JP3862399B2 - Electrophotographic photosensitive member manufacturing method, electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

（Ｘ ₁ は、炭素原子、または単結合（この際のＲ ₅ ，Ｒ ₆ はなし）、Ｒ ₁ 〜Ｒ ₄ は水素原子、ハロゲン原子、置換されてもよいアルキル基、アリール基を示し、Ｒ ₅ ，Ｒ ₆ はそれぞれ水素原子、ハロゲン原子、置換されてもよいアルキル基、アリール基、またはＲ ₅ とＲ ₆ が結合することによって形成されるアルキリデン基を示し、Ｒ ₇ 〜Ｒ ₁₀ はそれぞれ水素原子、ハロゲン原子、置換されてもよいアルキル基、アリール基を示す）
【００１５】
【化６】

（Ｘ ₂ は、炭素原子、または単結合（この際のＲ ₁₅ ，Ｒ ₁₆ はなし）、Ｒ ₁₁ 〜Ｒ ₁₄ は水素原子、ハロゲン原子、置換されてもよいアルキル基、アリール基を示し、Ｒ ₁₅ ，Ｒ ₁₆ はそれぞれ水素原子、ハロゲン原子、置換されてもよいアルキル基、アリール基、またはＲ ₁₅ とＲ ₁₆ が結合することによって形成されるアルキリデン基を示す）
【００１６】
【化７】

（Ｒ ₁₇ 〜Ｒ ₂₂ はそれぞれ水素原子、ハロゲン原子、置換されてもよいアルキル基、アリール基を示し、ｎは正の整数を示す）
【００１７】
【化８】

（Ｘ ₃ は、炭素原子、または単結合（この際のＲ ₂₇ ，Ｒ ₂₈ はなし）、Ｒ ₂₃ 〜Ｒ ₂₆ はそれぞれ水素原子、ハロゲン原子、置換されてもよいアルキル基、アリール基を示し、Ｒ ₂₇ ，Ｒ ₂₈ はそれぞれ水素原子、ハロゲン原子、置換されてもよいアルキル基、アリール基、またはＲ ₂₇ とＲ ₂₈ が結合することによって形成されるアルキリデン基を示す）
また、本発明に従って、上記製造方法により製造されたことを特徴とする電子写真感光体が提供される。
また、本発明に従って、上記電子写真感光体を有するプロセスカートリッジ及び電子写真装置が提供される。
【００１８】
【発明の実施の形態】
式（１）乃至（４）中、ハロゲン原子としてはフッ素原子、塩素原子、臭素原子等が挙げられ、アルキル基としては低級アルキル基、例えばメチル基、エチル基、プロピル基、ブチル基等が挙げられ、アリール基としてはフェニル基、ナフチル基等が挙げられ、シクロアルキリデン基としてはシクロヘキシリデン基等が挙げられる。上記アルキル基、アリール基、シクロアルキリデン基が有してもよい置換基としては、メチル基、エチル基、プロピル基、ブチル基等の如き低級アルキル基、フェニル基、ナフチル基等の如きアリール基、フッ素原子、塩素原子、臭素原子等のハロゲン原子等が挙げられる。ｎは正の整数を示し、１〜２００であることが好ましい。
【００１９】
式（１）で示される構成単位の具体例を表１〜４に示すが、本発明はこれらに限られるものではない。
【００２０】
【表１】

【００２１】
【表２】

【００２２】
【表３】

【００２３】
【表４】

本発明において用いられる、式（１）で示される構成単位を有する重合体は、通常、溶解性や剛直性の制御のため、テレフタル酸塩化物、イソフタル酸塩化物の混合物と各種ビスフェノールとを、アルカリ下で溶媒／水系中で攪拌し乍ら界面重合させることにより得られる。すなわち表１〜４に示した式は、テレフタル酸塩化物、イソフタル酸塩化物の混合系から調製された形として表わした。しかし、テレフタル酸塩化物、イソフタル酸塩化物の比率はその重合体の溶解性を考慮して決定されるもので、定説はない。ただし、いずれかの塩化物が３０ｍｏｌ％以下になると、合成した重合体の溶解性が極端に低下するので注意が必要である。通常は１／１の比率で合成するのが好ましい。本発明の電子写真感光体においては、式（１）で示される構成単位が同一のもので構成されるモノ重合体でも、式（１）で示される２種類以上の別種の構成単位からなる共重合体でもよい。
【００２４】
式（２）で示される構成単位の具体例を表５〜７に示すが、本発明はこれらに限られるものではない。
【００２５】
【表５】

【００２６】
【表６】

【００２７】
【表７】

式（３）で示される構成単位の具体例を表８及び９に示すがこれらに限られるものではない。
【００２８】
【表８】

【００２９】
【表９】

式（４）については、表５〜７に示された式（２）と同一であるので、式（４）の例は、表５〜７の例を適用する。
【００３０】
本発明に用いられるフッ素系樹脂粉体の具体例としては、四フッ化エチレン樹脂、三フッ化塩化エチレン樹脂、四フッ化エチレン六フッ化プロピレン樹脂、フッ化ビニル樹脂、フッ化ビニリデン樹脂、二フッ化二塩化エチレン樹脂及びそれらの共重合体があげられる。好ましい例としては、四フッ化エチレン樹脂、フッ化ビニリデン樹脂があげられ、特に好ましい例としては、四フッ化エチレン樹脂があげられる。
【００３１】
また、本発明に用いられるケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体は、ケイ素原子を側鎖に有し末端に重合性の官能基を有する単量体と、ケイ素原子を持たない重合性の単量体もしくは末端に重合性の官能基を有する分子量１０００から１００００程度の比較的低分子量のオリゴマーからなるマクロモノマーとを共重合して得られるものであり、主鎖に対してケイ素原子を含有する側鎖が枝状にぶら下がった構造をしている。ケイ素原子を側鎖に有する重合性単量体としては以下のような化合物があげられるが、本発明はこれらの例に限られるものではない。
【００３２】
【化９】

