜厚が０．７μｍの中間層を形成した。
【００７２】
次に、この中間層上に実施例６と同様にして電荷発生層と電荷輸送層を順次塗工し、実施例７の電子写真感光体を作製した。
【００７３】
（比較例３）
実施例７において中間層に例示化合物Ｎｏ．１９を含有させなかった以外は、実施例７と全く同様にして比較例３の電子写真感光体を作製した。
【００７４】
（比較例４）
実施例７において中間層に例示化合物Ｎｏ．１９ ０．５部を下記化合物に代えた以外は、実施例７と全く同様にして比較例４の電子写真感光体を作製した。
【００７５】
【化７】

【００７６】
（実施例８）
ヒドロキシプロピルセルロース（東京化成工業社製）７５部、ジルコニウムテトラ−ｎ−ブトキサイド（関東化学社製）２５部、例示化合物Ｎｏ．１０ １０部、アセチルアセトン１０部及び水５部をトルエン３００部／ブタノール３００部の混合溶媒に溶解、混合して塗布液を調製した。この塗布液をアルミニウムシリンダー（直径３０ｍｍ×長さ２６０．５ｍｍ）上に浸漬塗布し、膜厚が０．３μｍの中間層を形成した。
【００７７】
次に、この中間層上に実施例６と同様にして電荷発生層と電荷輸送層を順次塗工し、実施例８の電子写真感光体を作製した。
【００７８】
（比較例５）
実施例８において中間層に例示化合物Ｎｏ．１０を含有させなかった以外は、実施例８と全く同様にして比較例５の電子写真感光体を作製した。
【００７９】
これら作製した各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。評価機に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）を現像バイアスが可変できるように改造して使用した。
【００８０】
明部電位の測定は、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て行った。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、電子写真感光体軸方向のほぼ中央、電子写真感光体表面からのギャップを３ｍｍとした。画像データは全面黒画像とした。
【００８１】
ゴースト画像評価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）又は全面白画像とした。ゴースト画像サンプルは、３通りの現像バイアスボリューム、Ｆ１（濃度高い）、Ｆ５（中心値）、Ｆ９（濃度薄い）の各モードでサンプリングした。評価は目視で行い、ゴーストの程度で、
ランク１：いずれのモードでもゴーストは全く見えないレベル
ランク２：いずれかのモードでゴーストがうっすら見えるレベル
ランク３：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：いずれのモードでもゴーストが見えるレベル
のようにランク付けした。
【００８２】
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、同環境下で１分間４枚プリントの間欠モードで約０．５ｍｍ幅の線を縦１０ｍｍ間隔のパターンを印字するモードで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。
【００８３】
次に、作製した各電子写真感光体を評価機と共に、１５℃／１０％ＲＨの低温低湿（Ｌ／Ｌ）環境下で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。
【００８４】
以上の結果を表４に示す。
【００８５】
【表４】

