JP3789075B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

【００１４】
式（１）中、ｎは４〜８の整数を示し、Ｒ_１は同一または異なって、水素原子、置換基を有してもよいアルキル基を示し、少なくとも１つは置換基を有してもよいアルキル基を示し、Ｒ_２は同一または異なって、水素原子または置換基を有してもよいアルキル基を示し、Ａｒは同一または異なって、置換基を有してもよい芳香族炭化水素環または置換基を有してもよい複素環、また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。
【００１５】
また、本発明にしたがって、上記電子写真感光体、および帯電手段、現像手段およ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１つの手段を一体に支持し、電子写真装置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が提供される。
【００１６】
さらに、本発明にしたがって、上記電子写真感光体、帯電手段、露光手段、現像手段および転写手段を有することを特徴とする電子写真装置が提供される。
【００１７】
【発明の実施の形態】
本発明に用いられるアゾ化カリックス［ｎ］アレーン化合物は、下記式（１）で示される。
【００１８】
【外４】

【００１９】
式（１）中、ｎは４〜８の整数を示し、Ｒ_１は同一または異なって、水素原子、置換基を有してもよいアルキル基を示し、少なくとも１つは置換基を有してもよいアルキル基を示し、Ｒ_２は同一または異なって、水素原子または置換基を有してもよいアルキル基を示し、Ａｒは同一または異なって、置換基を有してもよい芳香族炭化水素環または置換基を有してもよい複素環、また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。
【００２０】
上記表現のアルキル基としてはメチル、エチル、プロピルおよびブチルなどの基が挙げられるが、Ｒ_２は水素原子であることが特に好ましい。
【００２１】
また、上記表現の芳香族炭化水素環または複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、フルオランテンおよびピレンなどの炭化水素系芳香環、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、シンノリンおよびベンゾシンノリンなどの複素環、さらに上記芳香環または複素環を直接あるいは芳香族性基または非芳香族性基で結合したものとしては、例えば、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およびテトラフェニルベンジジンなどが挙げられる。
【００２２】
Ａｒはベンゼン環に電子求引性を有するシアノ基、ニトロ基、カルボキシル基、ハロゲン原子が結合した基が特に好ましい。
【００２３】
前記各基が有してもよい置換基としては、メチル、エチル、プロピルおよびブチルなどのアルキル基、メトキシおよびエトキシなどのアルコキシ基、ジメチルアミノおよびジエチルアミノなどのジアルキルアミノ基、メトキシカルボニルおよびエトキシカルボニルなどのアルコキシカルボニル基、フッ素原子、塩素原子および臭素原子などのハロゲン原子、ヒドロキシ基、ニトロ基、シアノ基またはハロメチル基などが挙げられる。
【００２４】
なお、式（１）において、ｎが４〜８であり、４〜８個のＲ_１およびＡｒ、８〜１６個あるＲ_２はそれぞれ同一でも異なっていてもよい。
【００２５】
次に、本発明において用いられるアゾ化カリックス［ｎ］アレーン化合物の例を表１〜表５に示すが、本発明は、これらに限定されるものではない。
【００２６】
表１〜表４の基本型Ｉ｛式（１）で示される化合物｝
【００２７】
【外５】

【００２８】
【表１】

【００２９】
【表２】

【００３０】
【表３】

【００３１】
【表４】

【００３２】
表５の基本型ＩＩＩ｛式（１）で示される化合物｝
【００３３】
【外６】

【００３４】
【表５】

【００３５】
これらの中では、例示化合物１〜１２および２４が好ましく、さらには、例示化合物１、３および９が好ましい。その中でも特に、例示化合物１が好ましい。
【００３６】
式（１）で示されるアゾ化カリックス［ｎ］アレーン化合物は、式（１）においてＲ_１が水素であるアゾ化カリックス［ｎ］アレーン化合物のフェノール性ＯＨをアルカリの存在下ハロゲン化アルキルと処理することにより合成でき、導入したいアルキルの種類およびアルキル化度はアルカリの種類、ハロゲン化アルキルの量および反応条件によりコントロールすることができる。アルキルとしては、水素化ナトリウム、水酸化カリウム、水酸化ナトリウム、炭酸カリウム、炭酸ナトリウム、水酸化バリウムおよび炭酸セシウムなどが挙げられ、ハロゲン化アルキルとしては、ヨードメタン、ヨードエタン、１−ヨードプロパン、１−ブロモプロパン、２−ヨードプロパン、１−ヨードブタン、ブロモ酢酸エチル、４−ブロモ酪酸エチルおよびクロロメチルメチルエーテルなどが挙げられる。
【００３７】
この方法以外にもジアゾメタンで処理する方法、ジメチル硫酸／水酸化バリウムを用いる方法で合成することができる。
【００３８】
以下、「部」は、「質量部」を意味する。
【００３９】
合成例
＜例示化合物１の合成＞
窒素雰囲気下、下記化合物１０部をＮ，Ｎ−ジメチルホルムアミド５００部に分散させた後、
【００４０】
【外７】