【００３３】
【化１０】

【００３４】
【化１１】

【００３５】
【化１２】

【００３６】
【化１３】

上記の式中においてＲはＨまたはＣＨ₃である。
【００３７】
一方の重合性単量体、もしくはマクロモノマーは上記グラフト重合体を添加しようとする樹脂と親和性のあるものが選択され、たとえばアクリル酸エステル類、メタクリル酸エステル類、スチレン及びスチレン誘導体等が用いられる。共重合比はケイ素原子を側鎖に有する重合性単量体の含有率として５ｗｔ％以上が好ましい。得られた重合体の分子量は重量平均分子量として５００から１０００００、特に１０００から５０００が好ましい。
【００３８】
詳細なメカニズムは十分には解明できてはいないが、式（１）で示される構成単位を有するポリアリレート、及び式（２）で示される構成単位を有するポリカーボネート、及び式（３）及び式（４）で示される構成単位を有する共重合体の各ポリマーを混合使用し、さらにフッ素系樹脂粉体を含有することにより耐久初期から耐久後まで安定して表面潤滑性、耐ソルベントクラック性などを向上させることができる。これは、ポリアリレート構造とポリカーボネート構造とシロキサン構造が各々の分子鎖間に入り込んで各々の結晶性を崩し、さらにフッ素系樹脂粉体を膜内部に分散させていることによって、膜内部にフッ素系樹脂粉体をコアとした無数の分子団および分子内配向秩序を作りだし、これにより高い耐摩耗性を保持したまま耐久後までの高い表面潤滑性、耐ソルベントクラック性を向上させることができるものと推察される。
【００３９】
さらにケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体を含有することにより耐久初期から耐久後まで安定して表面潤滑性、耐ソルベントクラック性などを向上させることができる。ケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体は表面移行性が強いことが知られており、従って加えたケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体は大部分が膜表面近傍に局在化して耐久初期の表面潤滑性を向上させるであろうことは容易に理解できるが、本発明による構成では耐久初期から耐久後まで安定して表面潤滑性を向上させていることは驚きである。これは、ポリアリレート構造とポリカーボネート構造とシロキサン構造が各々の分子鎖間に入り込んで各々の結晶性を崩し、さらにケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体が膜表面近傍のみならず膜内部にも存在することによって、膜内部にケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体を含む分子団および分子内配向秩序を作りだし、これにより高い耐摩耗性を保持したまま耐久後までの高い表面潤滑性、耐ソルベントクラック性を向上させることができるものと推察される。
【００４０】
またこの効果は、本発明の構成要素であるポリアリレート構造とポリカーボネート構造とシロキサン構造とケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体が全てそろった場合に有効に発現されるものであり、構成要素の一つが欠けても大幅に効果が損なわれることから、従来より知られているシロキサン構造やケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体のもつ潤滑性、耐ソルベントクラック性を遥かに上回る新たな効果を、上記の本発明の構成要素間の相互作用によって発現しているものと推察される。
【００４１】
また、詳細なメカニズムは十分には解明できてはいないが、式（１）におけるＲ₁，Ｒ₂，Ｒ₅，Ｒ₆がメチル基でありＲ₃，Ｒ₄，Ｒ₇，Ｒ₈，Ｒ₉，Ｒ₁₀が水素原子である構成単位を有するポリアリレートを含有し、かつ、式（２）におけるＲ₁₁〜Ｒ₁₄が水素原子でありＲ₁₅，Ｒ₁₆がＸとともにシクロヘキシリデン基である構成単位を有するポリカーボネートを含有し、かつ、式（３）におけるＲ₁₇〜Ｒ₂₀がメチル基でありＲ₂₁，Ｒ₂₂が水素原子であり式（４）におけるＲ₂₃〜Ｒ₂₆が水素原子でありＲ₂₇，Ｒ₂₈がＸとともにシクロヘキシリデン基である構成単位を有する共重合体の各ポリマーを混合使用し、さらにフッ素系樹脂粉体及び／又はケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体を含有することにより耐久初期から耐久後まで特に安定して表面潤滑性、耐ソルベントクラック性などを向上させることができる。これは、ポリアリレート構造が式（１）におけるＲ₁，Ｒ₂，Ｒ₅，Ｒ₆がメチル基であり、Ｒ₃，Ｒ₄，Ｒ₇，Ｒ₈，Ｒ₉，Ｒ₁₀が水素原子であり、ポリカーボネート構造が式（２）におけるＲ₁₁〜Ｒ₁₄が水素原子であり、Ｒ₁₅，Ｒ₁₆がＸと共にシクロヘキシリデン基であり、シロキサン構造が式（３）におけるＲ₁₇〜Ｒ₂₀がメチル基であり、Ｒ₂₁，Ｒ₂₂が水素原子であり、式（４）におけるＲ₂₃〜Ｒ₂₆が水素原子であり、Ｒ₂₇，Ｒ₂₈がＸとともにシクロヘキシリデン基であることと密接に関係し、各々の分子鎖間への入り込み方、各々の結晶性の崩れ方、さらに膜内部でのフッ素系樹脂粉体及び／又はケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体を含む分子団及び分子内配向秩序の出来方に違いがあるものと推察され、これにより高い耐摩耗性を保持したまま耐久後までの高い表面潤滑性、耐ソルベントクラック性を向上させることができるものと推察される。
【００４２】
また、式（１）で示される構成単位を有するポリアリレート、及び式（２）で示される構成単位を有するポリカーボネート、及び式（３）、及び式（４）で示される構成単位を有する共重合体を良溶媒中に溶解混合し、貧溶媒により再沈殿して得られたブレンド材料を含有することにより、本発明の効果をより発現することが可能である。溶解−再沈殿の方法は常法で行い、たとえば、ジクロロメタン、クロロフォルムなどの良溶媒に式（１）で示される構成単位を有するポリアリレート、及び式（２）で示される構成単位を有するポリカーボネート、及び式（３）及び式（４）で示される構成単位を有する共重合体を十分に溶解させる。次に、この混合ポリマー溶液をメタノールや水などの貧溶媒から再沈殿させて綿状のポリマーが得られる。これを真空乾燥させてブレンド材料が得られる。かくして得られたこの材料は、式（１）で示される構成単位を有するポリアリレート、及び式（２）で示される構成単位を有するポリカーボネート、及び式（３）及び式（４）で示される構成単位を有する共重合体の単純ブレンドより溶解性、塗料安定性が向上している。この方法はいずれの式（１）で示される構成単位を有するポリアリレート、及び式（２）で示される構成単位を有するポリカーボネート、及び式（３）及び式（４）で示される構成単位を有する共重合体でも有効であるが、特に溶解性の劣るポリカーボネートＡ型やポリアリレートＺ型では特性改良に効果的である。
【００４３】
詳細なメカニズムは十分には解明できてはいないが、各ポリマーをあらかじめ溶液中にてブレンドすることにより式（１）で示される構成単位を有するポリアリレート構造、及び式（２）で示される構成単位を有するポリカーボネート構造、及び式（３）及び式（４）で示される構成単位を有する共重合体構造が高度にブレンドでき、得られたブレンド材料は、各々の分子鎖間に入り込んでいるためフッ素系樹脂粉体及び／又はケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体との相互作用による新たな特性を発現しやすくなったと推定される。
【００４４】
まず、溶解性の低いポリカーボネートＡ型やポリアリレートＺ型などでは、異なる構造の分子がブレンドされることにより、各々の結晶性を崩していると考えられることから各成分の溶媒への溶解性を向上していると考えられ、さらに保存時のゲル化等も抑制することが可能となったと推定される。また、電子写真特性の低下が少なくなる要因としては、次のように推測される。ポリアリレートが機械的強度に優れている要因の一つであるフタル酸エステル構造は、電荷輸送材料との組み合わせによりキャリアのトラップ要因の一つになると予想されているが、本発明では式（２）で示される構成単位を有するポリカーボネート及び式（３）及び式（４）で示される構成単位を有する共重合体が分子レベルで式（１）で示される構成単位を有するポリアリレートの近傍に存在するため、フタル酸エステル構造との間で何らかの相互作用が起こり、フタル酸エステル構造に起因するキャリアのトラップを軽減していると推測される。さらに、ポリマー中の残留不純物（残モノマー、塩化物など）は、諸特性の悪化要因のひとつであるが、本発明のブレンド系では溶解性の向上により精製のレベルが上がり、電子写真特性の悪化を抑制していると考えられる。
【００４５】
この分子レベルにおけるブレンドが分子内密度を上げ且つ非晶質部分と結晶質部分を同一分子内に併せ持つため塗膜形成時に発生する分子内応力をも緩和することができ、それによりソルベントクラックの要因となる薬品が侵入しても内部応力を維持しクラックが生じないと推定される。
【００４６】
なお、本発明においては、式（１）で示される構成単位を有するポリアリレート、及び式（２）で示される構成単位を有するポリカーボネート、及び式（３）及び式（４）で示される構成単位を有する共重合体の粘度平均分子量は１０，０００〜２００，０００であることが好ましく、特には１５，０００〜１００，０００であることが好ましい。また、式（１）で示される構成単位を有するポリアリレートの粘度平均分子量（Ｍａ）と、式（２）で示される構成単位を有するポリカーボネートの粘度平均分子量（Ｍｃ）と、式（３）及び式（４）で示される構成単位を有する共重合体の粘度平均分子量（Ｍｓ）は、Ｍａ≧Ｍｃ≧Ｍｓであることが好ましい。
【００４７】
また、式（１）で示される構成単位を有するポリアリレートの重量混合比（Ｗａ）と、式（２）で示される構成単位を有するポリカーボネートの重量混合比（Ｗｃ）と、式（３）及び式（４）で示される構成単位を有する共重合体の重量混合比（Ｗｓ）は、Ｗａ／Ｗｃ＝９５／５〜５／９５であることが好ましく、Ｗｓ／（Ｗａ＋Ｗｃ）＝１／９９〜３０／７０であることが好ましい。
【００４８】
また、フッ素系樹脂粉体の重量混合比（Ｗｆ）は、Ｗｆ／（Ｗａ＋Ｗｃ＋Ｗｓ）＝１／１００〜５０／１００であることが好ましい。またケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体の混合重量比（Ｗｆ）はＷｆ／（Ｗａ＋Ｗｃ＋Ｗｓ）＝０．０２／１００〜２０／１００であることが好ましい。
【００４９】
以下本発明に用いる電子写真感光体の構成について説明する。
【００５０】
本発明における電子写真感光体は、感光層が電荷輸送材料と電荷発生材料を同一の層に含有する単層型であっても、電荷輸送層と電荷発生層に分離した積層型でもよいが電子写真特性からは積層型が好ましい。いずれの場合も、少なくとも電子写真感光体の表面層が、前述のとおり式（１）で示される繰返し単位を有するポリアリレート、及び式（２）で示される繰返し単位を有するポリカーボネート、式（３）で示される繰返し単位及び式（４）で示される繰返し単位を有する共重合体、並びに、フッ素系樹脂粉体又はケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体を含有する。
【００５１】
使用する導電性支持体は、導電性を有するものであればよく、アルミニウム、ステンレス等の金属、あるいは導電層を設けた金属、紙、プラスチック等が挙げられ、形状はシート状、円筒状等が挙げられる。特に、ＬＢＰ等の画像入力がレーザー光の場合は、散乱による干渉縞防止、または支持体の傷を被覆することを目的とした導電層を設けることが好ましい。これはカーボンブラック、金属粒子等の導電性粉体をバインダー樹脂に分散させて形成することができる。導電層の膜厚は５〜４０μｍ、好ましくは１０〜３０μｍが適当である。
【００５２】
その上に必要に応じて接着機能及びバリアー機能を有する中間層を設けることができる。中間層の材料としては、ポリアミド、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、カゼイン、ポリウレタン、ポリエーテルウレタン等が挙げられる。これらは適当な溶剤に溶解して塗布される。中間層の膜厚は０．０５〜５μｍ、好ましくは０．３〜１μｍが適当である。
【００５３】
機能分離型の場合、その上には電荷発生層が形成される。本発明に用いられる電荷発生材料としては、セレン−テルル、ピリリウム、チアピリリウム系染料、フタロシアニン、アントアントロン、ジベンズピレンキノン、トリスアゾ、シアニン、ジスアゾ、モノアゾ、インジゴ、キナクリドン、非対称キノシアニン系の各顔料が挙げられる。電荷発生層は前記電荷発生材料を０．３〜４倍量のバインダー樹脂及び溶剤とともにホモジナイザー、超音波分散、ボールミル、振動ボールミル、サンドミル、アトライター、ロールミル及び液衝突型高速分散機等を使用してよく分散し、分散液を塗布、乾燥させて形成される。電荷発生層の膜厚は５μｍ以下、好ましくは０．１〜２μｍが適当である。
【００５４】
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。用いられる電荷輸送材料としては、トリアリールアミン系化合物、ヒドラゾン化合物、スチルベン化合物、ピラゾリン系化合物、オキサゾール系化合物、トリアリルメタン系化合物、チアゾール系化合物等が挙げられる。
【００５５】
これらは０．５〜２倍量のバインダー樹脂と組み合わされ、塗布、乾燥して電荷輸送層を形成する。電荷輸送層の膜厚は５〜４０μｍ、好ましくは１５〜３０μｍが適当である。
【００５６】
感光層が単層型の場合は、上述のような電荷発生材料や電荷輸送材料を上述のようなバインダー樹脂に分散、溶解した溶液を塗布、乾燥することによって形成される。膜厚は５〜４０μｍ、好ましくは１５〜３０μｍが適当である。
【００５７】
図１に本発明の電子写真感光体を有するプロセスカートリッジを有する電子写真装置の概略構成を示す。
【００５８】
図において、１はドラム状の本発明の電子写真感光体であり、軸２を中心に矢印方向に所定の周速度で回転駆動される。感光体１は、回転過程において、一次帯電手段３によりその周面に正または負の所定電位の均一帯電を受け、次いで、スリット露光やレーザービーム走査露光等の像露光手段（不図示）からの画像露光光４を受ける。こうして感光体１の周面に静電潜像が順次形成されていく。
【００５９】
形成された静電潜像は、次いで現像手段５によりトナー現像され、現像されたトナー現像像は、不図示の給紙部から感光体１と転写手段６との間に感光体１の回転と同期取り出されて給紙された転写材７に、転写手段６により順次転写されていく。
【００６０】
像転写を受けた転写材７は、感光体面から分離されて像定着手段８へ導入されて像定着を受けることにより複写物（コピー）として装置外へプリントアウトされる。
【００６１】
像転写後の感光体１の表面は、クリーニングブレード９によって転写残りトナーの除去を受けて清浄面化され、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。
【００６２】
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可能に構成しても良い。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つを感光体１と共に一体に支持してカートリッジ化して、装置本体のレール１２等の案内手段を用いて装置本体に着脱可能なプロセスカートリッジ１１とすることができる。
【００６３】
また、画像露光光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アレイの駆動及び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。
【００６４】
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、液晶プリンター、レーザー製版等電子写真応用分野にも広く用いることができる。
【００６５】
以下、実施例に従って説明する。
【００６６】
本発明で用いる式（１）で示される構成単位を有するポリアリレート、及び式（２）で示される構成単位を有するポリカーボネート、及び式（３）及び式（４）で示される構成単位を有する共重合体は常法により合成した。
【００６７】
式（１）で示される構成単位を有するポリアリレート、及び式（２）で示される構成単位を有するポリカーボネート、及び式（３）及び式（４）で示される構成単位を有する共重合体のブレンドの手段としては、各ポリマーを粉体でブレンドする方法、良溶媒中で溶解しながらブレンドする方法等が適用可能であるが、本発明では、良溶媒中で溶解し貧溶媒で再沈殿させてブレンドする方法が効果的である。手順としては、まず各ポリマーを任意の混合比で秤量し１０倍量（ｗｔ）のジクロロメタンに十分に溶解した。ついで溶解溶媒の１０倍量（ｗｔ）のメタノールを攪拌しながら、このポリマー溶液を徐々に滴下した。このメタノール中で白色綿状のブレンドポリマーを得た。これを真空乾燥しフレーク状にして用いた。
［実施例１］
３０φ２５４ｍｍのＡｌシリンダーを支持体とし、これに、以下の材料より構成される塗料を支持体上に浸漬法で塗布し、１４０℃、３０分熱硬化して膜厚１５μｍの導電層を形成した。
【００６８】
導電性顔料：ＳｎＯ₂コート処理硫酸バリウム １０部
抵抗調節用顔料：酸化チタン ２部
バインダー樹脂：フェノール樹脂 ６部
レベリング材：シリコーンオイル ０．００１部
溶剤：メタノール、メトキシプロパノール０．２／０．８ ２０部
次にこの導電層上に、Ｎ−メトキシメチル化ナイロン３部及び共重合ナイロン３部をメタノール６５部、ｎ−ブタノール３０部の混合溶媒に溶解した溶液を浸漬法で塗布し、膜厚０．５μｍの中間層を形成した。
【００６９】
次にＣｕＫαのＸ線回折における回折角２θ±０．２°が９．０°、１４．２°、２３．９°、２７．１°に強いピークを有するＴｉＯＰｃ４部とポリビニルブチラール（商品名：エスレックＢＭ２、積水化学製）２部及びシクロヘキサノン６０部をφ１ｍｍガラスビーズを用いたサンドミル装置で４時間分散したあと、エチルアセテート１００部を加えて電荷発生層用分散液を調製した。これを浸漬法で塗布し、膜厚０．３μｍの電荷発生層を形成した。
【００７０】
次に、電荷輸送層を形成するために、電荷輸送層用の塗料を調製した。ビスフェノールＣ型（例１−２）のポリアリレート５０部及びビスフェノールＺ型（例２−３）のポリカーボネート４０部および例３−１と例２−１３に示される変性ポリカーボネート１０部を用いて調製したブレンドポリマーを用いた。このブレンドポリマー１００部、ポリ四フッ化エチレン（商品名ルブロンＬ−２、ダイキン工業（株）製）１０部、フッ素系グラフトポリマー（商品名アロンＧＦ３００、東亞合成化学工業（株）製）０．５部を、モノクロロベンゼン５００部、ジクロロメタン５００部中に溶解し、ステンレス製ボールミルにて４８時間分散した。
【００７１】
得られた分散液に下記構造式のアミン化合物９０部
【００７２】
【化１４】