【００８６】
【発明の効果】
上述のように、本発明の電子写真感光体は、連続プリント時における電位変動が少なく、ゴースト等の画像欠陥のない画像を提供できるという顕著な効果を奏する。また、この電子写真感光体を有するプロセスカートリッジならびに電子写真装置においても同様の効果を奏する。
【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備えた電子写真装置の概略構成の例を示す図である。
【符号の説明】
１ 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 案内手段[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member, a process cartridge, and an electrophotographic apparatus. More specifically, the present invention relates to an electrophotographic photosensitive member containing a specific resorcinarene compound in an intermediate layer, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus. .
[0002]
[Prior art]
Organic electrophotographic photoreceptors have the advantage that they are non-polluting and easy to manufacture compared to conventional inorganic electrophotographic photoreceptors, and the degree of freedom in functional design is high due to the variety of selection of constituent materials. Due to the rapid spread of laser beam printers in recent years, it has become widely used in the market.
[0003]
There are two major types of photosensitive layers of organic electrophotographic photoreceptors. One is a laminated photosensitive layer in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are laminated, and the other is a dispersion or dispersion of the charge generation material and the charge transport material in the same layer. It is a dissolved single-layer type photosensitive layer.
[0004]
Between the conductive support and the photosensitive layer, coating of defects on the conductive support, imparting adhesion of the photosensitive layer, prevention of interference fringes, protection against electrical breakdown of the photosensitive layer, from the conductive support to the photosensitive layer In many cases, an intermediate layer is provided for the purpose of preventing hole injection into the substrate.
[0005]
This intermediate layer has the above-mentioned merit, but also has a demerit that charges are easily accumulated. For this reason, the potential fluctuation becomes large during continuous printing, causing image defects. For example, when used in a development process (a so-called reversal development system) in which a dark portion potential portion that is currently widely used in printers is a non-development portion and a light portion potential portion is a development portion (so-called reversal development system), When the light is exposed to light at the time of printing, the sensitivity becomes faster, and when a whole white image is taken at the time of the next printing, a so-called ghost phenomenon (positive ghost) in which the previous printed portion is blackened appears remarkably.
[0006]
On the other hand, the sensitivity of light exposure at the time of the previous printing is slowed by the rise of the bright part potential, and if the entire black image is taken at the time of the next printing, the so-called ghost phenomenon (negative ghost) that the white part of the previous printing will appear is remarkable. Will appear.
[0007]
Various methods have been proposed in order to improve the durability by reducing the potential fluctuation due to the increase in the residual potential or the decrease in the initial potential during continuous printing when the intermediate layer is provided. For example, a polycyclic quinone pigment is contained in JP-A-9-258468, a perylene pigment is contained in JP-A-9-15889, and a naphthalenetetracarboxylic acid diimide compound is incorporated in JP-A-5-27469. Although an electrophotographic photoreceptor is disclosed, it has not been completely solved.
[0008]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member that supplies an image free from image defects such as ghosts with little potential fluctuation during continuous printing, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member. .
[0009]
[Means for Solving the Problems]
According to the present invention, in an electrophotographic photosensitive member having a photosensitive layer containing a charge generation material and a charge transport material on a conductive support, an intermediate layer provided between the conductive support and the photosensitive layer has the following formula ( An electrophotographic photoreceptor comprising the resorcinarene compound represented by 1), a process cartridge and an electrophotographic apparatus having the electrophotographic photoreceptor are provided.
[0010]
[Chemical Formula 3]

[0011]
Where R₁Represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent, and R₂Represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group or an Ar—N═N— group, and Ar is the same or different and may have an aromatic hydrocarbon ring which may have a substituent; A monovalent group of a heterocyclic ring which may have a group or a plurality of aromatic hydrocarbon rings which may have a substituent or a plurality of heterocyclic rings which may have a substituent is bonded.
[0012]
  In the present invention, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, an undecyl group, and a tridecyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Benzene group, naphthalene group, fluorene group, phenanthrene group, anthracene group, fluoranthene group, pyrene group, etc., and the heterocyclic ring includes furan group, thiophene group, pyridine group, indole group, benzothiazole group, carbazole group, benzol group. Carbazole group, acridone group, dibenzothiophene group, benzoxazole group, benzotriazole group, oxathiazole group, thiazole group, phenazine group, cinnoline group, benzocinnoline group, etc., and multiple aromatic hydrocarbon rings or heterocyclic rings Combined with TeIsBiphenyl, terphenyl, binaphthyl, fluorenone, phenanthrenequinone, anthraquinone, benzanthrone, diphenyloxazoleas well asPhenylbenzoxazoleBasicsIs mentioned.
[0013]
Substituents 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, dimethylamino and diethylamino And dialkylamino groups such as phenylamino group and diphenylamino group, halogen atoms such as fluorine atom, chlorine atom and bromine atom, hydroxy group, nitro group, cyano group and halomethyl group.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0015]
Examples of resorcinarene compounds used in the present invention are shown below, but the present invention is not limited to these compounds.
[0016]
[Table 1]

[0017]
[Table 2]

[0018]
[Table 3]