【００４１】
水酸化バリウム８水和物９．５部、酸化バリウム８．９部を加え、４０℃で３０分間攪拌させた。その溶液の中に１−ヨードプロパン５１部を滴下し、そのままの温度で２時間攪拌した後、１Ｎ−塩酸５０００部に注加し、クロロホルムで抽出し、水洗後、硫酸マグネシウムで乾燥後、溶媒を留去した。残さをシリカゲルカラムクロマトグラフィー（展開溶媒：トルエン）で精製し、黄色結晶の例示化合物（１）を９．５部（収率８３％）得た。
【００４２】
以下に得られた化合物の^１Ｈ−ＮＭＲおよびＩＲのデータを示す。
^１Ｈ−ＮＭＲ（ＣＤＣＬ３，２４℃）δ１．４１（ｔ，６Ｈ，Ｊ＝７．３Ｈｚ），２．１９（ｍ，４Ｈ），３．７２（ｄ，４Ｈ，Ｊ＝１３．２Ｈｚ），４．１５（ｔ，４Ｈ，Ｊ＝６．１Ｈｚ），４．４７（ｄ，４Ｈ，Ｊ＝１３．２Ｈｚ），７．４０（ｔ，２Ｈ，Ｊ＝８．１Ｈｚ），７．５６（ｔ，２Ｈ，Ｊ＝８．１Ｈｚ），７．６０（ｓ，４Ｈ），７．９０（ｄ，２Ｈ，Ｊ＝８．１Ｈｚ），７．９５（ｓ，４Ｈ），８．０７（ｄ，２Ｈ），８．１５（ｄ，２Ｈ），８．２０（ｄ，２Ｈ，Ｊ＝８．１Ｈｚ），８．３９（ｓ，２Ｈ），８．６８（ｓ，２Ｈ），８．８４（ｓ，２Ｈ）
ＩＲ（ＫＢｒ）３４３５，１５２９，１３５０ｃｍ^−１
これらの結果から、得られた化合物が例示化合物（１）であることが確認できた。
【００４３】
本発明においては、電荷発生材料としてアゾ顔料またはフタロシアニン顔料を用いることが好ましい。
【００４４】
用いられるアゾ顔料としては、ビスアゾ、トリスアゾおよ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。
【００４５】
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およ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。
【００４６】
さらに、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°、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°、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。さらには、ＣｕＫα特性Ｘ線回折におけるブラッグ角２θの７．４°±０．２°、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の７．３°、２４．９°、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°、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°、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°、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。
【００４７】
本発明における電子写真感光体の層構成は、支持体上に式（１）で示されるアゾ化カリックス［ｎ］アレーン化合物と電荷発生材料およ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、支持体上にアゾ化カリックス［ｎ］ア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が、電荷発生層と電荷輸送層を積層する感光層を有する層構成であることが好ましい。また、電荷発生層と電荷輸送層の積層関係はどちらが上であってもよいが、電荷発生層が下層であることが好ましい。
【００４８】
支持体は、導電性を有するものであればよく、アルミニウムやステンレスなどの金属あるいは導電層を設けた金属、プラスチックおよ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。
【００４９】
支持体と感光層の間には、バリア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、にかわおよびゼラチンなどが用いられる。これらは、過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。
【００５０】
さらに、支持体と下引き層との間に、支持体のムラや欠陥の被覆、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、金属粒子およ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、特には１０〜３０μｍであることが好ましい。
【００５１】
単一層からなる感光層を形成する場合、本発明のアゾ化カリックス［ｎ］ア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乾燥して形成される。
【００５２】
積層構造からなる感光層を形成する場合、電荷発生層は、アゾ化カリックス［ｎ］アレーン化合物と電荷発生材料を過当なバインダー樹脂溶液と共に分散し、この分散液を塗布乾燥して形成する方法が挙げられる。
【００５３】
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およびトリアリルメタン系化合物などが挙げられるが、本発明の特定のアゾ化カリックス［ｎ］アレーン化合物と組み合わせる電荷発生材料としては、トリアリールアミン系化合物が好ましい。
【００５４】
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およびポリビニルベンザールなどの樹脂が用いられるが、本発明の特定のアゾ化カリックス［ｎ］アレーン化合物を分散させる樹脂としては、ポリビニルブチラール、ポリビニルベンザールが好ましい。
【００５５】
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およびビームコーティング法などの塗布方法を用いることができる。
【００５６】
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、特には１０〜３０μｍであることが好ましい。積層構造の場合、電荷発生層の膜厚は０．０１〜１０μｍであることが好ましく、特には０．０５〜５μｍであることが好ましい、電荷輸送層の膜厚は５〜４０μｍであることが好ましく、特には１０〜３０μｍであることが好ましい。
【００５７】
感光層が積層構造の場合、アゾ化カリックス［ｎ］アレーン化合物の含有量は、電荷発生層全質量に対して０．０００１〜１０質量％であることが好ましく、さらには０．００１〜５質量％であることが好ましい。電荷発生材料の含有量は、電荷発生層全質量に対して３０〜９０質量％であることが好ましく、さらには５０〜８０質量％であることが好ましい。電荷輸送材料の含有量は、電荷輸送層全質量に対して２０〜８０質量％であることが好ましく、さらには３０〜７０質量％であることが好ましい。
【００５８】
感光層が単一層の場合、アゾ化カリックス［ｎ］アレーン化合物の含有量は、感光層全質量に対して０．００００１〜１質量％であることが好ましい。電荷発生材料の含有量は、感光層全質量に対して３〜３０質量％であることが好ましい。電荷輸送材料の含有量は、感光層全質量に対して３０〜７０質量％であることが好ましい。
【００５９】
いずれの場合においても、特定のアゾ化カリックス［ｎ］アレーン化合物の含有量は、電荷発生材料に対して０．３〜１０質量％であることが好ましく、特に０．５〜５質量％であることが好ましい。
【００６０】
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、変性ポリカーボネートなど）、ナイロン、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およびスチレン−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、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ませてもよい。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。
【００６１】
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。
【００６２】
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する。該電子写真感光体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（スリット露光あるいはレーザービーム走査露光など）により露光光Ｌを受ける。これにより電子写真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、そのトナー現像像がコロナ転写手段５により不図示の給紙部から電子写真感光体１と転写手段５との間に電子写真感光体１の回転と同期取りされて給送された転写材９の面に順次転写されていく。像転写を受けた転写材９は、電子写真感光体面から分離されて像定着手段８へ導入されて像定着を受けて複写物（コピー）として機外ヘプリントアウトされる。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６にて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。
【００６３】
また、図２に示す装置では、少なくとも電子写真感光体１、帯電手段２および現像手段４を容器２０に納めてプロセスカートリッジとし、そのプロセスカートリッジを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。
【００６４】
また、図３および図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を電子写真感光体１に接触させることにより電子写真感光体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および図４に示す装置では、電子写真感光体１上のトナー像も接触帯電部材２３で転写材９に転写される。即ち、電圧印加された接触帯電部材２３を転写材９に接触させることにより電子写真感光体１上のトナー像を転写材９に転写させる。
【００６５】
さらに、図４に示す装置では、少なくとも電子写真感光体１および接触帯電部材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。
【００６６】
なお、帯電手段２が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。
【００６７】
露光光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したがって、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。
【００６８】
【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部およ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φ１ｍｍ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。
【００６９】
アルミニウムシリンダー（φ３０ｍｍ×２６０．５ｍｍ）上に、上記塗料を浸漬塗布し、１４０℃で３０分間乾燥させ、膜厚が２０μｍの導電層を形成した。
【００７０】
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ディッピング法で塗布、乾燥し、膜厚が１μｍの下引き層を設けた。
【００７１】
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°および２８．３°に強いピークを有する結晶型のヒドロキシガリウムフタロシアニン１０部と前記例示化合物（１）０．０１部およ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１ｍｍφ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。
【００７２】
次に、下記構造式
【００７３】
【外８】

