JP2004325871A - Electrophotographic receptor, process cartridge having the electrophotographic receptor, and electrophotographic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which has excellent mechanical strength and surface lubricity in combination until after used and moreover has good electrophotographic characteristics, a process cartridge having the electrophotographic photoreceptor, and an electrophotographic apparatus. <P>SOLUTION: The electrophotographic photoreceptor which has a photosensitive layer on a conductive support and has a region increased in the oxygen atom percentage content on the surface of the photosensitive layer within a range of 0.8 to 3.4% before the image output by performing image output of 3,000 sheets, the process cartridge having the electrophotographic photoreceptor and the electrophotographic apparatus, in which the electrophotographic photoreceptor has the excellent mechanical strength and surface lubricity in combination until after the duration and has the good electrophotographic characteristics. More particularly, the electrophotographic photoreceptor with which the absence of the occurrence of peeling of a cleaning blade with the excellent durability is attained can be obtained. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

下記構造式のアミン化合物１０部
【００３８】
【化２】

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。
【００３９】
この塗料を浸漬法でシリンダー上端から３ｍｍの位置以降シリンダー下端までの領域を塗布し１２０℃、５０分乾燥して、シリンダー上端から１５ｍｍ以降シリンダー下端から１２．５ｍｍまでの領域において２５±１μｍに制御された電荷輸送層を形成した。
【００４０】
次に、評価について説明する。
【００４１】
装置はキヤノン製ＬＢＰ「Ｉｍａｇｅ Ｃｌａｓｓ ４０００」（プロセススピード１４４．５ｍｍ／ｓｅｃ）を用いた。本装置においては、画像形成域はシリンダー上端から４３ｍｍ以降シリンダー下端から３５．５ｍｍまでの領域であり、その外側は非画像形成域であった。また、転写手段としての転写ローラはシリンダー上端から３２ｍｍ以降シリンダー下端から２４．５ｍｍまでの領域、現像手段としての現像スリーブコート幅はシリンダー上端から３２ｍｍ以降シリンダー下端から２４．５ｍｍまでの領域、帯電手段としての帯電ローラはシリンダー上端から２８．５ｍｍ以降シリンダー下端から２１ｍｍまでの領域、クリーニング手段としてのクリーニングブレードはシリンダー上端から１５ｍｍ以降シリンダー下端から１２．５ｍｍまでの領域にそれぞれ配置されていた。
【００４２】
電位測定は、初期に、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、３０００枚をプリントしたところで上記電位を測定し、引き続き１０，０００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５０，０００枚の通紙耐久を行った。シーケンスはプリント２枚ごとに１回停止する間欠モードとし、５００枚ごとに１０分間プリントを休止し、１０００枚ごとにカートリッジを出し入れすることを繰り返し、５０，０００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。なお、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。また、フォトメモリーの測定は電位測定と同様にして行った。即ち、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、３０００枚をプリントしたところで上記電位を測定した後、電子写真感光体の一部に白色蛍光灯の光を電子写真感光体表面が１５００ルクスとなるようにして２０分間照射し、５分間暗所放置後に再び電位測定を行い、光照射部のＶｌと非照射部のＶｌとの差をフォトメモリーとし、フォトメモリー２０Ｖ以内を良好、２０Ｖを超えるものを不良として評価した。更に、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、各電荷輸送層用塗料を室温（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。
【００４３】