[0019]
The resorcinol compound represented by the formula (1) can be prepared from resorcinol derivatives and various aldehyde compounds as described in known examples (for example, J. Am. Chem. Soc., Vol. 111, No. 14, 1989 p5397-5404). It can be synthesized by dehydration condensation using acids such as sulfuric acid and hydrochloric acid. In addition, R₂The method of introducing an azo group into R₂Can be synthesized by an azo coupling reaction between a resorcinarene compound of hydrogen and a diazo compound derivative (literature example: CHEMISTRY LETTERS, pp. 1219-1222, 1990).
[0020]
Next, a synthesis example of a resorcinarene compound will be described. Here, “%” and “part” mean “% by mass” and “part by mass”, respectively.
[0021]
<Synthesis Example 1 ... Synthesis of Exemplified Compound 15>
In a nitrogen atmosphere, add 25.6 parts of resorcinol, 42.3 parts of dodecyl aldehyde and 230 parts of ethanol to an eggplant flask equipped with a condenser, add 37 parts of concentrated hydrochloric acid, and treat at 70 ° C. for 10 hours. After cooling, the resulting crystals were sufficiently washed with hot water, dried, and recrystallized with methanol to obtain 17.3 parts of Exemplified Compound 15 as white crystals. Of the resulting compound¹H-NMR and IR data are shown below.
[0022]
¹H-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)
[0023]
IR (KBr) cm^-1
= 3548, 3492, 2924, 2852, 1618, 1508, 1465, 1432, 1302, 1196, 1167, 903, 837
[0024]
<Synthesis Example 2 ... Synthesis of Exemplified Compound 1>
Under a nitrogen atmosphere, a solution prepared by dissolving 4.4 parts of Exemplified Compound 15 in 360 parts of N, N-dimethylformamide (DMF) was cooled to 0 ° C., and then 5.6 parts of the compound shown below.
[0025]
[Formula 4]