【００７４】
で示される電荷輸送材料１０部と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作製し、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℃の温度で１時間乾燥し、膜厚が２５μｍの電荷輸送層を形成し、電子写真感光体を作製した。
【００７５】
（実施例２）
例示化合物（１）の添加量を０．００１部に代えた以外は、実施例１と同様にして実施例２の電子写真感光体を作製した。
【００７６】
（実施例３）
例示化合物（１）の添加量を０．１部に代えた以外は、実施例１と同様にして実施例３の電子写真感光体を作製した。
【００７７】
（実施例４）
例示化合物（１）を例示化合物（３）に代えた以外は、実施例１と同様にして実施例４の電子写真感光体を作製した。
【００７８】
（実施例５）
例示化合物（１）を例示化合物（９）に代えた以外は、実施例１と同様にして実施例５の電子写真感光体を作製した。
【００７９】
（実施例６）
実施例１に用いた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°および２８．３°に強いピークを有する結晶型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°および２７．１°に強いピークを有する結晶型のオキシチタニウムフタロシアニンに代えた以外は、実施例１と同様にして実施例６の電子写真感光体を作製した。
【００８０】
（実施例７）
実施例１と同様にして電荷発生層を形成した。
【００８１】
次に、下記構造式の化合物
【００８２】
【外９】

【００８３】
で示される電荷輸送材料１０部と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１００部に溶解した溶液を作製し、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℃の温度で３０分間乾燥し、膜厚が１５μｍの電荷輸送層を形成し、実施例７の電子写真感光体を作製した。
【００８４】
（実施例８）
実施例１と同様にして電荷発生層を形成した。
【００８５】
次に、下記構造式の化合物
【００８６】
【外１０】

【００８７】
で示される電荷輸送材料７部と下記構造式の化合物
【００８８】
【外１１】

【００８９】
で示される電荷輸送材料３部、およびポリカーボネート樹脂（商品名：ユーピロンＺ−２００、三菱ガス化学社製）１０部をモノクロロベンゼン７０部に溶解した溶液を作製し、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℃の温度で１時間乾燥し、膜厚が３２μｍの電荷輸送層を形成し、実施例８の電子写真感光体を作製した。
【００９０】
（比較例１）
実施例１に用いた例示化合物（１）を添加しなかった以外は、実施例１と同様にして比較例１の電子写真感光体を作製した。
【００９１】
（比較例２）
実施例６に用いた例示化合物（１）を添加しなかった以外は、実施例６と同様にして比較例２の電子写真感光体を作製した。
【００９２】
（比較例３）
実施例６に用いた例示化合物（１）の代わりに下記構造式のビスアゾ顔料
【００９３】
【外１２】

【００９４】
３部を添加した以外は、実施例６と同様に比較例３の電子写真感光体を作製した。
【００９５】
これら電子写真感光体を用いて明部電位測定およ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およ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および１５時間後での明部電位の測定およびゴースト画像の評価を行った。
【００９６】
次に、これらの電子写真感光体を評価機と共に、温度１５℃／１０％ＲＨの低温低湿（Ｌ／Ｌ）の環境下で３日間放置した後、明部電位の測定およびゴースト画像の評価を行った。
【００９７】
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おきに印字するモードで行った。
【００９８】
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）および全面白画像をプリントした。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）で各々サンプリングした。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。
ランク１は「いずれのモードでの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」
【００９９】
以上の結果を表６にまとめた。
【０１００】
【表６】