電子写真感光体の非画像形成領域における感光層表面の酸素原子含有率は、使用前と３０００枚プリント後および１０，０００枚プリント後を比較して行った。上記のごとく作成した電子写真感光体を上記の装置で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、３０００枚をプリントしたところでの非画像形成領域における感光層表面の酸素原子含有率を３０００枚プリント後酸素原子含有率とした。なお、測定領域はシリンダー上端から２８．５ｍｍから３２ｍｍの領域、およびシリンダー下端から２１ｍｍ以上２４．５ｍｍ以下の領域とした。同様にして１０，０００枚まで通紙耐久を行った感光体の非画像形成領域における感光層表面の酸素原子含有率を１０，０００枚プリント後酸素原子含有率とした。分析には英国ＶＧ Ｓｃｉｅｎｔｉｆｉｃ社製「ＥＳＣＡＬＡＢ２２０ｉＸＬ」を用いた。Ｘ線源として単結晶分光ＡｌＫα線、分析領域として１０００μｍφ，出力１０ｋＶ １８ｍＡ、アナライザーモードとしてＣｏｎｓｔａｎｔ Ａｎａｌｙｚｅｒ Ｅｎｅｒｇｙ （ＣＡＥ） Ｍｏｄｅ， Ｐａｓｓ ｅｎｅｒｇｙ・・・Ｗｉｄｅ ｓｃａｎ：１００ｅＶ， Ｎａｒｒｏｗ ｓｃａｎ：３０ｅＶ、分解能としてはＡｇ３ｄ５／２ ＦＷＨＭ＝０．８ｅＶ、真空度は〜１×１０−９Ｔｏｒｒ、ジオメトリーはθ＝９０°（θ：試料表面に対する検出器の傾き）、データ処理はｓｍｏｏｔｈｉｎｇ ９−ｐｏｉｎｔｓ， ｐｅａｋ ａｒｅａ ｍｅａｓｕｒｅｍｅｎｔ， ｂａｃｋｇｒｏｕｎｄ ｓｕｂｔｒａｃｔｉｏｎ， ｐｅａｋ ｓｙｎｔｈｅｓｉｓ、横軸補正として中性炭素Ｃ１ｓを２８４．６ｅＶにして行った。得られた元素組成（ａｔｏｍ％）の結果より酸素原子含有率の変化を比較した。非画像形成領域における感光層表面の酸素原子含有率は、使用前１１．９ａｔｏｍ％に対し３０００枚プリント後および１０，０００枚プリント後はいずれも１２．５ａｔｏｍ％であり、５．０％の増加であった。
【００４４】
電位評価結果は、初期の暗部電位、明部電位、残留電位、３０００枚プリント後のこれら電位、フォトメモリーともいずれも良好であった。また、ソルベントクラック性およびポットライフは、いずれも良好であった。しかしながら、高温高湿下においてクリーニングブレードのめくれが発生し、５０，０００枚を耐久することはできなかった。
【００４５】
［実施例１］
３０ｍｍφ×３５７．５ｍｍ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シリンダー上端から３ｍｍの位置以降シリンダー下端までの領域を塗布し、１４５℃、３０分熱硬化して、シリンダー上端から４３ｍｍ以降シリンダー下端から３５．５ｍｍまでの領域において１５±１μｍに制御され、シリンダー上端から２３．５ｍｍ以降３７ｍｍまでの領域およびシリンダー下端から２９．５ｍｍ以降１６ｍｍまでの領域が１８±１μｍに制御されたコブ状領域を有する導電層を形成した。
【００４６】
導電性顔料：ＳｎＯ_２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
【００４７】
この導電層の絶縁破壊電圧は、シリンダー上端から４３ｍｍ以降シリンダー下端から３５．５ｍｍまでの領域において２００±１００Ｖであり、シリンダー上端から２３．５ｍｍ以降３７ｍｍまでの領域およびシリンダー下端から２９．５ｍｍ以降１６ｍｍまでの領域において８００±４００Ｖであった。
【００４８】
この導電層を形成した以外は比較例１と同様にして電子写真感光体を作成し、評価を行った。非画像形成領域における感光層表面の酸素原子含有率は、使用前１１．９ａｔｏｍ％に対し３０００枚プリント後および１０，０００枚プリント後はいずれも１２．０ａｔｏｍ％であり、０．８％の増加であった。
【００４９】
結果を表１に示す。
【００５０】
［実施例２］
比較例１で形成した導電層の上に、Ｎメトキシメチル化ナイロン３部および共重合ナイロン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シリンダー上端から８ｍｍの位置以降シリンダー下端までの領域を塗布し１００℃、１０分乾燥して、シリンダー上端から４３ｍｍ以降シリンダー下端から３５．５ｍｍまでの領域において０．５±０．１μｍに制御され、シリンダー上端から２３．５ｍｍ以降３７ｍｍまでの領域およびシリンダー下端から２９．５ｍｍ以降１６ｍｍまでの領域が１．０±０．１μｍに制御されたコブ状領域を有する中間層を形成した。
【００５１】
この中間層の絶縁破壊電圧は、シリンダー上端から４３ｍｍ以降シリンダー下端から３５．５ｍｍまでの領域において３０±２０Ｖであり、シリンダー上端から２３．５ｍｍ以降３７ｍｍまでの領域およびシリンダー下端から２９．５ｍｍ以降１６ｍｍまでの領域において１５０±５０Ｖであった。
【００５２】
この中間層を形成した以外は比較例１と同様にして電子写真感光体を作成し、評価を行った。非画像形成領域における感光層表面の酸素原子含有率は、使用前１１．９ａｔｏｍ％に対し３０００枚プリント後および１０，０００枚プリント後はいずれも１２．１ａｔｏｍ％であり、１．７％の増加であった。
【００５３】
結果を表１に示す。
【００５４】
［実施例３］
実施例１で形成した導電層を用い、その上に実施例２で形成した中間層を適用した以外は、比較例１と同様にして電子写真感光体を作成し、評価を行った。非画像形成領域における感光層表面の酸素原子含有率は、使用前１１．９ａｔｏｍ％に対し３０００枚プリント後および１０，０００枚プリント後はいずれも１２．０ａｔｏｍ％であり、０．８％の増加であった。
【００５５】
結果を表１に示す。
【００５６】
［比較例２］
ホーニング処理により表面を粗面化した３０ｍｍφ×３５７．５ｍｍのＡｌシリンダーを支持体とし、それに、Ｎメトキシメチル化ナイロン３部および共重合ナイロン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シリンダー上端から８ｍｍの位置以降シリンダー下端までの領域を塗布し１００℃、１０分乾燥して、シリンダー上端から１５ｍｍ以降シリンダー下端から１２．５ｍｍまでの領域において０．６５±０．１μｍに制御された中間層を形成した。
【００５７】
この中間層の絶縁破壊電圧は、シリンダー上端から１５ｍｍ以降シリンダー下端から１２．５ｍｍまでの領域において６０±３０Ｖであった。
【００５８】
この中間層の上に比較例１と同様にして電荷発生層および電荷輸送層を形成し、比較例１と同様にして評価を行った。非画像形成領域における感光層表面の酸素原子含有率は、使用前１１．９ａｔｏｍ％に対し３０００枚プリント後および１０，０００枚プリント後はいずれも１２．５ａｔｏｍ％であり、５．０％の増加であった。
【００５９】
電位評価結果は、初期の暗部電位、明部電位、残留電位、３０００枚プリント後のこれら電位、フォトメモリーともいずれも良好であった。また、ソルベントクラック性およびポットライフは、いずれも良好であった。しかしながら、高温高湿下においてクリーニングブレードのめくれが発生し、５０，０００枚を耐久することはできなかった。
【００６０】
［実施例４］
ホーニング処理により表面を粗面化した３０ｍｍφ×３５７．５ｍｍのＡｌシリンダーを支持体とし、それに、Ｎメトキシメチル化ナイロン３部および共重合ナイロン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シリンダー上端から８ｍｍの位置以降シリンダー下端までの領域を塗布し１００℃、１０分乾燥して、シリンダー上端から４３ｍｍ以降シリンダー下端から３５．５ｍｍまでの領域において０．６５±０．１μｍに制御され、シリンダー上端から２３．５ｍｍ以降３７ｍｍまでの領域およびシリンダー下端から２９．５ｍｍ以降１６ｍｍまでの領域が１．０±０．１μｍに制御されたコブ状領域を有する中間層を形成した。