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. IR data of the obtained compound are shown below.
[0026]
IR (KBr) cm^-1
= 3101, 2925, 1542, 1491, 1342
[0027]
The layer structure of the electrophotographic photoreceptor of the present invention has an intermediate layer containing a resorcinarene compound represented by the above formula (1) on a conductive support, and a charge generation material and a charge transport material are formed on the intermediate layer. It is a layer structure which has the photosensitive layer to contain. Further, a protective layer may be provided on the photosensitive layer as necessary.
[0028]
The support may be any material as long as it has conductivity, and examples thereof include metals such as aluminum, stainless steel, and nickel, or metals provided with a conductive layer, plastic, paper, and the like, and examples of the shape include a cylindrical shape and a film shape. It is done.
[0029]
The intermediate layer covers defects on the conductive support, imparts adhesion to the photosensitive layer, prevents interference fringes, protects against electrical breakdown of the photosensitive layer, blocks holes from the conductive support to the photosensitive layer, etc. For the purpose, it is provided between the conductive support and the photosensitive layer.
[0030]
The intermediate layer is composed of a resorcinarene compound represented by the formula (1) and a binder resin, and these are dissolved or dispersed in a solvent to prepare a coating solution, and a thin layer is provided by coating. The binder resin to be used is not particularly limited. For example, phenol resin, epoxy resin, polyurethane, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyamideimide, polyamic acid, polyethylene, polystyrene, styrene-acrylic copolymer Polymer, acrylic resin, polymethacrylate, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, polyvinyl formal, polyacrylonitrile, polyacrylamide, acrylonitrile-butadiene copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, cellulose, melamine resin , Amylose, amylopectin, polysulfone, polyethersulfone, silicone resin, etc. are used as appropriate, and one kind or two or more kinds are mixed. It can be used. Among these, phenol resin, polyurethane, polyamide, polyimide, polyamideimide, polyamic acid, polyvinyl acetal, polyvinyl butyral, epoxy resin, acrylic resin, cellulose resin, melamine resin, and polyester are preferable.
[0031]
Moreover, in order to adjust the volume resistance, dielectric constant, etc. of the intermediate layer, a conductive substance may be contained. Examples of the conductive material include metals such as aluminum powder and copper powder, metal oxides such as aluminum oxide, tin oxide, indium oxide, titanium oxide, zirconium oxide, zinc oxide, silicon oxide, tantalum oxide, molybdenum oxide and tungsten oxide, Examples thereof include zirconium tetra-n-butoxide, titanium tetra-n-butoxide, organometallic compounds such as aluminum isopropoxide and methylmethoxysilane, and carbon black. Further, a mixture thereof can also be used.
[0032]
Further, the intermediate layer includes a first intermediate layer containing at least one kind of the conductive material and a second intermediate layer containing at least one kind of the binder resin, and the first intermediate layer and the second intermediate layer You may make the both layers of a layer contain the resorcinarene compound shown by said Formula (1).
[0033]
When the intermediate layer is laminated, the second intermediate layer may be formed on the first intermediate layer, or the first intermediate layer may be formed on the second intermediate layer.
[0034]
The content of the resorcinarene compound represented by the formula (1) is 0.01% by mass to 100% by mass, and more preferably 0.1% by mass to 50% by mass with respect to the intermediate layer. In the case of 100% by mass, the coating property and the stability of the coating solution are deteriorated, which is not preferable. On the other hand, when the content is less than 0.01% by mass, the content of the resorcinarene compound represented by the formula (1) becomes too low, and the effect cannot be expected. In addition, the resorcinarenes represented by the formula (1) can be used singly or in combination of two or more.
[0035]
The coating solution used for the intermediate layer can be obtained by dissolving or dispersing the resorcinarene compound represented by the formula (1) and the binder resin in a suitable solvent.
[0036]
The solvent used is not particularly limited. For example, benzene, toluene, xylene, tetralin, chlorobenzene, dichloromethane, chloroform, trichloroethylene, tetrachloroethylene, carbon tetrachloride, methyl acetate, ethyl acetate, propyl acetate, methyl formate, ethyl formate Use solvents such as acetone, methyl ethyl ketone, cyclohexanone, diethyl ether, dipropyl ether, dioxane, methylal, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, butyl alcohol, methyl cellosolve, methoxypropanol, dimethylformamide, dimethylacetamide and dimethylsulfoxide Can do.
[0037]
Examples of the coating method include coating methods such as a dipping method, a spray coating method, a spinner coating method, a bead coating method, a blade coating method, and a beam coating method. The film thickness is preferably about 0.01 to 30 μm, particularly 0. .1 to 20 μm is preferable.
[0038]
There are the following two types of photosensitive layers. One is a laminated photosensitive layer in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are laminated, and the other is a dispersion or dispersion of the charge generation material and the charge transport material in the same layer. It is a dissolved single-layer type photosensitive layer. In the stacked type, the stacking relationship between the charge generation layer and the charge transport layer may be reversed, but it is preferable to stack the charge transport layer on the charge generation layer in terms of electrophotographic characteristics.
[0039]
As the charge generation material, an azo pigment or a phthalocyanine pigment is preferably used. As the azo pigment used, any azo pigment such as bisazo, trisazo, and tetrakisazo can be used. Among them, benzanthrone-based azo pigments disclosed in JP-A-59-31962 and JP-A-1-183663 are exemplified. Since the present invention has excellent sensitivity characteristics and ghosts are easily generated, the present invention is effective and preferable.
[0040]
In addition, as the phthalocyanine pigment, any phthalocyanine such as metal-free phthalocyanine or metal phthalocyanine which may have an axial ligand may be used and may have a substituent, but oxytitanium phthalocyanine and gallium phthalocyanine are particularly excellent. Since the present invention has sensitivity and ghosts are easily generated, the present invention is effective and 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, CuKα Characteristic with Strong Peaks at 7.4 °, 16.6 °, 25.5 ° and 28.3 ° with Bragg Angle 2θ ± 0.2 ° in X-ray Diffraction The crystalline form of oxytitanium phthalocyanine having a strong peak at 27.2 ° ± 0.2 ° with a Bragg angle 2θ in X-ray diffraction has particularly excellent sensitivity characteristics, and ghosts are easily generated, so that the present invention is effective. This is preferable.
[0041]
Examples of the charge transport material include triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, triallylmethane compounds, enamine compounds, butadiene compounds, and the like.
[0042]
In the case of forming a laminate type photosensitive layer, the charge generation layer may be formed by dissolving or dispersing a pigment, a suitable solvent and a binder resin together, applying this coating solution on the intermediate layer and drying it. It is done. The charge transport layer is formed by applying a coating solution in which a charge transport material and a binder resin are mainly dissolved in a solvent, and applying and drying the coating solution.
[0043]
A photosensitive layer of a single layer type is formed by dispersing a pigment and a charge transport material in an appropriate solvent and a binder resin, applying this coating solution on the intermediate layer, and drying.
[0044]
As the solvent and the binder resin used in preparing the coating solution for the photosensitive layer, the same ones as mentioned in the preparation of the coating solution for the intermediate layer can be used. As for the coating method of the photosensitive layer, the same methods as those mentioned for the intermediate layer are used.
[0045]
When the photosensitive layer is a laminate type, the thickness of the charge generation layer is preferably 0.01 to 10 μm, particularly preferably 0.05 to 5 μm, and the thickness of the charge transport layer is 5 to 40 μm. It is preferable that it is 10-30 micrometers especially. When the photosensitive layer is a single layer type, the film thickness is preferably 5 to 40 μm, and particularly preferably 10 to 30 μm.
[0046]
A protective layer may be provided on the photosensitive layer as necessary. For the protective layer, a resin such as polyvinyl butyral, polyester, polycarbonate (polycarbonate Z, modified polycarbonate, etc.), polyamide, polyimide, polyarylate, polyurethane, phenol, styrene-butadiene copolymer, ethylene-acrylic acid copolymer or styrene-acrylonitrile copolymer is suitable. It is dissolved in an organic solvent and applied and dried on the photosensitive layer. 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.
[0047]
FIG. 1 shows a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.
[0048]
In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 in a direction indicated by an arrow with a predetermined peripheral speed (process speed). In the rotating process, the electrophotographic 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 from an exposure unit (not shown) such as slit exposure or laser beam scanning exposure. The exposure light 4 subjected to intensity modulation corresponding to the time-series electric digital image signal of the target image information to be output is received. In this way, electrostatic latent images corresponding to the target image information are sequentially formed on the peripheral surface of the electrophotographic photoreceptor 1.
[0049]
The formed electrostatic latent image is visualized as a transferable particle image (toner image) by regular development or reversal development with charged particles (toner) in the developing means 5 and is electrophotographic from a paper supply unit (not shown). A toner image formed and carried on the surface of the electrophotographic photosensitive member 1 is transferred to the transfer material 7 which is taken out and fed between the photosensitive member 1 and the transfer unit 6 in synchronization with the rotation of the electrophotographic photosensitive member 1. The images are sequentially transferred by the transfer means 6. At this time, a bias voltage having a polarity opposite to the charge held in the toner is applied to the transfer means from a bias power source (not shown).
[0050]
The transfer material 7 that has received the transfer of the toner image is separated from the surface of the electrophotographic photosensitive member, conveyed to the image fixing means 8, and subjected to a toner image fixing process to be printed out of the apparatus as an image formed product (print, copy). Be out.
[0051]
The surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by removing the deposits such as residual toner by the cleaning means 9. In recent years, a cleanerless system has been studied, and the transfer residual toner can be directly collected by a developing device or the like. Further, after being subjected to charge removal processing by pre-exposure light 10 from pre-exposure means (not shown), it is 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 always necessary.
[0052]
In the present invention, among the above-described components such as the electrophotographic photosensitive member 1, the primary charging unit 3, the developing unit 5 and the cleaning unit 9, a plurality of components are housed in a container and integrally combined as a process cartridge. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the electrophotographic photosensitive member 1 to form a cartridge, and is attached to and detached from the apparatus main body using the guide unit 12 such as a rail of the apparatus main body. A flexible process cartridge 11 can be obtained.
[0053]
Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is reflected or transmitted light from the original, or the original is read by a sensor and converted into a signal, and a laser beam scanning performed according to this signal is performed. The light emitted by driving the LED array or the liquid crystal shutter array.
[0054]
The electrophotographic photosensitive member of the present invention can be used not only for electrophotographic copying machines but also widely applicable to electrophotographic application fields such as laser beam printers, CRT printers, LED printers, FAX, liquid crystal printers, and laser plate making. It is.
[0055]
【Example】
Hereinafter, the present invention will be described in more detail with reference to specific examples. However, embodiments of the present invention are not limited to these. In the examples, “%” and “part” mean “% by mass” and “part by mass”, respectively.
[0056]
(Example 1)
50 parts of titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of resol type phenolic resin, Exemplified Compound No. 1 1 part, 20 parts of methyl cellosolve, 5 parts of methanol and 0.002 part of silicone oil (polydimethylsiloxane / polyoxyalkylene copolymer, average molecular weight 3000) were dispersed for 2 hours in a sand mill using 1 mm diameter glass beads. Thus, a first intermediate layer coating solution was prepared. This coating solution was dip-coated on an aluminum cylinder (diameter 30 mm × length 260.5 mm) and dried at 140 ° C. for 30 minutes to form a first intermediate layer having a thickness of 15 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 / 25 parts of butanol was dip-coated on the first intermediate layer, and the film thickness was 1 μm. The second intermediate layer was formed.
[0058]
Next, the Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction are 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 °. A sand mill using glass beads having a diameter of 1 mm, adding 10 parts of crystalline hydroxygallium phthalocyanine having a strong peak and 5 parts of polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) to 250 parts of cyclohexanone. Disperse in an apparatus for 3 hours, add 250 parts of ethyl acetate and dilute it, dip coat this coating solution on the second intermediate layer, dry at 100 ° C. for 10 minutes, and have a film thickness of 0.16 μm. The charge generation layer was formed.
[0059]
Next, 10 parts of the charge transport material shown below,
[0060]
[Chemical formula 5]