下記構造式のアミン化合物１０部
【００７３】
【化１５】

を溶解し、電荷輸送層用の塗料を得た。
【００７４】
この塗料を浸漬法で塗布し１２０℃２時間乾燥し２５μｍの電荷輸送層を形成した。
【００７５】
次に評価について説明する。
【００７６】
装置はビューレットパッカード製ＬＢＰ「レーザージェット４ｐｌｕｓ」（プロセススピード７１ｍｍ／ｓｅｃ）を改造して用いた。改造は帯電器の直前にヒューズランプによる前露光を取り付け、残留電位測定時のみ点灯させて使用した。電位測定は、暗部をＶｄ、レーザー光照射部をＶｌ、前露光照射部をＶｒとして行った。作成した電子写真感光体をこの装置で２３℃、５５％ＲＨ下で通紙耐久を行った。シーケンスはプリント１枚ごとに１回停止する間欠モードとし１０００枚をプリントしたところで電位を測定し、続けて５０００枚まで通紙耐久を行い感光体の削れ量を測定した。また３２．５℃、８５％ＲＨの高温高湿環境で１５０００枚の通紙耐久を行った。シーケンスはプリント１枚ごとに１回停止する間欠モードとし、５００枚毎に１０分間プリントを休止し、１０００枚毎にカートリッジを出し入れすることを繰り返し、１５０００枚を耐久してクリーニングブレードのめくれを評価した。尚、必要に応じ１０分間のプリント休止中にトナー補給を行った。さらにソルベントクラック性は表面に指脂を付着させ２４時間放置し顕微鏡観察によりソルベントクラックの有無を観察した。ポットライフの評価として、各電荷輸送層塗料を室温（２３℃）にて密閉容器中にて１週間静置した後、溶解状態を観察した。
［実施例２］
用いるブレンドポリマーとしてビスフェノールＺ型（例１−２３）及びビスフェノールＣ型（例１−２）を１／１で共重合したポリアリレートを用い、表１０に示す条件とした以外は実施例１と同様にして行った。結果を表１２に示す。
［実施例３〜６、参考例１〜６］
用いるポリマー、フッ素系樹脂粉体、混合比、及びブレンドポリマーとして用いたか各ポリマーを別々に用いたかの別を表１０に示す条件とした以外は実施例１と同様にして行った。結果を表１２に示す。
［比較例１〜１８］
用いるポリマー、フッ素系樹脂粉体、混合比、及びブレンドポリマーとして用いたか各ポリマーを別々に用いたかの別を表１１に示す条件とした以外は実施例１と同様にして行った。結果を表１２に示す。
【００７７】
【表１０】

【表１１】

【００７８】
【表１２】

＊：「再沈殿」は、溶解／再沈殿によりブレンドしたもの
「別々」は、溶解時に順次加えてたもの
＊＊：クラックがなかったもの＝○
クラックの発生があったもの＝×
＊＊＊：溶解していたもの＝○
ゲル化または溶解しなかったもの＝×
＊＊＊＊：クリーニングブレードがめくれなかったもの＝○
クリーニングブレードがめくれたもの＝×
クリーニングブレードはめくれなかったが１５０００枚迄プリントできなかったもの＝（○）
このように、本発明で示したポリアリレートとポリカーボネートと変性ポリカーボネートとフッ素系樹脂粉体を含有する事により、優れた機械的強度と表面潤滑性を耐久後まで併せ持つ電子写真感光体を提供することができる。さらに電子写真特性が良好であり、かつ製造時の塗工性及び塗料ポットライフが良好であり、一般的なクリーニングブレードでも捲れの起こらない電子写真感光体を提供することができる。
【００７９】
以下の実施例で用いたケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体（化合物Ｎｏ．４−１〜４−４）は表に示す如くである。
【００８０】
【表１３】