【０１０１】
【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少ない画像を供給する電子写真感光体が提供され、またその電子写真感光体を有するプロセスカートリッジおよび電子写真装置が提供される。
【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別の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別の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 転写材
１０，２３ 接触帯電部材
１２ 案内手段
２０，２１，２２ 容器
Ｌ 露光光[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 phthalocyanine pigments have advantages such as pollution-free and high productivity compared to inorganic photoconductive materials, but their sensitivity is low and their practical application It was difficult. For this reason, several sensitization methods have been proposed. As an effective method, the use of a function-separated type electrophotographic photosensitive member in which a charge generation layer and a charge transport layer are laminated becomes mainstream and put to practical use. It has become like this.
[0003]
  On the other hand, in recent years, non-impact printers using electrophotographic technology have been widely used in place of conventional impact printers as terminal printers. These are laser beam printers mainly using laser light as a light source, and a semiconductor laser is used as the light source from the viewpoint of cost, size of the apparatus, and the like.
[0004]
  Currently, semiconductor lasers that are mainly used have a long wavelength of 650 to 820 nm, and therefore, development of electrophotographic photoreceptors 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, and in particular, azo pigments are disclosed in JP-A-59-31962 and JP-A-1-183663. . As phthalocyanine pigments, oxytitanium phthalocyanine and gallium phthalocyanine have excellent sensitivity characteristics as compared with conventional phthalocyanine pigments, and so far, JP-A-61-239248 and JP-A-61-217050. JP, 62-67094, JP 63-218768, JP 64-17066, JP 5-98181, JP 5-263007, and JP 10-67946. Various crystal types are disclosed in publications and the like. JP-A-7-128888 and JP-A-9-34149 disclose combinations with specific azo pigments in order to improve the problems of phthalocyanine pigments, but maintain higher sensitivity characteristics. However, an electrophotographic photoreceptor that provides an image free from image defects has been desired.
[0006]
  An electrophotographic photosensitive member using an azo pigment or a phthalocyanine pigment has such excellent sensitivity characteristics, but the generated photo carrier tends to remain in the photosensitive layer, and is likely to cause potential fluctuation as a kind of memory. There were drawbacks.
[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) in which the dark part potential part currently used widely in printers is a non-development part and the bright part potential part is a development part, the sensitivity at which the light hits during pre-printing When the white image is taken at the time of the next printing, a so-called ghost phenomenon (hereinafter referred to as a 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 so-called ghost phenomenon (hereinafter referred to as “negative ghost”), in which the sensitivity of the area exposed to light at the time of the previous printing is slowed down and the entire black image is taken out at the time of the next print, Prominently appear. Of these phenomena, negative ghosts often appear at the beginning of printing and positive ghosts appear during continuous printing.
[0010]
  This phenomenon is particularly remarkable in electrophotographic photosensitive members using an undercoat layer as an adhesive layer for the charge generation layer, and the volume resistance of the charge generation layer and the undercoat layer to electrons increases in an environment such as low temperature and low humidity. Therefore, there is a drawback that electrons are easily filled in the charge generation layer, and a ghost phenomenon is likely to occur.
[0011]
[Problems to be solved by the invention]
  An object of the present invention is to provide an electrophotographic photosensitive member that supplies an image with few image defects while maintaining high sensitivity, particularly high sensitivity characteristics in a semiconductor laser wavelength region, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member. There is to do.
[0012]
[Means for Solving the Problems]
  According to the present invention, an electrophotographic photosensitive member having a photosensitive layer on a support, wherein the photosensitive layer contains an azolated calix [n] arene compound represented by the following formula (1): The body is provided.
[0013]
[Outside 3]

[0014]
  formula(1)N represents an integer of 4 to 8, R₁Are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, at least one represents an alkyl group which may have a substituent, and R₂Are the same or different and each represents a hydrogen atom or an alkyl group which may have a substituent, and Ar may be the same or different and may have an aromatic hydrocarbon ring or a substituent which may have a substituent. A monovalent group of a good heterocycle or a plurality of aromatic hydrocarbon rings which may have a substituent or a combination of a plurality of heterocycles which may have a substituent is shown.
[0015]
  According to the present invention, the electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means are integrally supported and detachable from the electrophotographic apparatus. A process cartridge is provided.
[0016]
  Further, according to the present invention, there is provided an electrophotographic apparatus comprising the electrophotographic photosensitive member, a charging unit, an exposing unit, a developing unit and a transfer unit.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
  The azolated calix [n] arene compound used in the present invention is represented by the following formula (1).
[0018]
[Outside 4]