A solution in which 10 parts of a polycarbonate resin (trade name: Iupilon Z-200, manufactured by Mitsubishi Gas Chemical Company) was dissolved in 70 parts of monochlorobenzene was prepared, dip-coated on the charge generation layer, dried at 110 ° C. for 1 hour, A charge transport layer having a thickness of 25 μm was formed to produce an electrophotographic photosensitive member.
[0061]
(Example 2)
In Example 1, Exemplified Compound No. 1 1 part was added to Exemplified Compound No. 1 2 An electrophotographic photoreceptor of Example 2 was produced in exactly the same manner as in Example 1 except that 1 part was used.
[0062]
(Example 3)
In Example 1, Exemplified Compound No. 1 1 part 35 An electrophotographic photoreceptor of Example 3 was produced in exactly the same manner as in Example 1 except that the amount was changed to 5 parts.
[0063]
(Example 4)
In Example 3, Exemplified Compound No. 1 was used for the first intermediate layer. 3 In the state of containing 5 parts, the exemplified compound No. 1 was further added to the second intermediate layer. 15 An electrophotographic photosensitive member of Example 4 was produced in the same manner as in Example 3 except that 0.5 part was contained.
[0064]
(Example 5)
In Example 4, Exemplified Compound No. 1 was used for the first intermediate layer. An electrophotographic photoreceptor of Example 5 was produced in the same manner as Example 4 except that 3 was not included.
[0065]
(Comparative Example 1)
In Example 1, Exemplified Compound No. 1 was used for the first intermediate layer. An electrophotographic photosensitive member of Comparative Example 1 was produced in the same manner as in Example 1 except that 1 was not contained.
[0066]
(Example 6)
Polyamide resin (trade name: Amilan CM-8000, manufactured by Toray Industries, Inc.) 5 parts, Exemplified Compound No. 4 0.5 part was dissolved in a mixed solvent of 60 parts of methanol / 30 parts of butanol and dispersed for 1 hour in a sand mill apparatus using glass beads having a diameter of 1 mm to prepare an intermediate layer coating solution. This coating solution was dip-coated on an aluminum cylinder (diameter 30 mm × length 260.5 mm) to form an intermediate layer having a film thickness of 0.3 μm.
[0067]
Next, crystalline oxytitanium phthalocyanine having strong peaks at 9.0 °, 14.2 °, 23.9 °, and 27.1 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction 10 parts 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, and dispersed in a sand mill apparatus using glass beads having a diameter of 1 mm for 3 hours. A portion of ethyl acetate was added for dilution, and this coating solution was dip-coated on the intermediate layer and dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.16 μm.
[0068]
Next, 10 parts of the charge transport material shown below,
[0069]
[Chemical 6]