【００６１】
この中間層の絶縁破壊電圧は、シリンダー上端から４３ｍｍ以降シリンダー下端から３５．５ｍｍまでの領域において６０±３０Ｖであり、シリンダー上端から２３．５ｍｍ以降３７ｍｍまでの領域およびシリンダー下端から２９．５ｍｍ以降１６ｍｍまでの領域において１８０±６０Ｖであった。
【００６２】
この中間層を形成した以外は比較例２と同様にして電子写真感光体を作成し、評価を行った。非画像形成領域における感光層表面の酸素原子含有率は、使用前１１．９ａｔｏｍ％に対し３０００枚プリント後および１０，０００枚プリント後はいずれも１２．１ａｔｏｍ％であり、１．７％の増加であった。
【００６３】
結果を表１に示す。
【００６４】
［実施例５］
３０ｍｍφ×３５７．５ｍｍのＡｌシリンダーを支持体とし、シリンダー上端から３７ｍｍまでの領域およびシリンダー下端から２９．５ｍｍ以降シリンダー下端までの領域を硫酸電解液中で陽極酸化処理を行うことにより平均膜厚４μｍの陽極酸化被膜を形成した。つづいて硝酸ニッケルを主成分とする封孔処理剤中に浸漬した後、温水浴処理を行い、シリンダー上端から３７ｍｍまでの領域およびシリンダー下端から２９．５ｍｍ以降シリンダー下端までの領域にのみ陽極酸化被膜を形成した。
【００６５】
この陽極酸化被膜の形成された領域の絶縁破壊電圧は、２００±１２０Ｖであった。
【００６６】
比較例１における３０ｍｍφ×３５７．５ｍｍのＡｌシリンダーに代えて、この陽極酸化被膜を形成したＡｌシリンダーを支持体とした以外は比較例１と同様にして電子写真感光体を作成し、評価を行った。非画像形成領域における感光層表面の酸素原子含有率は、使用前１１．９ａｔｏｍ％に対し３０００枚プリント後および１０，０００枚プリント後はいずれも１２．２ａｔｏｍ％であり、２．５％の増加であった。
【００６７】
結果を表１に示す。
【００６８】
［実施例６］
ホーニング処理により表面を粗面化した３０ｍｍφ×３５７．５ｍｍのＡｌシリンダーを支持体とし、シリンダー上端から３７ｍｍまでの領域およびシリンダー下端から２９．５ｍｍ以降シリンダー下端までの領域を硫酸電解液中で陽極酸化処理を行うことにより平均膜厚４μｍの陽極酸化被膜を形成した。つづいて硝酸ニッケルを主成分とする封孔処理剤中に浸漬した後、温水浴処理を行い、シリンダー上端から３７ｍｍまでの領域およびシリンダー下端から２９．５ｍｍ以降シリンダー下端までの領域にのみ陽極酸化被膜を形成した。
【００６９】
この陽極酸化被膜の形成された領域の絶縁破壊電圧は、２００±１２０Ｖであった。
【００７０】
比較例２におけるホーニング処理により表面を粗面化した３０ｍｍφ×３５７．５ｍｍのＡｌシリンダーに代えて、このホーニング処理後陽極酸化被膜を形成したＡｌシリンダーを支持体とした以外は比較例２と同様にして電子写真感光体を作成し、評価を行った。非画像形成領域における感光層表面の酸素原子含有率は、使用前１１．９ａｔｏｍ％に対し３０００枚プリント後および１０，０００枚プリント後はいずれも１２．２ａｔｏｍ％であり、２．５％の増加であった。
【００７１】
結果を表１に示す。
【００７２】
［実施例７］
評価装置としてキヤノン製ＬＢＰ「Ｉｍａｇｅ Ｃｌａｓｓ ４０００」の改造機（プロセススピード２３５．５ｍｍ／ｓｅｃ）を用いた。改造は高圧設定の変更、駆動モーターの早回し、一次ＡＣ周波数のアップ、レーザーをシングルビームからダブルビームに変更、レーザー光量の変更、スキャナー回転速度の変更、および紙送りシーケンスの見直しにより行った。評価装置としてキヤノン製ＬＢＰ「Ｉｍａｇｅ Ｃｌａｓｓ ４０００」の改造機を用いた以外は実施例１と同様にして電子写真感光体を作成し、評価を行った。非画像形成領域における感光層表面の酸素原子含有率は、使用前１１．９ａｔｏｍ％に対し３０００枚プリント後および１０，０００枚プリント後はいずれも１２．３ａｔｏｍ％であり、３．４％の増加であった。
【００７３】
結果を表１に示す。
【００７４】
［比較例３］
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Ｚ型のシリコーン変性ポリカーボネート（粘度平均分子量６５０００）９０部、ビスフェノールＺ型のポリカーボネート（粘度平均分子量４２０００）１０部、下記構造式のアミン化合物９０部、
【００７５】
【化３】

下記構造式のアミン化合物１０部
【００７６】
【化４】

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。
【００７７】
この塗料を浸漬法でシリンダー上端から３ｍｍの位置以降シリンダー下端までの領域を塗布し１２０℃、５０分乾燥して、シリンダー上端から１５ｍｍ以降シリンダー下端から１２．５ｍｍまでの領域において２５±１μｍに制御された電荷輸送層を形成した他は、比較例１と同様に行った。非画像形成領域における感光層表面の酸素原子含有率は、使用前１５．９ａｔｏｍ％に対し３０００枚プリント後は１３．４ａｔｏｍ％、１０，０００枚プリント後は１１．７ａｔｏｍ％であり、減少が見られた。
【００７８】
電位評価結果は暗部電位、明部電位、残留電位、３０００枚プリント後電位、フォトメモリーともいずれも良好であった。また、ソルベントクラック性およびポットライフは、いずれも良好であった。しかしながら、耐久による削れが激しく、５０，０００枚を耐久することはできなかった。
【００７９】
【表１】

電位評価結果は、初期の暗部電位、明部電位、残留電位、３０００枚プリント後のこれら電位、フォトメモリーともいずれも良好であった。また、クラックが発生したもの、ゲル化したもの、溶解しなかったものは無く、ソルベントクラック性およびポットライフは、いずれも良好であった。
【００８０】
実施例１〜７では全ての評価項目に関し良好な結果であった。しかし、比較例１〜２はいずれも高温高湿下においてクリーニングブレードのめくれが発生し、５万枚まで耐久することはできなかった。また、比較例３は感光層の削れが激しく、５万枚まで耐久することはできなかった。
【００８１】
このように、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つことができ、更に、電子写真特性が良好であり、耐久性に優れ、かつ一般的なクリーニングブレードでもめくれが起こらない。
【００８２】
以上本発明の実施例について説明したが、本発明の好適な実施の態様を以下のとおり列挙する
［実施態様１］
導電性支持体上に感光層を有する電子写真感光体において、該電子写真感光体の非画像形成領域中に、感光層表面の酸素原子含有率が、３０００枚の画像出力を行うことにより画像出力前の０．８％以上３．４％以下の範囲で増加する領域を有することを特徴とする電子写真感光体。
【００８３】
［実施態様２］
前記電子写真感光体を帯電させるための帯電手段、および電子写真感光体から潜像もしくは可視化されたトナー像を転写媒体へ転写するための転写手段、の少なくとも一方が、該電子写真感光体に直接接触することを特徴とする実施態様１に記載の電子写真感光体。