[0019]
  formula(1)N represents an integer of 4 to 8, R₁Are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, at least one represents an alkyl group which may have a substituent, and R₂Are the same or different and each represents a hydrogen atom or an alkyl group which may have a substituent, and Ar may be the same or different and may have an aromatic hydrocarbon ring or a substituent which may have a substituent. A monovalent group of a good heterocycle or a plurality of aromatic hydrocarbon rings which may have a substituent or a combination of a plurality of heterocycles which may have a substituent is shown.
[0020]
  Alkyl groups of the above expression include groups such as methyl, ethyl, propyl and butyl, but R₂Is particularly preferably a hydrogen atom.
[0021]
  In addition, aromatic hydrocarbon rings or heterocycles of the above expressions include hydrocarbon aromatic rings such as benzene, naphthalene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene, furan, thiophene, pyridine, indole, benzothiazole, carbazole, benzo Heterocycles such as carbazole, acridone, dibenzothiophene, benzoxazole, benzotriazole, oxathiazole, thiazole, phenazine, cinnoline and benzocinnoline, and the aromatic ring or heterocycle directly or aromatic group or non-aromatic group For example, triphenylamine, diphenylamine, N-methyldiphenylamine, biphenyl, terphenyl, binaphthyl, fluorenone, phenanthrenequinone, an Rakinon, benzanthrone, diphenyloxazole, phenyl benzoxazole, diphenylmethane, diphenyl sulfone, diphenyl ether, benzophenone, stilbene, distyryl benzene, tetraphenyl -p- phenylenediamine and tetraphenyl benzidine and the like.
[0022]
  Ar is particularly preferably a group in which a cyano group, a nitro group, a carboxyl group, or a halogen atom having an electron withdrawing property is bonded to a benzene ring.
[0023]
  Examples of the substituent that each group may have include alkyl groups such as methyl, ethyl, propyl and butyl, alkoxy groups such as methoxy and ethoxy, dialkylamino groups such as dimethylamino and diethylamino, methoxycarbonyl and ethoxycarbonyl, etc. Alkoxycarbonyl groups, halogen atoms such as fluorine atom, chlorine atom and bromine atom, hydroxy group, nitro group, cyano group or halomethyl group.
[0024]
  In the formula (1), n is 4 to 8, and 4 to 8 R₁And Ar, 8-16 R₂May be the same or different.
[0025]
  Next, examples of the azolated calix [n] arene compounds used in the present invention are shown in Tables 1 to 1.5However, the present invention is not limited to these.
[0026]
  Basic type I {compound represented by formula (1)} in Tables 1 to 4
[0027]
[Outside 5]

[0028]
[Table 1]

[0029]
[Table 2]

[0030]
[Table 3]

[0031]
[Table 4]

[0032]
  table5Basic type III {compound represented by formula (1)}
[0033]
[Outside 6]

[0034]
[Table 5]

[0035]
  Among these, exemplary compounds 1 to 12and24 is preferable, and further, exemplified compounds 1, 3And 9Is preferred. Among these, Exemplified Compound 1 is particularly preferable.
[0036]
  The azolated calix [n] arene compound represented by the formula (1) is represented by R in the formula (1).₁Can be synthesized by treating a phenolic OH of an azolized calix [n] arene compound with hydrogen with an alkyl halide in the presence of an alkali. The type of alkyl to be introduced and the degree of alkylation depend on the type of alkali and the alkyl halide. It can be controlled by the amount and reaction conditions. Examples of the alkyl include sodium hydride, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, barium hydroxide and cesium carbonate. Examples of the alkyl halide include iodomethane, iodoethane, 1-iodopropane, 1-iodopropane, Examples include bromopropane, 2-iodopropane, 1-iodobutane, ethyl bromoacetate, ethyl 4-bromobutyrate, and chloromethyl methyl ether.
[0037]
  In addition to this method, it can be synthesized by a method using diazomethane or a method using dimethyl sulfate / barium hydroxide.
[0038]
  Hereinafter, “part” means “part by mass”.
[0039]
  Synthesis example
  <Synthesis of Exemplified Compound 1>
  After dispersing 10 parts of the following compound in 500 parts of N, N-dimethylformamide under a nitrogen atmosphere,
[0040]
[Outside 7]