A solution in which 10 parts of a polycarbonate resin (trade name: Iupilon Z-400, manufactured by Mitsubishi Gas Chemical Company) was dissolved in 70 parts of monochlorobenzene was prepared, dip-coated on the charge generation layer, and dried at 110 ° C. for 1 hour. A charge transport layer having a thickness of 25 μm was formed, and an electrophotographic photosensitive member of Example 6 was produced.
[0070]
(Comparative Example 2)
In Example 6, the exemplary compound No. An electrophotographic photosensitive member of Comparative Example 2 was produced in the same manner as in Example 6 except that 4 was not included.
[0071]
(Example 7)
7 parts of polyamide resin (trade name: Amilan CM-4000, manufactured by Toray Industries, Inc.), 15 parts of titanium dioxide powder (trade name: Taipei R-670, manufactured by Ishihara Sangyo Co., Ltd.), Exemplified Compound No. 19 0.5 part was dissolved in a mixed solvent of 50 parts of methanol / 20 parts of isopropyl alcohol and dispersed for 1 hour in a sand mill using glass beads having a diameter of 1 mm to prepare a coating solution for an intermediate layer. This coating solution was dip-coated on an aluminum cylinder (diameter 30 mm × length 260.5 mm) to form an intermediate layer having a thickness of 0.7 μm.
[0072]
Next, a charge generation layer and a charge transport layer were sequentially coated on the intermediate layer in the same manner as in Example 6 to produce an electrophotographic photoreceptor of Example 7.
[0073]
(Comparative Example 3)
In Example 7, Exemplified Compound No. An electrophotographic photosensitive member of Comparative Example 3 was produced in the same manner as in Example 7 except that 19 was not contained.
[0074]
(Comparative Example 4)
In Example 7, Exemplified Compound No. 19 An electrophotographic photosensitive member of Comparative Example 4 was produced in the same manner as in Example 7 except that 0.5 part was replaced with the following compound.
[0075]
[Chemical 7]