【００８４】
［実施態様３］
前記帯電手段がローラー状であり、直流電圧に交流電圧を重畳させた電圧を印加する実施態様２に記載の電子写真感光体。
【００８５】
［実施態様４］
実施態様１乃至３のいずれかに記載の電子写真感光体を、帯電手段、現像手段およびクリーニング手段から選ばれる少なくとも１つの手段と共に一体に支持し、電子写真装置本体に着脱自在であることを特徴とするプロセスカートリッジ。
【００８６】
［実施態様５］
実施態様１乃至３のいずれかに記載の電子写真感光体を帯電手段、現像手段およびクリーニング手段手段から選ばれる少なくとも１つの手段と共に一体に支持したプロセスカートリッジを有することを特徴とする電子写真装置。
【００８７】
【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。特に、耐久性に優れ、かつクリーニングブレードのめくれが起こらないことを両立した電子写真感光体を提供することが可能となった。また、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。また、上記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]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member, and particularly to an electrophotographic photosensitive member having high durability, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.
[0002]
[Prior art]
Conventionally, corona chargers such as corotrons and scorotrons have been widely used for charging electrophotographic devices such as laser beam printers and copiers.However, a high voltage is required, and a large amount of ozone is generated. There is a disadvantage that deterioration is accelerated. In recent years, contact charging methods such as roller charging and brush charging, that is, direct charging methods in which a voltage is directly applied to a charging member to apply a charge to an electrophotographic photosensitive member are becoming mainstream (for example, see Patent Documents 1 and 2). . This is a method in which a roller-shaped charging member made of a conductive rubber or the like is brought into direct contact with an electrophotographic photoreceptor to apply an electric charge. This charging method requires a low applied voltage, and the amount of generated ozone. It has the characteristic that there is little.
[0003]
However, in these contact charging methods such as roller charging and brush charging, when a charging member such as a charging roller or a conductive brush comes into direct contact with the photoconductor and is charged, pinhole leak due to inflow of a charging current or a portion of the photosensitive layer is caused. Problem of permanent deterioration. In addition, with the recent increase in the speed of electrophotographic devices such as copiers and laser beam printers, AC voltage is often superimposed on DC voltage in order to make charging uniform, the amount of current flowing in and the frequency also increase. It tends to increase.
[0004]
On the other hand, as a matter of course, the electrophotographic photoreceptor is required to have sensitivity, electrical characteristics, and optical characteristics according to the applied electrophotographic process. In particular, in the case of a repetitively used electrophotographic photoreceptor, an external electrical or mechanical force such as corona or direct charging, image exposure, toner development, transfer process, surface cleaning, etc. is directly applied to the electrophotographic photoreceptor surface. Therefore, durability for them is also required.