[0041]
9.5 parts of barium hydroxide octahydrate and 8.9 parts of barium oxide were added and stirred at 40 ° C. for 30 minutes. 51 parts of 1-iodopropane was added dropwise to the solution, stirred at the same temperature for 2 hours, poured into 5000 parts of 1N hydrochloric acid, extracted with chloroform, washed with water, dried over magnesium sulfate, and solvent. Was distilled off. The residue was purified by silica gel column chromatography (developing solvent: toluene) to obtain 9.5 parts (yield 83%) of exemplary compound (1) as yellow crystals.
[0042]
  Of the compound obtained below¹1 shows H-NMR and IR data.
  ¹H-NMR (CDCL3, 24 ° C.) δ 1.41 (t, 6H, J = 7.3 Hz), 2.19 (m, 4H), 3.72 (d, 4H, J = 13.2 Hz), 4. 15 (t, 4H, J = 6.1 Hz), 4.47 (d, 4H, J = 13.2 Hz), 7.40 (t, 2H, J = 8.1 Hz), 7.56 (t, 2H) , J = 8.1 Hz), 7.60 (s, 4H), 7.90 (d, 2H, J = 8.1 Hz), 7.95 (s, 4H), 8.07 (d, 2H), 8.15 (d, 2H), 8.20 (d, 2H, J = 8.1 Hz), 8.39 (s, 2H), 8.68 (s, 2H), 8.84 (s, 2H)
  IR (KBr) 3435, 1529, 1350 cm^-1
  From these results, it was confirmed that the obtained compound was Exemplified Compound (1).
[0043]
  In the present invention, it is preferable to use an azo pigment or a phthalocyanine pigment as the charge generation material.
[0044]
  As the azo pigment to be used, any azo pigment such as bisazo, trisazo and tetrakisazo can be used. Since the present invention has excellent sensitivity characteristics and ghosts are easily generated, the present invention is effective and preferable.
[0045]
  Further, as the phthalocyanine pigment, any phthalocyanine such as metal-free phthalocyanine and metal phthalocyanine which may have an axial ligand can 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.
[0046]
  Further, any crystalline form may be used, and among them, 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 having strong peaks at 7.4 °, 16.6 °, 25.5 °, and 28.3 ° with Bragg angles 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. 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, and in CuKα characteristic X-ray diffraction, Crystalline 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 Bragg angles 2θ of 7.3 °, 24.9 °, and 28.1 ° in CuKα characteristic X-ray diffraction, and Bragg angle 2θ in CuKα characteristic X-ray diffraction. Crystal form hydroxygallium phthalocyanine having strong peaks at ± 0.2 ° 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 °, 28.3 °, CuKα characteristic X Crystalline oxytitanium phthalocyanine having strong peaks at 9.0 °, 14.2 °, 23.9 °, and 27.1 ° with a Bragg angle 2θ ± 0.2 ° in line diffraction, Bragg in CuKα characteristic X-ray diffraction Crystal forms having strong peaks at angles 9.5 °, 9.7 °, 11.7 °, 15.0 °, 23.5 °, 24.1 °, 27.3 ° with an angle 2θ ± 0.2 ° Oxytitanium phthalocyanine Preferred.
[0047]
  The layer structure of the electrophotographic photosensitive member in the present invention is such that a photosensitive layer comprising a single layer containing simultaneously an azolated calix [n] arene compound represented by formula (1), a charge generating material and a charge transporting material on a support. And a layer structure having a photosensitive layer on which a charge generating layer containing an azolated calix [n] arene compound and a charge generating material and a charge transporting layer containing a charge transporting material are laminated on a support, A layer structure having a photosensitive layer in which a charge generation layer and a charge transport layer are laminated is preferable. In addition, the stacking relationship between the charge generation layer and the charge transport layer may be either upper, but the charge generation layer is preferably the lower layer.
[0048]
  The support only needs to have conductivity, and examples thereof include metals such as aluminum and stainless steel, metals provided with a conductive layer, plastics, paper, and the like, and examples of the shape include a cylindrical shape and a film shape.
[0049]
  An undercoat layer having a barrier function and an adhesive function can be provided between the 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 an appropriate solvent and coated on the conductive support. The film thickness is 0.2 to 3.0 μm.
[0050]
  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 and 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 particularly preferably 10 to 30 μm.
[0051]
  In the case of forming a photosensitive layer comprising a single layer, the azolated calix [n] arene compound of the present invention, a charge generating material and a charge transporting material are mixed in a suitable binder resin solution, and this mixed solution is used as a conductive support. It is formed by applying and drying on.
[0052]
  In the case of forming a photosensitive layer having a laminated structure, the charge generation layer is formed by dispersing an azolated calix [n] arene compound and a charge generation material together with an appropriate binder resin solution, and coating and drying the dispersion. Can be mentioned.
[0053]
  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. As the charge generation material to be combined with the azolated calix [n] arene compound, a triarylamine compound is preferable.
[0054]
  Examples of the binder resin used for each layer include resins such as polyester, acrylic resin, polyvinyl carbazole, phenoxy resin, polycarbonate, polyvinyl butyral, polystyrene, polyvinyl acetate, polysulfone, polyarylate, vinylidene chloride, acrylonitrile copolymer, and polyvinyl benzal. As the resin for dispersing the specific azolated calix [n] arene compound of the present invention, polyvinyl butyral and polyvinyl benzal are preferable.
[0055]
  As a method for applying the photosensitive layer, application 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 can be used.
[0056]
  When the photosensitive layer is a single layer, the film thickness is preferably 5 to 40 μm, particularly preferably 10 to 30 μm. In the case of a laminated structure, 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. In particular, the thickness is preferably 10 to 30 μm.
[0057]
  When the photosensitive layer has a laminated structure, the content of the azolated calix [n] arene compound is preferably 0.0001 to 10% by mass, more preferably 0.001 to 5% by mass with respect to the total mass of the charge generation layer. % Is preferred. 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 total mass of 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 total mass of the charge transport layer.
[0058]
  When the photosensitive layer is a single layer, the content of the azolated calix [n] arene compound is preferably 0.00001 to 1% by mass relative to the total mass of the photosensitive layer. The content of the charge generating material is preferably 3 to 30% by mass with respect to the total mass of the photosensitive layer. The content of the charge transport material is preferably 30 to 70% by mass with respect to the total mass of the photosensitive layer.
[0059]
  In any case, the content of the specific azolated calix [n] arene compound is preferably 0.3 to 10% by mass, particularly 0.5 to 5% by mass with respect to the charge generating material. It is preferable.
[0060]
  A protective layer may be provided on the photosensitive layer as necessary. The protective layer is made of a suitable organic resin such as polyvinyl butyral, polyester, polycarbonate (polycarbonate Z, modified polycarbonate, etc.), nylon, polyimide, polyarylate, polyurethane, styrene-butadiene copolymer, styrene-acrylic acid copolymer, and styrene-acrylonitrile copolymer. It can be formed by dissolving in a solvent and coating and drying 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.
[0061]
  Next, an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention will be described.
[0062]
  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 electrophotographic photosensitive member 1 is charged uniformly at a predetermined positive or negative potential on its peripheral surface by the charging means 2 during its rotation process, and then exposed to an exposure means (not shown) (slit exposure or laser beam scanning) in the exposure unit 3. Exposure light L is received by exposure or the like. As a result, electrostatic latent images corresponding to the exposure images are sequentially formed on the peripheral surface of the electrophotographic photosensitive member. The electrostatic latent image is then developed with toner by the developing means 4, and the toner developed image is transferred between the electrophotographic photosensitive member 1 and the transfer means 5 from a paper feeding unit (not shown) by the corona transfer means 5. The images are sequentially transferred onto the surface of the transfer material 9 fed in synchronism with the rotation of 1. The transfer material 9 that has received the image transfer is separated from the surface of the electrophotographic photosensitive member, introduced into the image fixing means 8, undergoes image fixing, and is printed out as a copy (copy). The surface of the electrophotographic photosensitive member 1 after the image transfer is cleaned by the removal of the transfer residual toner by the cleaning unit 6, is subjected to a charge removal process by the pre-exposure unit 7, and is repeatedly used for image formation.
[0063]
  In the apparatus shown in FIG. 2, at least the electrophotographic photosensitive member 1, the charging means 2 and the developing means 4 are accommodated in a container 20 to form a process cartridge, and the process cartridge is attached and detached using a guide means 12 such as a rail of the apparatus main body. It is configured freely. The cleaning means 6 may or may not be disposed in the container 20.
[0064]
  Further, as shown in FIGS. 3 and 4, the contact charging member 10 is used as charging means, and the electrophotographic photosensitive member 1 is charged by bringing the contact charging member 10 to which voltage is applied into contact with the electrophotographic 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 electrophotographic photosensitive member 1 is also transferred to the transfer material 9 by the contact charging member 23. That is, the toner image on the electrophotographic photosensitive member 1 is transferred to the transfer material 9 by bringing the contact charging member 23 to which voltage is applied into contact with the transfer material 9.
[0065]
  Further, in the apparatus shown in FIG. 4, at least the electrophotographic photosensitive member 1 and the contact charging member 10 are stored in the first container 21 as the first process cartridge, and at least the developing means 4 is stored in the second container 22. 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.
[0066]
  When the charging unit 2 is a contact charging unit, pre-exposure is not always necessary.
[0067]
  When the electrophotographic apparatus is used as a copying machine or a printer, the exposure light L uses reflected light or transmitted light from an original, or scans and emits a laser beam using this signal according to a signal read from the original. This is performed by driving a diode array or a liquid crystal shutter array.
[0068]
【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, A conductive layer coating material was prepared by dispersing 0.002 part of (average molecular weight 3000) in a sand mill using φ1 mm glass beads for 2 hours.
[0069]
  The paint was dip-coated on an aluminum cylinder (φ30 mm × 260.5 mm) and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.
[0070]
  On top of this, 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 applied and dried by a dipping method, and the film thickness was 1 μm. An undercoat layer was provided.
[0071]
  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, 0.01 part of the exemplified compound (1) and 5 parts of a polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) are added to 250 parts of cyclohexanone and 1 mmφ The mixture was dispersed for 1 hour in a sand mill using glass beads, diluted with 250 parts of ethyl acetate, coated on the undercoat layer, dried at 100 ° C. for 10 minutes, and the film thickness was reduced to 0. A charge generation layer of .16 μm was formed.
[0072]
  Next, the following structural formula
[0073]
[Outside 8]