［実施例７］
実施例１と同様の方法で膜厚１５μｍの導電層、膜厚０．５μｍの中間層、膜厚０．３μｍの電荷発生層を形成した。
【００８１】
次に、電荷輸送層を形成するために、電荷輸送層用の塗料を調製した。ビスフェノールＣ型（例１−２）のポリアリレート５０部及びビスフェノールＺ型（例２−３）のポリカーボネート４０部及び例３−１と例２−１３に示される変性ポリカーボネート１０部を用いて調製したブレンドポリマーを用いた。このブレンドポリマー１００部、ケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体（化合物Ｎｏ．４−１）２部、下記構造式のアミン化合物９０部及び
【００８２】
【化１６】

下記構造式のアミン化合物１０部
【００８３】
【化１７】

を、モノクロロベンゼン５００部、ジクロロメタン５００部中に溶解し、電荷輸送層用の塗料を得た。この塗料を浸漬法で塗布し１２０℃、２時間乾燥し２５μｍの電荷輸送層を形成した。次に実施例１と同様に評価された結果を表１６に示す。
［実施例８］
用いるブレンドポリマーとしてビスフェノールＺ型（例１−２３）およびビスフェノールＣ型（例１−２）を１／１で共重合したポリアリレートを用い、表１４に示す条件とした以外は実施例１と同様にして行った。結果を表１６に示す。
［実施例９〜１２、参考例７〜１２］
用いるポリマー、ケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体、混合比、及びブレンドポリマーとして用いたか各ポリマーを別々に用いたかの別を表１４に示す条件とした以外は実施例１と同様にして行った。結果を表１６に示す。
［比較例１９〜３６］
用いるポリマー、ケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体、混合比、及びブレンドポリマーとして用いたか各ポリマーを別々に用いたかの別を表１５に示す条件とした以外は実施例１と同様にして行った。結果を表１６に示す。
【００８４】
【表１４】

【表１５】

【００８５】
【表１６】

表中の＊、＊＊、＊＊＊、＊＊＊＊は表１０及び１１の備考と同じ
このように、本発明で示したポリアリレートとポリカーボネートと変性ポリカーボネートとケイ素原子を側鎖に有する重合性単量体を構成成分として有するグラフト重合体を含有することにより、優れた機械的強度と表面潤滑性を耐久後まで併せ持つ電子写真感光体を提供することができる。さらに電子写真特性が良好であり、かつ製造時の塗工性及び塗料ポットライフが良好であり、一般的なクリーニングブレードでも捲れの起こらない電子写真感光体を提供することができる。
【００８６】
【発明の効果】
以上に説明したように本発明の電子写真感光体は、優れた機械的強度と表面潤滑性を耐久後まで併せ持ち、良好な電子写真特性を持っている。また、溶解性、ポットライフの改善により、材料（構成単位）の選択の幅が広がり、利用目的に応じた電子写真感光体の提供が可能となった。
【図面の簡単な説明】
【図１】 本発明の電子写真感光体を有するプロセスカートリッジを有する電子写真装置の概略構成の例を示す図である。
【符号の説明】
１ 本発明の電子写真感光体
２ 軸
３ 一次帯電手段
４ 画像露光光
５ 現像手段
６ 転写手段
７ 転写材
８ 像定着手段
９ クリーニングブレード
１０ 前露光光
１１ プロセスカートリッジ
１２ レール[0001]
BACKGROUND OF THE INVENTION
  The present invention, Production method of electrophotographic photosensitive member,Electrophotographic photoreceptor, Process cartridge and electrophotographic apparatusFor more information,An electrophotographic photosensitive member having a photosensitive layer containing a specific resin on the surface layerManufacturing method, electrophotographic photosensitive member,AndThe present invention relates to a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.
[0002]
[Prior art]
  In the electrophotographic method, as shown in U.S. Pat. No. 2,297,691, the electrical conductivity changes depending on the dose received during image exposure, and in the dark, a photoconductive film comprising a support coated with an insulating material. Uses a functional material. The basic characteristics required for an electrophotographic photosensitive member using this photoconductive material are (1) that it can be charged to an appropriate potential in a dark place, (2) there is little potential dissipation in the dark place, (3) Dissipating charges quickly by light irradiation, and the like.
[0003]
  Conventionally, as an electrophotographic photosensitive member, an inorganic photosensitive member having a photosensitive layer mainly composed of an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide has been widely used. However, these satisfy the above conditions (1) to (3), but are not necessarily satisfactory in terms of thermal stability, moisture resistance, durability and productivity. In order to overcome the disadvantages of inorganic photoreceptors, electrophotographic photoreceptors based on various organic photoconductive compounds as main components have been actively developed in recent years. For example, US Pat. No. 3,378,851 discloses a photoreceptor having a charge transport layer containing triallyl pyrazoline, US Pat. No. 3,871,880 discloses a charge generation layer comprising a derivative of perylene pigment, and condensation of 3-propylene and formaldehyde. Known are photoreceptors comprising a charge transport layer comprising a body.
[0004]
  Furthermore, the organic photoconductive compound can freely select the photosensitive wavelength range of the electrophotographic photosensitive member depending on the compound. For example, for azo pigments, JP-A 61-272754 and JP-A 56-167759. The substances disclosed in the gazette are disclosed as having high sensitivity in the visible region, and the compounds disclosed in JP-A-57-19576 and JP-A-61-228453 are sensitive to the infrared region. Is shown. Among these materials, those showing sensitivity in the infrared region are used in laser beam printers (hereinafter abbreviated as LBP) and LED printers that have made remarkable progress in recent years, and the demand frequency thereof is increasing. Electrophotographic photoreceptors using these organic photoconductive compounds are used as function-separated photoreceptors in which a charge transport layer and a charge generation layer are laminated in order to satisfy both electrical and mechanical properties. There are many cases. On the other hand, as a matter of course, the electrophotographic photosensitive member is required to have sensitivity, electrical characteristics, and optical characteristics according to the applied electrophotographic process. In particular, in an electrophotographic photoreceptor that is used repeatedly, the surface of the electrophotographic photoreceptor is directly subjected to electrical and mechanical external forces such as corona or direct charging, image exposure, toner development, transfer process, and surface cleaning. , Durability against them is also required.
[0005]
  Specifically, it can be used for electrical degradation due to ozone and nitrogen oxides during charging, mechanical degradation in which the surface is worn or scratched due to discharge during charging, and rubbing of the cleaning member, and electrical degradation. Durability is required. The electrical deterioration is particularly problematic in that a carrier stays in a portion irradiated with light and an electrical difference occurs from a portion not irradiated with light, which occurs as a photo memory. Mechanical degradation is particularly different from inorganic photoreceptors, and organic photoreceptors, which are often soft in material, are inferior in durability against mechanical degradation, and improvement in durability is particularly desired. Various attempts have been made to satisfy the durability characteristics required for the photoreceptor as described above.
[0006]
  Polycarbonate resin with bisphenol A as a skeleton is attracting attention as a resin that is often used for the surface layer and has good wear and electrical properties. However, it cannot solve all of the above-mentioned problems. It has the following problems. (1) These solvents are poor in solubility, exhibit good solubility only in a part of halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane, and these solvents have low boiling points. When a photoconductor is produced using the coating solution prepared in step 1, the coated surface is likely to be whitened. It also takes time to manage the solid content of the coating liquid. (2) Solvents other than halogenated aliphatic hydrocarbons are partially soluble in tetrahydrofuran, dioxane, cyclohexanone or a mixed solvent thereof, but the solution is gelable in a few days. Unfortunately, it is not suitable for photoconductor production. (3) Even if the above (1) and (2) are improved, solvent cracks are likely to occur in the polycarbonate resin having bisphenol A as a skeleton. (4) In addition, with the conventional polycarbonate resin, the film formed with the resin does not have lubricity, so the photoconductor is easily damaged, and the image is not cleaned in a cleaning setting that reduces the wear amount of the electrophotographic photoconductor. In some cases, defects may occur, cleaning defects due to early deterioration of the cleaning blade, toner fusion, and the like may occur.
[0007]
  The solution stability listed in the above (1) and (2) can be solved by using a polycarbonate Z resin having a bulky cyclohexylene group as a polymer structural unit or by copolymerizing with bisphenol Z, bisphenol C or the like. It has been.
[0008]
  On the other hand, polyarylate has a structure similar to that of polycarbonate, but various properties are different. For example, although the mechanical strength is superior, the solubility of Z-type having a cyclohexylidene group is low. There are also differences in the characteristics of the electrophotographic photosensitive member. In particular, when used as a binder resin for a charge transport layer, each memory, residual potential, and the like are easily changed (deteriorated) depending on the structure of the charge transport material used.
[0009]
  In addition, since the coating film formed is tougher than the conventional polycarbonate resin and the cleaning method using a general rubber blade does not roughen the surface of the polycarbonate, the cleaning blade is in contact with the counter direction due to the increase in the contact area. The phenomenon that the cleaning blade is swollen easily occurs.
[0010]
  Solvent cracks can also be solved by using silicon-modified polycarbonate or ether-modified polycarbonate as disclosed in JP-A-6-51544 and JP-A-6-75415. However, these modified polycarbonates have a structure that provides flexibility against internal stress in the polymer in order to prevent solvent cracks compared to conventional polycarbonate resins, resulting in the mechanical properties of the polymer body. There was a drawback that the strength decreased.
[0011]
  In recent years, a direct charging method in which a charge is applied to an electrophotographic photosensitive member by directly applying a voltage to a charging member as disclosed in Japanese Patent Application Laid-Open Nos. 57-17826 and 58-40566 has been mainly used. It is becoming. This is a method in which a roller-shaped charging member made of conductive rubber or the like is directly brought into contact with the electrophotographic photosensitive member to apply electric charge. Compared to scorotron, etc., the amount of ozone generated is significantly smaller. Around 80% of the current flowing through the charger flows through the shield and is wasted, whereas direct charging has the advantage of being very economical because there is no waste.
[0012]
[Problems to be solved by the invention]
  The object of the present invention is to solve the problem of having a conventional polycarbonate resin or polyarylate resin as a surface layer, and to consistently combine both high mechanical strength and high lubricity until after durability. Another object is to provide an electrophotographic photosensitive member. Another object is to provide an electrophotographic photosensitive member that has good electrophotographic characteristics, has good coatability and paint pot life at the time of manufacture, and does not wrinkle even with a general cleaning blade.
[0013]
[Means for Solving the Problems]
  In accordance with the present invention, a conductive support and a photosensitive layerHaveElectrophotographic photoreceptorManufacturing methodIn
A polyarylate having a repeating unit represented by the following formula (1), a polycarbonate having a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3) and the following formula (4) A step of obtaining a mixed polymer solution by dissolving and mixing a copolymer having repeating units in a good solvent;
Polyarylate having a repeating unit represented by the following formula (1) dissolved in the mixed polymer solution, a polycarbonate having a repeating unit represented by the following formula (2), and a repeating represented by the following formula (3) By reprecipitating a copolymer having a unit and a repeating unit represented by the following formula (4) using a poor solvent, a polyarylate having a repeating unit represented by the following formula (1), A step of obtaining a blend material of a polycarbonate having a repeating unit shown, and a copolymer having a repeating unit shown by the following formula (3) and a repeating unit shown by the following formula (4):
The surface layer of the electrophotographic photosensitive member is formed using the blend material and a paint containing a fluoropolymer powder and / or a graft polymer having a polymerizable monomer having a silicon atom in the side chain as a constituent component. And a process of
HaveAn electrophotographic photosensitive member characterized byManufacturing methodIs provided.
[0014]
[Chemical formula 5]