[0005]
Specifically, electrical deterioration due to ozone and nitrogen oxides during charging, discharge during charging, mechanical deterioration in which the surface is worn or scratched due to rubbing of the cleaning member, durability against electrical deterioration Sex is required. The electrical deterioration is particularly problematic in that carriers stay in a portion irradiated with light and a potential difference is generated in a portion not irradiated with light, and this phenomenon occurs as a photo memory. The mechanical deterioration is particularly different from the inorganic photoreceptor, and the organic photoreceptor having many soft materials is inferior in the durability against the mechanical deterioration, and the improvement of the durability is particularly desired. Various attempts have been made to satisfy the durability characteristics required for the photoreceptor as described above.
[0006]
[Patent Document 1]
JP-A-57-17826
[Patent Document 2]
JP-A-58-40566
[0007]
[Problems to be solved by the invention]
The surface of the photoconductor is gradually scraped by the cleaning blade that is in contact with the photoconductor. In addition to the scraping by the cleaning blade, the photosensitive member surface is gradually scraped by the seal of the cleaning container in contact with the photosensitive member. The seal of the cleaning container has a large contact area, and when the toner enters the eyes of the sponge, the seal scrapes the photosensitive member surface more than the cleaning blade.
[0008]
In addition, at the ends of the charging member and the transfer member, the discharge region tends to be wide, and a large amount of current flows. When a large amount of current flows, a radical reaction more easily occurs on the surface of the photoreceptor, and promotes oxidation and reduction of the molecular weight of the binder on the surface of the photoreceptor, thereby facilitating scraping by the cleaning blade.
[0009]
In particular, in a high-speed machine, the frequency increases at the same time as the current increases, so that more current flows and the action of lowering the molecular weight of the binder on the surface of the photoreceptor becomes stronger.
[0010]
Accordingly, an object of the present invention is to provide an electrophotographic photoreceptor having excellent mechanical strength and surface lubricating properties until the end of its durability and excellent electrophotographic characteristics, and a process cartridge and an electrophotographic apparatus having the electrophotographic photoreceptor. Is to provide.
[0011]
[Means for Solving the Problems]
According to the present invention, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, an image is output when the surface of the photosensitive layer has an oxygen atom content of 3000 sheets in a non-image forming region of the electrophotographic photosensitive member. An electrophotographic photoreceptor characterized in that the electrophotographic photoreceptor has a region which increases by 0.8% to 3.4% before image output.
[0012]
Further, the present invention is a process cartridge and an electrophotographic apparatus having the above electrophotographic photosensitive member.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the configuration of the electrophotographic photosensitive member of the present invention will be described.
[0014]
The electrophotographic photoreceptor of the present invention may be a single layer type in which the photosensitive layer contains a charge transport material and a charge generation material in the same layer, or a laminated type in which a charge transport layer and a charge generation layer are separated. From the photographic characteristics, a laminated type is preferable. In any case, at least an electrophotographic photosensitive member having a photosensitive layer on a conductive support, in the non-image forming region of the electrophotographic photosensitive member, the oxygen atom content of the photosensitive layer surface is 3000 sheets By performing image output, there is an area that increases in the range of 0.8% or more and 3.4% or less before image output.
[0015]
The conductive support to be used is not limited as long as it has conductivity, and may be a metal such as aluminum or stainless steel, or a metal provided with a conductive layer, paper, plastic, or the like. No. In particular, when an image input from a laser beam printer or the like is a laser beam, it is preferable to provide a conductive layer for the purpose of preventing interference fringes due to scattering or covering a scratch 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 preferably 5 to 40 μm, more preferably 10 to 30 μm.
[0016]
An intermediate layer having a barrier function can be provided on the conductive support or the conductive layer. Examples of the intermediate layer include an anodized aluminum film, an inorganic layer such as aluminum oxide and aluminum hydroxide, and an organic layer such as polyamide, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, casein, polyurethane, and polyether urethane. These organic layers are applied by dissolving in an appropriate solvent, and the film thickness is preferably 0.05 to 5 μm, more preferably 0.3 to 1 μm. Further, an organic layer such as polyamide can be provided on an inorganic layer such as an aluminum anodic oxide film.
[0017]
In the case of the function separation type, a charge generation layer is formed thereon. As the charge generating material used in the present invention, selenium-tellurium, pyrylium, thiapyrylium-based dye, phthalocyanine, anthantrone, dibenzpyrenequinone, trisazo, cyanine, disazo, monoazo, indigo, quinacridone, asymmetric quinocyanine-based pigments No. The charge generating layer is a homogenizer, an ultrasonic dispersion, a ball mill, a vibrating ball mill, a sand mill, an attritor, a roll mill, a liquid collision type high-speed disperser and the like, together with a binder resin and a solvent in an amount of 0.3 to 4 times the mass of the charge generation material. Is formed by applying a dispersion liquid and then drying. The thickness of the charge generation layer is preferably 5 μm or less, more preferably 0.1 to 2 μm.
[0018]
The charge transport layer is formed by applying a coating material in which a charge transport material and a binder resin are dissolved in a solvent and drying the coating material. Examples of the charge transport material used include a triarylamine compound, a hydrazone compound, a stilbene compound, a pyrazoline compound, an oxazole compound, a triarylmethane compound, and a thiazole compound.