[0076]
(Example 8)
Hydroxypropyl cellulose (manufactured by Tokyo Chemical Industry Co., Ltd.) 75 parts, zirconium tetra-n-butoxide (manufactured by Kanto Chemical Co., Inc.) 25 parts, Exemplified Compound No. 10 parts, 10 parts of acetylacetone and 5 parts of water were dissolved and mixed in a mixed solvent of 300 parts of toluene / 300 parts of butanol to prepare a coating solution. This coating solution was dip-coated on an aluminum cylinder (diameter 30 mm × length 260.5 mm) to form an intermediate layer having a film thickness of 0.3 μm.
[0077]
Next, a charge generation layer and a charge transport layer were sequentially coated on the intermediate layer in the same manner as in Example 6 to produce an electrophotographic photoreceptor of Example 8.
[0078]
(Comparative Example 5)
In Example 8, the exemplified compound No. An electrophotographic photoreceptor of Comparative Example 5 was produced in exactly the same manner as Example 8 except that 10 was not included.
[0079]
Using each of the electrophotographic photoreceptors thus produced, bright part potential measurement and ghost image evaluation were performed. A laser beam printer (trade name: Laser Jet 4000, manufactured by Hewlett Packard) was used as the evaluation machine with modification so that the developing bias could be varied.
[0080]
The light portion potential was measured by removing the developing cartridge from the evaluator and inserting a potential measuring device there. The potential measuring device is configured by arranging a potential measuring probe at the developing position of the developing cartridge, and the position of the potential measuring probe with respect to the electrophotographic photosensitive member is substantially in the center in the axial direction of the electrophotographic photosensitive member. The gap from the body surface was 3 mm. The image data was a full black image.
[0081]
The ghost image evaluation was as follows. The ghost image was printed as an arbitrary number of 5 mm square black square patterns for one round of the drum, and then an entire halftone image (an image having a dot density of one dot and one space) or an entire white image. The ghost image sample was sampled in each of three development bias volumes, F1 (high density), F5 (center value), and F9 (low density) modes. The evaluation is made visually, and the degree of ghost is
Rank 1: Level in which no ghost is visible in any mode
Rank 2: Level at which ghosts can be seen slightly in either mode
Rank 3: A level where you can see a ghost in any mode.
Rank 4: Level at which ghosts can be seen in any mode
Ranked as follows.
[0082]
After measuring the initial bright area potential and ghost image evaluation under 23 ° C / 55% RH environment, lines of about 0.5mm width were separated at 10mm length in the intermittent mode of 4 prints per minute under the same environment. A 1,000 sheet passing durability test was performed in a mode for printing the pattern, and the bright part potential was measured immediately after the durability and 15 hours later, and the ghost image was evaluated.
[0083]
Next, each produced electrophotographic photosensitive member is allowed to stand together with an evaluation machine in a low-temperature and low-humidity (L / L) environment at 15 ° C./10% RH for 3 days, and then the bright part potential is measured and the ghost image is evaluated. It was.
[0084]
The results are shown in Table 4.
[0085]
[Table 4]