(X ₁ Is a carbon atom or a single bond (in this case R _Five , R ₆ None), R ₁ ~ R _Four Represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group or an aryl group, and R _Five , R ₆ Are each a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group, or R _Five And R ₆ Represents an alkylidene group formed by bonding, R ₇ ~ R _Ten Each represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group or an aryl group)
[0015]
[Chemical 6]

(X ₂ Is a carbon atom or a single bond (in this case R ₁₅ , R ₁₆ None), R ₁₁ ~ R ₁₄ Represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group or an aryl group, and R ₁₅ , R ₁₆ Are each a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group, or R ₁₅ And R ₁₆ Represents an alkylidene group formed by bonding)
[0016]
[Chemical 7]

(R ₁₇ ~ R _{twenty two} Each represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group or an aryl group, and n represents a positive integer)
[0017]
[Chemical 8]

(X _Three Is a carbon atom or a single bond (in this case R ₂₇ , R ₂₈ None), R _{twenty three} ~ R ₂₆ Each represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group or an aryl group, and R ₂₇ , R ₂₈ Are each a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group, or R ₂₇ And R ₂₈ Represents an alkylidene group formed by bonding)
  According to the present invention, there is also provided an electrophotographic photoreceptor produced by the above production method.
  In addition, according to the present invention, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member are provided.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
  In the formulas (1) to (4), the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and the like, and the alkyl group includes a lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the cycloalkylidene group include a cyclohexylidene group. Examples of the substituent that the alkyl group, aryl group, and cycloalkylidene group may have include a lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, an aryl group such as a phenyl group and a naphthyl group, Halogen atoms such as fluorine atom, chlorine atom, bromine atom and the like can be mentioned. n represents a positive integer and is preferably 1 to 200.
[0019]
  Specific examples of the structural unit represented by the formula (1) are shown in Table 1.~ 4However, the present invention is not limited to these.
[0020]
[Table 1]

[0021]
[Table 2]

[0022]
[Table 3]

[0023]
[Table 4]

  The polymer having the structural unit represented by the formula (1) used in the present invention usually contains terephthalic acid chloride, a mixture of isophthalic acid chloride, and various bisphenols for the control of solubility and rigidity. It can be obtained by interfacial polymerization with stirring in a solvent / water system under alkali. That is, Table 1~ 4The formula shown in FIG. 5 was expressed as a form prepared from a mixed system of terephthalic acid chloride and isophthalic acid chloride. However, the ratio of terephthalic acid chloride and isophthalic acid chloride is determined in consideration of the solubility of the polymer, and there is no established theory. However, it should be noted that if any chloride is 30 mol% or less, the solubility of the synthesized polymer is extremely lowered. Usually, it is preferable to synthesize at a ratio of 1/1. In the electrophotographic photoreceptor of the present invention, even a monopolymer composed of the same structural unit represented by the formula (1) may be composed of two or more different structural units represented by the formula (1). It may be a polymer.
[0024]
  A specific example of the structural unit represented by formula (2)5-7However, the present invention is not limited to these.
[0025]
[Table 5]

[0026]
[Table 6]

[0027]
[Table 7]

  A specific example of the structural unit represented by Formula (3)8 and 9However, it is not limited to these.
[0028]
[Table 8]

[0029]
[Table 9]

  For formula (4),5-7Is the same as the equation (2) shown in FIG.5-7Apply the example.
[0030]
  Used in the present inventionRufuSpecific examples of the nitrogen-based resin powder include tetrafluoroethylene resin, trifluoroethylene chloride resin, tetrafluoroethylene hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluoride dichloride. Examples thereof include ethylene resins and copolymers thereof. Preferable examples include tetrafluoroethylene resin and vinylidene fluoride resin, and particularly preferable examples include tetrafluoroethylene resin.
[0031]
  Also used in the present inventionRukeA graft polymer having a polymerizable monomer having an iodine atom in the side chain as a constituent component is a monomer having a silicon atom in the side chain and having a polymerizable functional group at the terminal, and does not have a silicon atom. It is obtained by copolymerizing a polymerizable monomer or a macromonomer composed of a relatively low molecular weight oligomer having a molecular weight of about 1000 to 10,000 having a polymerizable functional group at the terminal, and is obtained by silicon with respect to the main chain. It has a structure in which side chains containing atoms hang from branches. Examples of the polymerizable monomer having a silicon atom in the side chain include the following compounds, but the present invention is not limited to these examples.
[0032]
[Chemical 9]

[0033]
[Chemical Formula 10]