[0019]
These are combined with a binder resin in an amount of 0.5 to 2 times by weight, applied, and dried to form a charge transport layer. The thickness of the charge transport layer is preferably 5 to 40 μm, more preferably 15 to 30 μm.
[0020]
When the photosensitive layer is a single-layer type, the photosensitive layer is formed by dispersing the above-described charge generating material or charge transporting material in the above-described binder resin, applying a dissolved solution, and drying. The thickness is preferably 5 to 40 μm, more preferably 15 to 30 μm.
[0021]
FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.
[0022]
In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around an axis 2 at a predetermined peripheral speed in a direction indicated by an arrow. In the rotation process, the photosensitive member 1 is uniformly charged with a predetermined positive or negative potential on the peripheral surface thereof by the primary charging means 3, and then receives a charge from an image exposure means (not shown) such as slit exposure or laser beam scanning exposure. It receives image exposure light 4. Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 1.
[0023]
The formed electrostatic latent image is then subjected to toner development by the developing unit 5, and the developed toner developed image is transferred between the photoconductor 1 and the transfer unit 6 by a rotation of the photoconductor 1 from a feeding unit (not shown). The transfer material 6 is sequentially transferred to the transfer material 7 taken out and fed synchronously.
[0024]
The transfer material 7 having undergone the image transfer is separated from the surface of the photoreceptor, introduced into the image fixing means 8 and subjected to image fixing to be printed out of the apparatus as a copy.
[0025]
The surface of the photoreceptor 1 after the image transfer is cleaned and cleaned by removing a transfer residual toner by a cleaning blade 9, and is further subjected to a static elimination process by a pre-exposure light 10 from a pre-exposure unit (not shown). 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 necessarily required.
[0026]
In the present invention, among the above-described components such as the electrophotographic photoreceptor 1, the primary charging unit 3, the developing unit 5, and the cleaning unit 9, a plurality of components are integrally connected as a process cartridge. May be detachably attached to a main body of an electrophotographic apparatus 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 photoreceptor 1 to form a cartridge, and the cartridge is detachably attached to the apparatus main body using guide means such as the rail 12 of the apparatus main body. The process cartridge 11 can be used.
[0027]
When the electrophotographic apparatus is a copier or a printer, the image exposure light 4 is reflected light or transmitted light from the original, or the original is read by a sensor and converted into a signal, and a laser beam is emitted according to the signal. Light emitted by scanning, driving of an LED array, driving of a liquid crystal shutter array, and the like.
[0028]
The electrophotographic photoreceptor of the present invention can be widely used not only for electrophotographic copying machines but also for electrophotographic applications such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making.
[0029]
【Example】
Hereinafter, description will be made according to examples. In the examples, "parts" indicates parts by mass.
[0030]
[Comparative Example 1]
A 30 mm φ × 357.5 mm Al cylinder was used as a support, and a coating composed of the following materials was applied on the support by a dipping method to apply a region from the position 3 mm from the top of the cylinder to the bottom of the cylinder. After 30 minutes of heat curing, a conductive layer controlled to 15 ± 1 μm was formed in a region 15 mm from the upper end of the cylinder to 12.5 mm from the lower end of the cylinder.
[0031]
Conductive pigment: SnO ₂ Coated barium sulfate 10 parts
Pigment for resistance adjustment: 2 parts of titanium oxide
Binder resin: 6 parts of phenolic resin
Leveling material: 0.001 part of silicone oil
Solvent: methanol, methoxypropanol 0.2 / 0.8 20 parts
[0032]
The dielectric breakdown voltage of this conductive layer was 200 ± 100 V in a region from 15 mm from the upper end of the cylinder to 12.5 mm from the lower end of the cylinder. The measurement of the dielectric breakdown voltage in the present invention was based on JIS C2110.
[0033]
On the conductive layer, a solution prepared by dissolving 3 parts of N-methoxymethylated nylon and 3 parts of copolymerized nylon in a mixed solvent of 65 parts of methanol and 30 parts of n-butanol was immersed by 8 mm from the top of the cylinder to the bottom of the cylinder. And dried at 100 ° C. for 10 minutes to form an intermediate layer controlled at 0.5 ± 0.1 μm in a region from the upper end of the cylinder to 15 mm and thereafter from the lower end of the cylinder to 12.5 mm.
[0034]
The dielectric breakdown voltage of this intermediate layer was 30 ± 20 V in a region from 15 mm from the upper end of the cylinder to 12.5 mm from the lower end of the cylinder.
[0035]
Next, 4 parts of oxytitanium phthalocyanine (TiOPc) having strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° at Bragg angles 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction. And 2 parts of polyvinyl butyral (trade name: Esrec BM2, manufactured by Sekisui Chemical Co., Ltd.) and 60 parts of cyclohexanone were dispersed in a sand mill using φ1 mm glass beads for 4 hours. Prepared. This is applied by dipping to a region from the position 3 mm from the upper end of the cylinder to the lower end of the cylinder, dried at 50 ° C. for 10 minutes, and 0.3 ± 0.5 mm from 15 mm from the upper end of the cylinder to 12.5 mm from the lower end of the cylinder. A charge generation layer controlled to 1 μm was formed.