[0074]
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 Company) are dissolved in 70 parts of monochlorobenzene is prepared and applied onto the charge generation layer by a dipping method. did. This was dried at a temperature of 110 ° C. for 1 hour to form a charge transport layer having a thickness of 25 μm, and an electrophotographic photosensitive member was produced.
[0075]
  (Example 2)
  An electrophotographic photoreceptor of Example 2 was produced in the same manner as in Example 1 except that the amount of Example Compound (1) added was changed to 0.001 part.
[0076]
  (Example 3)
  An electrophotographic photoreceptor of Example 3 was produced in the same manner as in Example 1 except that the amount of Example Compound (1) added was changed to 0.1 part.
[0077]
  Example 4
  An electrophotographic photosensitive member of Example 4 was produced in the same manner as in Example 1 except that the exemplified compound (1) was replaced with the exemplified compound (3).
[0078]
  (Example 5)
  An electrophotographic photosensitive member of Example 5 was produced in the same manner as in Example 1 except that the exemplified compound (1) was replaced with the exemplified compound (9).
[0079]
  (Example6)
  Bragg angle 2θ ± 0.2 ° of 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° in CuKα characteristic X-ray diffraction used in Example 1 Crystalline hydroxygallium phthalocyanine 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 Example 1 was carried out in the same manner as in Example 1 except that the crystal type oxytitanium phthalocyanine was changed.6An electrophotographic photoreceptor was prepared.
[0080]
  (Example7)
  A charge generation layer was formed in the same manner as in Example 1.
[0081]
  Next, the compound of the following structural formula
[0082]
[Outside 9]

[0083]
A solution in which 10 parts of a charge transport material and 10 parts of a polycarbonate resin (trade name: Iupilon Z-400, manufactured by Mitsubishi Gas Chemical Company) are dissolved in 100 parts of monochlorobenzene is prepared and applied onto the charge generation layer by a dipping method. did. This was dried at a temperature of 150 ° C. for 30 minutes to form a charge transport layer having a film thickness of 15 μm.7An electrophotographic photoreceptor was prepared.
[0084]
  (Example8)
  A charge generation layer was formed in the same manner as in Example 1.
[0085]
  Next, the compound of the following structural formula
[0086]
[Outside 10]

[0087]
7 parts of a charge transport material represented by the following formula:
[0088]
[Outside 11]

[0089]
A solution in which 3 parts of the charge transport material shown in FIG. 5 and 10 parts of polycarbonate resin (trade name: Iupilon Z-200, manufactured by Mitsubishi Gas Chemical Company) are dissolved in 70 parts of monochlorobenzene is prepared, and the solution is dipped on the charge generation layer. Applied. This was dried at 110 ° C. for 1 hour to form a charge transport layer having a thickness of 32 μm.8An electrophotographic photoreceptor was prepared.
[0090]
  (Comparative Example 1)
  An electrophotographic photosensitive member of Comparative Example 1 was produced in the same manner as in Example 1 except that Example Compound (1) used in Example 1 was not added.
[0091]
  (Comparative Example 2)
  Example6Except that the exemplified compound (1) used in the above was not added, Example6In the same manner, an electrophotographic photoreceptor of Comparative Example 2 was produced.
[0092]
  (Comparative Example 3)
  Example6A bisazo pigment having the following structural formula instead of the exemplified compound (1) used in
[0093]
[Outside 12]