[0034]
Embedded image

[0035]
Embedded image

[0036]
Embedded image

  In the above formula, R is H or CH_ThreeIt is.
[0037]
  One polymerizable monomer or macromonomer is selected to be compatible with the resin to which the graft polymer is to be added. For example, acrylic esters, methacrylic esters, styrene and styrene derivatives are used. It is done. The copolymerization ratio is preferably 5 wt% or more as the content of the polymerizable monomer having a silicon atom in the side chain. The molecular weight of the obtained polymer is preferably 500 to 100,000, particularly preferably 1,000 to 5,000, as a weight average molecular weight.
[0038]
  Although the detailed mechanism has not been fully elucidated, the polyarylate having the structural unit represented by the formula (1), the polycarbonate having the structural unit represented by the formula (2), and the formula (3) and the formula ( 4) Mixing and using each polymer of the copolymer having the structural unit represented byNiBy containing the nitrogen-based resin powder, surface lubricity, solvent crack resistance, and the like can be improved stably from the end of durability to the end of durability. This is because the polyarylate structure, the polycarbonate structure and the siloxane structure enter between the molecular chains, destroying the crystallinity of each, and further dispersing the fluorine resin powder inside the film, so Innumerable molecular groups and intramolecular orientational order with resin powder as a core can be created, which can improve high surface lubricity and solvent crack resistance after durability while maintaining high wear resistance. Inferred.
[0039]
  MoreNiBy including a graft polymer having a polymerizable monomer having an iodine atom in the side chain as a constituent component, surface lubricity, solvent crack resistance, etc. can be improved stably from the end of durability to after durability. . It is known that a graft polymer having a polymerizable monomer having a silicon atom in the side chain as a constituent component has a strong surface migration property, and therefore constitutes a polymerizable monomer having an added silicon atom in the side chain. It can be easily understood that the graft polymer as a component will mostly localize near the membrane surface and improve the surface lubricity at the initial stage of durability, but the structure according to the present invention is stable from the initial stage of durability to after the endurance. It is surprising that the surface lubricity is improved. This is a graft polymer in which a polyarylate structure, a polycarbonate structure, and a siloxane structure enter between each molecular chain to break each crystallinity, and a polymerizable monomer having a silicon atom as a side chain as a constituent component. By being present not only in the vicinity of the film surface but also in the film, a molecular group including a graft polymer having a polymerizable monomer having a silicon atom as a side chain in the film as a constituent component and an intramolecular alignment order are created. Thus, it is presumed that the high surface lubricity and the solvent crack resistance after the endurance can be improved while maintaining high wear resistance.
[0040]
  In addition, this effect is effective when all the graft polymers having a polyarylate structure, a polycarbonate structure, a siloxane structure, and a polymerizable monomer having a silicon atom in the side chain as constituent components are provided. Since it is expressed and the effect is greatly impaired even if one of the constituent elements is missing, it has a conventionally known siloxane structure or a polymerizable monomer having a silicon atom in the side chain as a constituent component It is presumed that a new effect far exceeding the lubricity and solvent crack resistance of the graft polymer is manifested by the interaction between the components of the present invention.
[0041]
  Further, although the detailed mechanism has not been fully elucidated, R in the formula (1)₁, R₂, R_Five, R₆Is a methyl group and R_Three, R_Four, R₇, R₈, R₉, R_TenContaining a polyarylate having a structural unit in which is a hydrogen atom, and R in the formula (2)₁₁~ R₁₄Is a hydrogen atom and R₁₅, R₁₆Contains a polycarbonate having a structural unit which is a cyclohexylidene group together with X, and R in the formula (3)₁₇~ R₂₀Is a methyl group and R_{twenty one}, R_{twenty two}Is a hydrogen atom and R in formula (4)_{twenty three}~ R₂₆Is a hydrogen atom and R₂₇, R₂₈Are used in combination with each polymer of a copolymer having a constitutional unit in which X is a cyclohexylidene group.NiContaining nitrogen-based resin powder and / or silicon atom in the side chainHas a polymerizable monomer as a constituentBy including the graft polymer, surface lubricity, solvent crack resistance and the like can be improved particularly stably from the initial durability period to after the durability period. This is because the polyarylate structure is R in formula (1).₁, R₂, R_Five, R₆Is a methyl group and R_Three, R_Four, R₇, R₈, R₉, R_TenIs a hydrogen atom and the polycarbonate structure is R in the formula (2)₁₁~ R₁₄Is a hydrogen atom and R₁₅, R₁₆Is a cyclohexylidene group together with X, and the siloxane structure is R in the formula (3)₁₇~ R₂₀Is a methyl group and R_{twenty one}, R_{twenty two}Is a hydrogen atom, R in formula (4)_{twenty three}~ R₂₆Is a hydrogen atom and R₂₇, R₂₈Is closely related to the fact that it is a cyclohexylidene group together with X, how to enter between each molecular chain, how each crystallinity breaks down,No fuContaining nitrogen-based resin powder and / or silicon atom in the side chainHas a polymerizable monomer as a constituentIt is inferred that there is a difference in the way the molecular groups including the graft polymer and the intramolecular orientation order are formed, thereby improving high surface lubricity and solvent crack resistance after durability while maintaining high wear resistance. It is assumed that it can be done.
[0042]
  Further, polyarylate having a structural unit represented by the formula (1), a polycarbonate having a structural unit represented by the formula (2), and a co-polymer having the structural units represented by the formula (3) and the formula (4) By containing the blend material obtained by dissolving and mixing the coalescence in a good solvent and reprecipitating with a poor solvent, the effects of the present invention can be further exhibited. The method of dissolution-reprecipitation is performed in a conventional manner, for example, a polyarylate having a structural unit represented by the formula (1) in a good solvent such as dichloromethane or chloroform, and a polycarbonate having a structural unit represented by the formula (2), And the copolymer which has a structural unit shown by Formula (3) and Formula (4) is fully dissolved. Next, the mixed polymer solution is reprecipitated from a poor solvent such as methanol or water to obtain a cotton-like polymer. This is vacuum dried to obtain a blend material. The material thus obtained includes a polyarylate having a structural unit represented by the formula (1), a polycarbonate having a structural unit represented by the formula (2), and a composition represented by the formulas (3) and (4). The solubility and paint stability are improved compared to a simple blend of copolymers having units. This method has any of the polyarylate having the structural unit represented by the formula (1), the polycarbonate having the structural unit represented by the formula (2), and the structural unit represented by the formulas (3) and (4). Copolymers are also effective, but polycarbonate A type and polyarylate Z type, which are particularly poor in solubility, are effective in improving characteristics.
[0043]
  Although the detailed mechanism has not been fully elucidated, a polyarylate structure having a structural unit represented by the formula (1) and a structure represented by the formula (2) are obtained by previously blending each polymer in a solution. A polycarbonate structure having units and a copolymer structure having structural units represented by the formulas (3) and (4) can be highly blended, and the resulting blended material penetrates between the molecular chains.MehuContaining nitrogen-based resin powder and / or silicon atom in the side chainHas a polymerizable monomer as a constituentIt is presumed that new characteristics due to the interaction with the graft polymer are easily developed.
[0044]
  First, in the low-solubility polycarbonate type A and polyarylate Z type, it is thought that the crystallinity of each component is broken by blending molecules of different structures, so the solubility of each component in the solvent is reduced. It is presumed that it has been improved, and further gelation during storage can be suppressed. Further, the reason for the decrease in electrophotographic characteristics is estimated as follows. The phthalate structure, which is one of the factors in which polyarylate is excellent in mechanical strength, is expected to become one of the carrier trapping factors in combination with the charge transporting material. ) And a copolymer having the structural unit represented by formula (3) and formula (4) are present in the vicinity of the polyarylate having the structural unit represented by formula (1) at the molecular level. Therefore, it is presumed that some kind of interaction occurs with the phthalate structure, and the trapping of carriers due to the phthalate structure is reduced. Furthermore, residual impurities (residual monomers, chlorides, etc.) in the polymer are one of the causes of deterioration of various characteristics. However, the blend system of the present invention increases the level of purification due to improved solubility and deteriorates electrophotographic characteristics. It is thought that it is suppressing.
[0045]
  This blend at the molecular level increases the intramolecular density and has both the amorphous and crystalline parts in the same molecule, so it can also reduce the intramolecular stress that occurs during the formation of the coating film. It is presumed that the internal stress is maintained and cracks do not occur even if the chemicals that enter become intruded.
[0046]
  In the present invention, polyarylate having a structural unit represented by the formula (1), a polycarbonate having a structural unit represented by the formula (2), and a structural unit represented by the formula (3) and the formula (4). The viscosity-average molecular weight of the copolymer having is preferably 10,000 to 200,000, and particularly preferably 15,000 to 100,000. Further, the viscosity average molecular weight (Ma) of the polyarylate having the structural unit represented by the formula (1), the viscosity average molecular weight (Mc) of the polycarbonate having the structural unit represented by the formula (2), the formula (3) and The viscosity average molecular weight (Ms) of the copolymer having the structural unit represented by the formula (4) is preferably Ma ≧ Mc ≧ Ms.
[0047]
  Further, the weight mixing ratio (Wa) of the polyarylate having the structural unit represented by the formula (1), the weight mixing ratio (Wc) of the polycarbonate having the structural unit represented by the formula (2), the formula (3) and The weight mixing ratio (Ws) of the copolymer having the structural unit represented by the formula (4) is preferably Wa / Wc = 95/5 to 5/95, and Ws / (Wa + Wc) = 1/99 to Preferably it is 30/70.
[0048]
  The weight mixing ratio (Wf) of the fluororesin powder is preferably Wf / (Wa + Wc + Ws) = 1/100 to 50/100. MaTakeWith iodine atom in the side chainHas a polymerizable monomer as a constituentThe mixing weight ratio (Wf) of the graft polymer is preferably Wf / (Wa + Wc + Ws) = 0.02 / 100 to 20/100.
[0049]
  The structure of the electrophotographic photoreceptor used in the present invention will be described below.
[0050]
  The electrophotographic photosensitive member in the present invention may be a single layer type in which the photosensitive layer contains the charge transport material and the charge generation material in the same layer, or a stacked type in which the charge transport layer and the charge generation layer are separated. From the viewpoint of photographic characteristics, the laminated type is preferable. In any case, at least the surface layer of the electrophotographic photosensitive member is represented by the formula (1) as described above.With repeating unitsPolyarylate and represented by formula (2)With repeating unitsPolycarbonate,formula(3)Repeating unit indicated byAnd expressed by equation (4)With repeating unitsCopolymerAndFluorine resin powder or silicon atom in side chainHas a polymerizable monomer as a constituentContains a graft polymer.
[0051]
  The conductive support to be used may be any conductive support, such as a metal such as aluminum or stainless steel, or a metal provided with a conductive layer, paper, plastic, etc. The shape may be a sheet shape, a cylindrical shape, or the like. Can be mentioned. In particular, when the image input such as LBP is laser light, it is preferable to provide a conductive layer for the purpose of preventing interference fringes due to scattering or covering scratches on the support. This can be formed by dispersing conductive powder such as carbon black and metal particles in a binder resin. The thickness of the conductive layer is 5 to 40 μm, preferably 10 to 30 μm.
[0052]
  An intermediate layer having an adhesive function and a barrier function can be provided thereon as necessary. Examples of the material for the intermediate layer include polyamide, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, casein, polyurethane, and polyether urethane. These are dissolved in an appropriate solvent and applied. The thickness of the intermediate layer is 0.05 to 5 μm, preferably 0.3 to 1 μm.
[0053]
  In the case of the function separation type, a charge generation layer is formed thereon. Examples of the charge generation material used in the present invention include selenium-tellurium, pyrylium, thiapyrylium dyes, phthalocyanine, anthanthrone, dibenzpyrenequinone, trisazo, cyanine, disazo, monoazo, indigo, quinacridone, and asymmetric quinocyanine pigments. Can be mentioned. The charge generation layer uses a homogenizer, an ultrasonic dispersion, a ball mill, a vibration ball mill, a sand mill, an attritor, a roll mill, a liquid collision type high-speed disperser, etc. with 0.3 to 4 times the amount of binder resin and solvent. It is well dispersed and formed by coating and drying the dispersion. The film thickness of the charge generation layer is 5 μm or less, preferably 0.1 to 2 μm.
[0054]
  The charge transport layer is formed by applying and drying a paint in which a charge transport material and a binder resin are mainly dissolved in a solvent. Examples of the charge transport material used include triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, triallylmethane compounds, thiazole compounds, and the like.
[0055]
  These are combined with 0.5 to 2 times the amount of binder resin, applied and dried to form a charge transport layer. The thickness of the charge transport layer is 5 to 40 μm, preferably 15 to 30 μm.
[0056]
  When the photosensitive layer is of a single layer type, it is formed by applying and drying a solution in which the charge generating material or charge transporting material as described above is dispersed and dissolved in the binder resin as described above. The film thickness is 5 to 40 μm, preferably 15 to 30 μm.
[0057]
  FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.
[0058]
  In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotated about a shaft 2 in the direction of an arrow at a predetermined peripheral speed. In the rotation process, the photoreceptor 1 is uniformly charged with a positive or negative predetermined potential on its peripheral surface by the primary charging unit 3, and then from an image exposure unit (not shown) such as slit exposure or laser beam scanning exposure. The image exposure light 4 is received. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the photoreceptor 1.
[0059]
  The formed electrostatic latent image is then developed with toner by the developing unit 5, and the developed toner developed image is rotated between the photosensitive member 1 and the transfer unit 6 from a sheet feeding unit (not shown). The image is sequentially transferred by the transfer means 6 to the transfer material 7 that is synchronously taken out and fed.
[0060]
  The transfer material 7 that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means 8, and subjected to image fixing, thereby being printed out as a copy (copy).
[0061]
  The surface of the photoconductor 1 after the image transfer is cleaned by removing the transfer residual toner by the cleaning blade 9, and is further subjected to charge removal processing by pre-exposure light 10 from a pre-exposure means (not shown), and then repeatedly. Used for imaging. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary.
[0062]
  In the present invention, a plurality of components such as the electrophotographic photosensitive member 1, the primary charging unit 3, the developing unit 5 and the cleaning unit 9 described above are integrally coupled as a process cartridge. 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 photosensitive member 1 to form a cartridge, and can be attached to and detached from the apparatus main body using guide means such as a rail 12 of the apparatus main body. The process cartridge 11 can be obtained.
[0063]
  Further, when the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 is a reflected light or transmitted light from a document, or a signal is read out from a document by a sensor, and a laser beam performed according to this signal. Light emitted by scanning, LED array driving, liquid crystal shutter array driving, and the like.
[0064]
  The electrophotographic photosensitive member of the present invention can be used not only in electrophotographic copying machines but also widely in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making.
[0065]
  Hereinafter, it demonstrates according to an Example.
[0066]
  The polyarylate having the structural unit represented by formula (1) and the polycarbonate having the structural unit represented by formula (2) and the co-polymer having the structural units represented by formula (3) and formula (4) are used. The polymer was synthesized by a conventional method.
[0067]
  Blend of polyarylate having the structural unit represented by formula (1), polycarbonate having the structural unit represented by formula (2), and copolymer having the structural unit represented by formula (3) and formula (4) As the means, a method of blending each polymer with powder, a method of blending while dissolving in a good solvent, and the like can be applied. In the present invention, the polymer is dissolved in a good solvent and reprecipitated with a poor solvent. The blending method is effective. As a procedure, first, each polymer was weighed at an arbitrary mixing ratio and sufficiently dissolved in 10 times the amount (wt) of dichloromethane. Subsequently, the polymer solution was gradually added dropwise while stirring 10 times (wt) of methanol as the dissolving solvent. A white flocculent blend polymer was obtained in methanol. This was vacuum dried and used in the form of flakes.
  [Example 1]
  A 30φ254 mm Al cylinder was used as a support, and a coating material composed of the following materials was applied on the support by a dipping method, and heat cured at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 15 μm.
[0068]
  Conductive pigment: SnO₂Coated barium sulfate 10 parts
  Resistance control pigment: Titanium oxide 2 parts
  Binder resin: 6 parts of phenol resin
  Leveling material: 0.001 part of silicone oil
  Solvent: methanol, methoxypropanol 0.2 / 0.8 20 parts
  Next, a solution prepared by dissolving 3 parts of N-methoxymethylated nylon and 3 parts of copolymer nylon in a mixed solvent of 65 parts of methanol and 30 parts of n-butanol was applied onto this conductive layer by a dipping method. A 5 μm intermediate layer was formed.
[0069]
  Next, 4 parts of TiOPc and polyvinyl butyral having a strong peak at 9.0 °, 14.2 °, 23.9 °, and 27.1 ° at diffraction angles 2θ ± 0.2 ° in X-ray diffraction of CuKα (trade name: 2 parts of ESREC BM2, manufactured by Sekisui Chemical Co., Ltd. and 60 parts of cyclohexanone were dispersed in a sand mill apparatus using φ1 mm glass beads for 4 hours, and then 100 parts of ethyl acetate was added to prepare a charge generation layer dispersion. This was applied by a dipping method to form a charge generation layer having a thickness of 0.3 μm.
[0070]
  Next, in order to form a charge transport layer, a paint for the charge transport layer was prepared. Prepared using 50 parts of polyarylate of bisphenol C type (Example 1-2) and 40 parts of polycarbonate of bisphenol Z type (Example 2-3) and 10 parts of the modified polycarbonate shown in Examples 3-1 and 2-13. A blend polymer was used. 100 parts of this blend polymer, 10 parts of polytetrafluoroethylene (trade name Lubron L-2, manufactured by Daikin Industries, Ltd.), fluorine-based graft polymer (trade name Aron GF300, manufactured by Toagosei Co., Ltd.) 5 parts were dissolved in 500 parts of monochlorobenzene and 500 parts of dichloromethane, and dispersed in a stainless steel ball mill for 48 hours.
[0071]
  In the resulting dispersion, 90 parts of an amine compound having the following structural formula
[0072]
Embedded image