[0036]
Next, in order to form a charge transport layer, a paint for the charge transport layer was prepared. 90 parts of bisphenol C type polyarylate (viscosity average molecular weight 65,000), 10 parts of bisphenol Z type polycarbonate (viscosity average molecular weight 42000), 90 parts of an amine compound having the following structural formula,
[0037]
Embedded image

10 parts of an amine compound having the following structural formula
[0038]
Embedded image

Was dissolved in 500 parts of monochlorobenzene and 500 parts of dichloromethane to obtain a paint for a charge transport layer.
[0039]
Apply this paint to the area from the top of the cylinder 3mm to the bottom of the cylinder by the dipping method, dry at 120 ° C for 50 minutes, and control it to 25 ± 1μm in the area from 15mm from the top of the cylinder to 12.5mm from the bottom of the cylinder. The resulting charge transport layer was formed.
[0040]
Next, evaluation will be described.
[0041]
The apparatus used was a Canon LBP “Image Class 4000” (process speed: 144.5 mm / sec). In this apparatus, the image forming area was an area from 43 mm from the upper end of the cylinder to 35.5 mm from the lower end of the cylinder, and the outside thereof was a non-image forming area. The transfer roller as a transfer means is a region from 32 mm from the upper end of the cylinder to 24.5 mm from the lower end of the cylinder, the developing sleeve coat width as the developing means is a region from 32 mm from the upper end of the cylinder to 24.5 mm from the lower end of the cylinder, The charging roller was disposed in a region from 28.5 mm from the upper end of the cylinder to 21 mm from the lower end of the cylinder, and the cleaning blade as a cleaning means was disposed in a region from 15 mm from the upper end of the cylinder to 12.5 mm from the lower end of the cylinder.
[0042]
The potential measurement was initially performed by setting the dark part to Vd, the laser light irradiation part to Vl, and the pre-exposure irradiation part to Vr. The produced electrophotographic photoreceptor was subjected to paper passing durability at 23 ° C. and 55% RH using this apparatus. The sequence was set to an intermittent mode in which the printing was stopped once for each print, and the potential was measured when 3000 prints were made. Then, the paper was passed until 10,000 prints, and the shaving amount of the photoreceptor was measured. Further, 50,000 sheets were passed 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 every two prints, pauses printing for every 500 prints for 10 minutes, repeatedly inserts and removes cartridges every 1000 prints, and durates the cleaning blade for 50,000 prints. Was evaluated. The toner was replenished as needed during the print pause for 10 minutes. The measurement of the photo memory was performed in the same manner as the potential measurement. That is, the prepared electrophotographic photosensitive member was subjected to paper passing durability at 23 ° C. and 55% RH using this apparatus. The sequence is an intermittent mode in which the printing is stopped once for each print. After the 3000 prints, the potential is measured, and then the light of a white fluorescent lamp is applied to a part of the electrophotographic photosensitive member, and the surface of the electrophotographic photosensitive member is 1500 lux. After exposure in a dark place for 5 minutes, the potential is measured again. The difference between Vl of the light-irradiated part and Vl of the non-irradiated part is used as a photo memory. Exceeding was evaluated as defective. Further, for the solvent cracking property, finger fat was adhered to the surface, left for 24 hours, and observed with a microscope for the presence or absence of solvent cracking. As an evaluation of the pot life, each paint for the charge transport layer was allowed to stand in a closed container at room temperature (23 ° C.) for one week, and then the dissolved state was observed.
[0043]
The oxygen atom content on the surface of the photosensitive layer in the non-image forming area of the electrophotographic photosensitive member was compared before use, after printing 3,000 sheets, and after printing 10,000 sheets. The electrophotographic photoreceptor prepared as described above was subjected to paper passing durability at 23 ° C. and 55% RH using the above apparatus. The sequence was an intermittent mode in which the printing was stopped once for each print, and the oxygen atom content on the surface of the photosensitive layer in the non-image forming area at the time when 3000 prints were performed was defined as the oxygen atom content after 3000 prints. The measurement region was a region from 28.5 mm to 32 mm from the upper end of the cylinder and a region from 21 mm to 24.5 mm from the lower end of the cylinder. Similarly, the oxygen atom content on the surface of the photosensitive layer in the non-image forming area of the photoreceptor subjected to the paper-passing durability up to 10,000 sheets was defined as the oxygen atom content after printing 10,000 sheets. “ESCALAB220iXL” manufactured by VG Scientific, UK was used for analysis. Single crystal spectroscopy AlKα ray as X-ray source, 1000 μmφ as analysis area, output 10 kV 18 mA, Constant Analyzer Energy (CAE) Mode as analyzer mode, Pass energy... 2 FWHM = 0.8 eV, degree of vacuum is １1 × 10 −9 Torr, geometry is θ = 90 ° (θ: inclination of the detector with respect to the sample surface), data processing is smoothing 9-points, peak area measurement, background subtraction, Peak synthesis was performed with neutral carbon C1s at 284.6 eV for horizontal axis correction. The change of the oxygen atom content was compared based on the obtained element composition (atom%). The oxygen atom content on the photosensitive layer surface in the non-image forming area was 11.9 atom% before use and 12.5 atom% after printing 3000 sheets and after printing 10,000 sheets, respectively, an increase of 5.0%. Met.
[0044]
As a result of the potential evaluation, all of the initial dark portion potential, light portion potential, residual potential, these potentials after printing 3000 sheets, and the photo memory were good. The solvent cracking property and the pot life were all good. However, the cleaning blade was turned up under high temperature and high humidity, and 50,000 sheets could not be durable.