[0086]
【The invention's effect】
As described above, the electrophotographic photosensitive member of the present invention has a remarkable effect that it can provide an image free from image defects such as ghosts with little potential fluctuation during continuous printing. In addition, the same effect can be obtained in the process cartridge and the electrophotographic apparatus having the electrophotographic photosensitive member.
[Brief description of the drawings]
FIG. 1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having the electrophotographic photosensitive member of the present invention.
[Explanation of symbols]
1 Electrophotographic photoreceptor
2 axis
3 Charging means
4 exposure light
5 Development means
6 Transfer means
7 Transfer material
8 Fixing means
9 Cleaning means
10 Pre-exposure light
11 Process cartridge
12 Guide means

Claims (10)

In an electrophotographic photoreceptor having a photosensitive layer containing a charge generation material and a charge transport material on a conductive support, an intermediate layer provided between the conductive support and the photosensitive layer is represented by the following formula (1). An electrophotographic photoreceptor comprising a resorcinarene compound.

(In the formula, R ₁ represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent, and R ₂ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group or Ar—N═ An N-group, Ar is the same or different, an aromatic hydrocarbon ring which may have a substituent, a heterocyclic ring which may have a substituent, or a plurality of aromatics which may have a substituent A monovalent group consisting of a hydrocarbon ring or a plurality of heterocyclic rings which may have a substituent. The electrophotographic photoreceptor according to claim 1, wherein the resorcinarene compound is a compound represented by the following formula (2).

(Wherein R ₁ represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent, Ar represents the same or different, an aromatic hydrocarbon ring which may have a substituent, a substituent; A monovalent group of a plurality of aromatic hydrocarbon rings which may have a substituent or a plurality of aromatic hydrocarbon rings which may have a substituent or a plurality of heterocyclic rings which may have a substituent; As the binder resin of the intermediate layer, at least one selected from the group consisting of phenol resin, polyurethane, polyamide, polyimide, polyamideimide, polyamic acid, polyvinyl acetal, polyvinyl butyral, epoxy resin, acrylic resin, cellulose resin, melamine resin and polyester The electrophotographic photosensitive member according to claim 1, comprising a seed. The electrophotographic photosensitive member according to claim 1, wherein the intermediate layer contains a conductive substance. A first intermediate layer containing a conductive substance and a binder resin such as phenol resin, polyurethane, polyamide, polyimide, polyamideimide, polyamic acid, polyvinyl acetal, polyvinyl butyral, epoxy resin, acrylic resin, cellulose resin, melamine resin, and In an electrophotographic photosensitive member having a laminated intermediate layer composed of a second intermediate layer containing at least one selected from the group consisting of polyesters, both the first intermediate layer and the second intermediate layer are represented by the above formula (1). The electrophotographic photosensitive member according to claim 1, comprising a resorcinarene compound. The electrophotographic photoreceptor according to claim 1, wherein the conductive material is at least one selected from the group consisting of metals, organometallic compounds, metal oxides, and carbon black. The electrophotographic photosensitive member according to claim 6, wherein the organometallic compound is at least one selected from the group consisting of zirconium tetra-n-butoxide, titanium tetra-n-butoxide, aluminum isopropoxide, and methylmethoxysilane. The electrophotographic photosensitive member according to claim 6, wherein the metal oxide is at least one selected from the group consisting of titanium oxide, tin oxide, and aluminum oxide. The electrophotographic photosensitive member according to claim 1, a charging means for charging the electrophotographic photosensitive member, a developing means for developing the electrophotographic photosensitive member on which an electrostatic latent image is formed, and a transfer step. A process cartridge which is integrally supported together with at least one means selected from the group consisting of cleaning means for collecting toner remaining on a later electrophotographic photosensitive member and is detachable from an electrophotographic apparatus main body. An electrophotographic photosensitive member according to any one of claims 1 to 8, a charging unit for charging the electrophotographic photosensitive member, an exposure unit for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, An electrophotographic apparatus comprising: a developing unit that develops toner on an electrophotographic photosensitive member on which a latent image is formed; and a transfer unit that transfers a toner image on the electrophotographic photosensitive member onto a transfer material.

Images