[0094]
Examples except that 3 parts were added6In the same manner, an electrophotographic photoreceptor of Comparative Example 3 was produced.
[0095]
  Using these electrophotographic photoreceptors, bright part potential measurement and ghost image evaluation were performed. For the evaluation, a laser beam printer (trade name: Laserjet 4000 manufactured by Hewlett Packard) was modified and used. First, after the initial bright part potential measurement and ghost image evaluation under a temperature of 23 ° C./55% RH environment, 1000 sheet passing durability tests were performed under the same environmental conditions. The bright part potential was measured and the ghost image was evaluated.
[0096]
  Next, these electrophotographic photoreceptors are allowed to stand together with an evaluation machine in a low-temperature and low-humidity (L / L) environment at a temperature of 15 ° C./10% RH for 3 days, and then the light potential is measured and the ghost image is evaluated. went.
[0097]
  The conditions for the paper passing durability were an intermittent mode of printing 4 sheets per minute, and the durability pattern was a mode in which lines of about 0.5 mm width were printed every 10 mm in length.
[0098]
  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) and an entire white image were printed. Ghost image samples were sampled at machine development volumes F5 (center value) and F9 (thin density), respectively. Evaluation was performed visually and ranked as follows according to the degree of ghost.
  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”
[0099]
  The above results6Summarized in
[0100]
[Table 6]

[0101]
【The invention's effect】
  As described above, according to the present invention, there is provided an electrophotographic photosensitive member for supplying an image with few image defects while maintaining high sensitivity, particularly high sensitivity characteristics in a semiconductor laser wavelength region, and the electrophotographic photosensitive member is provided. A process cartridge and an electrophotographic apparatus having a body 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 another 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 another 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 Transfer material
  10,23 Contact charging member
  12 Guide means
  20, 21, 22 container
  L Exposure light

Claims (16)

An electrophotographic photosensitive member having a photosensitive layer on a support, wherein the photosensitive layer contains an azolated calix [n] arene compound represented by the following formula (1).
[Outside 1]

(In the formula (1) , n represents an integer of 4 to 8, R ₁ is the same or different and represents a hydrogen atom or an alkyl group which may have a substituent, and at least one has a substituent. R ₂ is the same or different and R ₂ is a hydrogen atom or an alkyl group which may have a substituent, Ar is the same or different and an aromatic carbon which may have a substituent A monovalent ring formed by bonding a hydrogen ring or a heterocyclic ring 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. Group.)   The electrophotographic photoreceptor according to claim 1, wherein the photosensitive layer further contains a phthalocyanine pigment or an azo pigment as a charge generating material.   The electrophotographic photosensitive member according to claim 2, wherein the phthalocyanine pigment is oxytitanium phthalocyanine.   4. The electrophotographic photosensitive member according to claim 3, wherein the oxytitanium phthalocyanine has a crystal form having a strong peak at 27.2 ° ± 0.2 ° of the Bragg angle 2θ in CuKα characteristic X-ray diffraction.   The oxytitanium phthalocyanine is a crystal form 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. 4. The electrophotographic photosensitive member according to 4.   The electrophotographic photosensitive member according to claim 2, wherein the phthalocyanine pigment is gallium phthalocyanine.   The electrophotographic photosensitive member according to claim 6, wherein the gallium phthalocyanine pigment is hydroxygallium phthalocyanine.   The electron according to claim 7, wherein the hydroxygallium phthalocyanine is a crystal form having strong peaks at 7.4 ° ± 0.2 ° and 28.2 ° ± 0.2 ° of the Bragg angle 2θ in CuKα characteristic X-ray diffraction. Photoconductor.   9. The electron according to claim 8, wherein the hydroxygallium phthalocyanine has a crystal form having strong peaks at 7.3 °, 24.9 °, and 28.1 ° with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction. Photoconductor.   The hydroxygallium phthalocyanine is 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 °, 28.3 ° with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction. 9. The electrophotographic photosensitive member according to claim 8, wherein the electrophotographic photosensitive member is in a crystalline form having a strong peak.   The electrophotographic photosensitive member according to claim 1, wherein Ar is a group in which at least one group selected from the group consisting of a cyano group, a nitro group, a carboxyl group, and a halogen atom is bonded to a benzene ring. The electrophotographic photoreceptor according to claim 1, wherein the azolated calix [n] arene compound is an azolated calix [4] arene compound represented by the following formula (2).
[Outside 2]

(However, R ₃ in the above formula (2) is an n-propyl group, R ₄ is a hydrogen atom, R ₅ is an n-propyl group, R ₆ is a hydrogen atom, and R ₇ is a hydrogen atom. An atom, and R ₈ is an m-nitrophenyl group.)   The electrophotographic photosensitive member according to claim 1, wherein the content of the azolated calix [n] arene compound is 0.3 to 10% by mass with respect to the charge generation material.   The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer comprises at least two layers of a charge generation layer and a charge transport layer containing an azolated calix [n] arene compound represented by the formula (1).   15. The electrophotographic photosensitive member according to claim 1 and at least one unit selected from the group consisting of a charging unit, a developing unit, and a cleaning unit are integrally supported, and are detachable from the main body of the electrophotographic apparatus. 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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