  10 parts of amine compound of the following structural formula
[0073]
Embedded image

Was dissolved to obtain a paint for the charge transport layer.
[0074]
  This paint was applied by an immersion method and dried at 120 ° C. for 2 hours to form a 25 μm charge transport layer.
[0075]
  Next, evaluation will be described.
[0076]
  The apparatus used was a modified LBP “Laser Jet 4plus” (process speed 71 mm / sec) manufactured by Vulette Packard. In the modification, a pre-exposure with a fuse lamp was attached just before the charger, and it was turned on only when measuring the residual potential. In the potential measurement, the dark part was Vd, the laser light irradiation part was Vl, and the pre-exposure irradiation part was Vr. The prepared electrophotographic photosensitive member was subjected to paper passing durability at 23 ° C. and 55% RH with this apparatus. The sequence was an intermittent mode that stopped once for each printed sheet, and the potential was measured when 1000 sheets were printed, and then the endurance of the sheet to 5000 sheets was measured to measure the amount of abrasion of the photoreceptor. Further, 15000 sheets were passed through in a high temperature and high humidity environment of 32.5 ° C. and 85% RH. The sequence is an intermittent mode that stops once for each print. The print is paused for 10 minutes after every 500 prints, and the cartridge is inserted and removed every 1000 prints. did. Note that toner replenishment was performed during a 10-minute print pause as required. Further, the solvent cracking property was obtained by attaching finger grease to the surface and leaving it for 24 hours, and observing the presence or absence of the solvent crack by microscopic observation. As an evaluation of the pot life, each charge transport layer coating material was allowed to stand in a closed container at room temperature (23 ° C.) for 1 week, and then the dissolved state was observed.
  [Example 2]
  As the blend polymer used, polyarylate obtained by copolymerizing bisphenol Z type (Example 1-23) and bisphenol C type (Example 1-2) at 1/1 was used.10The same procedure as in Example 1 was performed except that the conditions shown in FIG. Table the results12Shown in
  [Example 36, Reference Examples 1-6]
  Shows the polymer used, fluororesin powder, mixing ratio, and whether it was used as a blend polymer or each polymer was used separately.10The same procedure as in Example 1 was performed except that the conditions shown in FIG. Table the results12Shown in
  [Comparative Examples 1 to 18]
  Shows the polymer used, fluororesin powder, mixing ratio, and whether it was used as a blend polymer or each polymer was used separately.11The same procedure as in Example 1 was performed except that the conditions shown in FIG. Table the results12Shown in
[0077]
[Table 10]

[Table 11]

[0078]
[Table 12]

*: “Reprecipitation” is blended by dissolution / reprecipitation
    "Separate" is added sequentially when dissolving
**: No crack = ○
      Those with cracks = ×
***: What was dissolved = ○
        What did not gel or dissolve = ×
＊＊＊＊: The cleaning blade did not turn = ○
          What the cleaning blade turned over = ×
          The cleaning blade was not turned up, but it could not print up to 15000 sheets = (○)
  Thus, by including the polyarylate, polycarbonate, modified polycarbonate, and fluororesin powder shown in the present invention, an electrophotographic photoreceptor having excellent mechanical strength and surface lubricity until after durability is provided. Can do. Furthermore, it is possible to provide an electrophotographic photosensitive member that has good electrophotographic characteristics, has good coatability and paint pot life at the time of manufacture, and does not wrinkle even with a general cleaning blade.
[0079]
  The graft polymers (Compound Nos. 4-1 to 4-4) having a polymerizable monomer having a silicon atom in the side chain as a constituent component used in the following examples are as shown in the table.
[0080]
[Table 13]

  [Example7]
  A conductive layer having a thickness of 15 μm, an intermediate layer having a thickness of 0.5 μm, and a charge generation layer having a thickness of 0.3 μm were formed in the same manner as in Example 1.
[0081]
  Next, in order to form a charge transport layer, a paint for the charge transport layer was prepared. Prepared using 50 parts of polyarylate of bisphenol C type (Example 1-2) and 40 parts of polycarbonate of bisphenol Z type (Example 2-3) and 10 parts of the modified polycarbonate shown in Examples 3-1 and 2-13. A blend polymer was used. 100 parts of this blend polymer, 2 parts of a graft polymer (compound No. 4-1) having a polymerizable monomer having a silicon atom in the side chain as a constituent, 90 parts of an amine compound having the following structural formula,
[0082]
Embedded image

10 parts of amine compound of the following structural formula
[0083]
Embedded image

Was dissolved in 500 parts of monochlorobenzene and 500 parts of dichloromethane to obtain a coating material for a charge transport layer. This paint was applied by an immersion method and dried at 120 ° C. for 2 hours to form a 25 μm charge transport layer. Next, the results evaluated in the same manner as in Example 1 are shown in Table.16Shown in
  [Example8]
  As the blend polymer to be used, polyarylate obtained by copolymerizing bisphenol Z type (Example 1-23) and bisphenol C type (Example 1-2) at 1/1 was used.14The same procedure as in Example 1 was performed except that the conditions shown in FIG. Table the results16Shown in
  [Example9~12, Reference Examples 7-12]
  Indicates the polymer to be used, the graft polymer having a polymerizable monomer having a silicon atom in the side chain as a constituent, the mixing ratio, and whether each polymer was used separately or as a blend polymer.14The same procedure as in Example 1 was performed except that the conditions shown in FIG. Table the results16Shown in
  [Comparative Examples 19 to 36]
  Indicates the polymer to be used, the graft polymer having a polymerizable monomer having a silicon atom in the side chain as a constituent, the mixing ratio, and whether each polymer was used separately or as a blend polymer.15The same procedure as in Example 1 was performed except that the conditions shown in FIG. Table the results16Shown in
[0084]
[Table 14]

[Table 15]

[0085]
[Table 16]

*, **, ***, *** in the table are the same as the remarks in Tables 10 and 11.
  Thus, by including the graft polymer having the polyarylate, the polycarbonate, the modified polycarbonate, and the polymerizable monomer having a silicon atom in the side chain as a constituent component according to the present invention, excellent mechanical strength and surface can be obtained. It is possible to provide an electrophotographic photosensitive member having lubricity even after durability. Furthermore, it is possible to provide an electrophotographic photosensitive member that has good electrophotographic characteristics, has good coatability and paint pot life at the time of manufacture, and does not wrinkle even with a general cleaning blade.
[0086]
【The invention's effect】
  As described above, the electrophotographic photosensitive member of the present invention has excellent mechanical strength and surface lubricity even after durability, and has good electrophotographic characteristics. In addition, improvement in solubility and pot life has broadened the range of selection of materials (constituent units), and it has become possible to provide electrophotographic photoreceptors according to the purpose of use.
[Brief description of the drawings]
FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member of the present invention.
[Explanation of symbols]
        1 Electrophotographic photoreceptor of the present invention
        2 axis
        3 Primary charging means
        4 Image exposure light
        5 Development means
        6 Transfer means
        7 Transfer material
        8 Image fixing means
        9 Cleaning blade
        10 Pre-exposure light
        11 Process cartridge
        12 rails

Claims (9)

In the method for producing an electrophotographic photosensitive member having a conductive support and a photosensitive layer,
A polyarylate having a repeating unit represented by the following formula (1), a polycarbonate having a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3) and the following formula (4) A step of obtaining a mixed polymer solution by dissolving and mixing a copolymer having repeating units in a good solvent;
Polyarylate having a repeating unit represented by the following formula (1) dissolved in the mixed polymer solution, a polycarbonate having a repeating unit represented by the following formula (2), and a repeating represented by the following formula (3) By reprecipitating a copolymer having a unit and a repeating unit represented by the following formula (4) using a poor solvent, a polyarylate having a repeating unit represented by the following formula (1), A step of obtaining a blend material of a polycarbonate having a repeating unit shown, and a copolymer having a repeating unit shown by the following formula (3) and a repeating unit shown by the following formula (4):
The surface layer of the electrophotographic photosensitive member is formed using the blend material and a paint containing a fluoropolymer powder and / or a graft polymer having a polymerizable monomer having a silicon atom in the side chain as a constituent component. And a process of
Process for producing an electrophotographic photoreceptor, characterized by have a.

(X ₁ represents a carbon atom or a single bond (in which R ₅ and R _{6 are} absent), R _{1 to} R ₄ represent a hydrogen atom, a halogen atom, an alkyl group which may be substituted, and an aryl group, and R ₅ , R ₆ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group, or an alkylidene group formed by combining R ₅ and R ₆ , and R _{7 to} R ₁₀ represent a hydrogen atom, respectively. , A halogen atom, an optionally substituted alkyl group, an aryl group)

(X ₂ represents a carbon atom or a single bond (in this case, R ₁₅ and R _{16 are} absent), R _{11 to} R ₁₄ represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group or an aryl group, and R ₁₅ , R ₁₆ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group, or an alkylidene group formed by combining R ₁₅ and R ₁₆ ).

(R _{17 to} R ₂₂ each represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group or an aryl group, and n represents a positive integer)

(X ₃ represents a carbon atom or a single bond (in this case, R ₂₇ and R _{28 are} absent), R _{23 to} R ₂₆ each represents a hydrogen atom, a halogen atom, an alkyl group which may be substituted, or an aryl group; ₂₇ and R ₂₈ each represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group, or an alkylidene group formed by combining R ₂₇ and R ₂₈ ) Formula R ₁ in _{(1), R 2, R} 5, R 6 is R ₃ I methyl _{der, R 4, R 7, R} 8, R 9, R 10 is Ri Oh a hydrogen atom, the formula _{(2) R 15 R 11 ~R} 14 is I Oh a hydrogen atom in, cyclohexylidene group der which R ₁₆ is formed with X ₂ is, the formula (3) in R ₁₇ to R ₂₀ is a methyl group R ₂₁ I der, R ₂₂ is a hydrogen atom, cyclohexylidene group R ₂₃ to R ₂₆ in the previous following formula (4) is formed R _27, R ₂₈ together with X ₃ I Oh hydrogen atom the method for producing an electrophotographic photosensitive member according to der Ru請 Motomeko 1. Before notated Tsu Motokei resin powder, tetrafluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene-hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluoride ethylene dichloride resin and method for producing an electrophotographic photosensitive member according to claim 1 or 2 which is a powder of at least one resin that is selected from the group consisting of copolymers thereof. Graft polymer having a polymerizable monomer having a pre-listen Lee atom in the side chain as a constituent component, a monomer having a polymerizable functional group at the terminal has a silicon atom in the side chain, the silicon atom 3. The production of an electrophotographic photosensitive member according to claim 1 or 2, which is a graft polymer obtained by copolymerizing a polymerizable monomer which is not present or a macromonomer comprising an oligomer having a polymerizable functional group at the end. Way . Before the mixing weight ratio of Kipo Riarireto and Wa, before the weight ratio of Kipo polycarbonate and Wc, a copolymer having a repeating unit represented by the repeating unit and the formula (4) represented by the formula (3) weight ratio was between Ws, before when the Wf weight ratio of notated Tsu-containing resin, Wa, Wc, electrophotographic photosensitive according to claim 1, 2 or 3 in which Ws and Wf satisfy the following relationship Body manufacturing method.
Wa / Wc = 95/5 to 5/95
Ws / (Wa + Wc) = 1 / 99-30 / 70
Wf / (Wa + Wc + Ws) = 1 / 100-50 / 100 Before the mixing weight ratio of Kipo Riarireto and Wa, before the weight ratio of Kipo polycarbonate and Wc, a copolymer having a repeating unit represented by the repeating unit and the formula (4) represented by the formula (3) when the weight ratio is Ws, and the Wf weight ratio of the graft polymer having a pre-listen Lee atom polymerizable monomers to organic in the side chain as a constituent, Wa, Wc, Ws and Wf is the following The method for producing an electrophotographic photosensitive member according to claim 1 , wherein the relationship is satisfied .
Wa / Wc = 95/5 to 5/95
Ws / (Wa + Wc) = 1 / 99-30 / 70
Wf / (Wa + Wc + Ws) = 0.02 / 100-20 / 100 An electrophotographic photoreceptor produced by the production method according to claim 1. 8. A process comprising: the electrophotographic photosensitive member according to claim 7 ; and at least one of a charging unit, a developing unit, and a cleaning unit, which are integrally supported and detachable from the main body of the electrophotographic apparatus. cartridge. The electrophotographic photosensitive member according to claim 7, charging means, image exposure means, developing means, transfer means and an electrophotographic apparatus characterized in that it comprises a cleaning hands stage.

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