[0045]
[Example 1]
A 30 mm φ × 357.5 mm Al cylinder was used as a support, and a coating composed of the following materials was applied on the support by a dipping method to apply a region from the position 3 mm from the top of the cylinder to the bottom of the cylinder. , Heat-hardened for 30 minutes, controlled to 15 ± 1 μm in the region from 43 mm from the top of the cylinder to 35.5 mm from the bottom of the cylinder, in the region from 23.5 mm to 37 mm from the top of the cylinder and 29.5 mm to 16 mm from the bottom of the cylinder A conductive layer having a bump-shaped region whose area up to 18 ± 1 μm was controlled was formed.
[0046]
Conductive pigment: SnO ₂ Coated barium sulfate 10 parts
Pigment for resistance adjustment: 2 parts of titanium oxide
Binder resin: 6 parts of phenolic resin
Leveling material: 0.001 part of silicone oil
Solvent: methanol, methoxypropanol 0.2 / 0.8 20 parts
[0047]
The dielectric breakdown voltage of this conductive layer is 200 ± 100 V in a region from 43 mm from the cylinder upper end to 35.5 mm from the cylinder lower end, a region from 23.5 mm to 37 mm from the cylinder upper end, and 29.5 mm to 16 mm from the cylinder lower end. Up to 800 ± 400V in the region up to
[0048]
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Comparative Example 1 except that this conductive layer was formed. The oxygen atom content of the photosensitive layer surface in the non-image forming area was 11.9 atom% before use and 12.0 atom% after printing 3000 sheets and after printing 10,000 sheets, respectively, an increase of 0.8%. Met.
[0049]
Table 1 shows the results.
[0050]
[Example 2]
On the conductive layer formed in Comparative Example 1, a solution prepared by dissolving 3 parts of N-methoxymethylated nylon and 3 parts of copolymerized nylon in a mixed solvent of 65 parts of methanol and 30 parts of n-butanol was immersed at a distance of 8 mm from the top of the cylinder. The area from the position to the bottom of the cylinder is applied, dried at 100 ° C. for 10 minutes, and controlled to 0.5 ± 0.1 μm in the area from 43 mm from the top of the cylinder to 35.5 mm from the bottom of the cylinder. An intermediate layer having a bump-shaped region in which a region from 5 mm to 37 mm and a region from 29.5 mm to 16 mm from the lower end of the cylinder were controlled to 1.0 ± 0.1 μm was formed.
[0051]
The dielectric breakdown voltage of this intermediate layer is 30 ± 20 V in a region from 43 mm from the top of the cylinder to 35.5 mm from the bottom of the cylinder, a region from 23.5 mm to 37 mm from the top of the cylinder, and 29.5 mm to 16 mm from the bottom of the cylinder. Up to 150 ± 50V.
[0052]
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Comparative Example 1 except that the intermediate layer was formed. The oxygen atom content on the surface of the photosensitive layer in the non-image forming area was 12.1 atom% after printing 3000 sheets and after printing 10,000 sheets, which was 11.9 atom% before use, and increased by 1.7%. Met.
[0053]
Table 1 shows the results.
[0054]
[Example 3]
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Comparative Example 1, except that the conductive layer formed in Example 1 was used, and the intermediate layer formed in Example 2 was applied thereon. The oxygen atom content of the photosensitive layer surface in the non-image forming area was 11.9 atom% before use and 12.0 atom% after printing 3000 sheets and after printing 10,000 sheets, respectively, an increase of 0.8%. Met.
[0055]
Table 1 shows the results.
[0056]
[Comparative Example 2]
A 30 mm φ × 357.5 mm Al cylinder whose surface was roughened by honing was used as a support, and 3 parts of N-methoxymethylated nylon and 3 parts of copolymerized nylon were mixed in a mixed solvent of 65 parts of methanol and 30 parts of n-butanol. The solution is applied to the region from the position 8 mm from the top of the cylinder to the bottom of the cylinder by an immersion method, dried at 100 ° C. for 10 minutes, and 0.65 ± 15 mm from the top of the cylinder to 12.5 mm from the bottom of the cylinder after 15 mm from the top of the cylinder. An intermediate layer controlled to 0.1 μm was formed.
[0057]
The dielectric breakdown voltage of the intermediate layer was 60 ± 30 V in a region from 15 mm from the upper end of the cylinder to 12.5 mm from the lower end of the cylinder.
[0058]
A charge generation layer and a charge transport layer were formed on the intermediate layer in the same manner as in Comparative Example 1, and the evaluation was performed in the same manner as in Comparative Example 1. The oxygen atom content on the photosensitive layer surface in the non-image forming area was 11.9 atom% before use and 12.5 atom% after printing 3000 sheets and after printing 10,000 sheets, respectively, an increase of 5.0%. Met.
[0059]
As a result of the potential evaluation, all of the initial dark portion potential, light portion potential, residual potential, these potentials after printing 3000 sheets, and the photo memory were good. The solvent cracking property and the pot life were all good. However, the cleaning blade was turned up under high temperature and high humidity, and 50,000 sheets could not be durable.
[0060]
[Example 4]
A 30 mm φ × 357.5 mm Al cylinder whose surface was roughened by honing was used as a support, and 3 parts of N-methoxymethylated nylon and 3 parts of copolymerized nylon were mixed in a mixed solvent of 65 parts of methanol and 30 parts of n-butanol. The dissolved solution is applied to the area from the position 8 mm from the top of the cylinder to the bottom of the cylinder by an immersion method, dried at 100 ° C. for 10 minutes, and 0.65 ± 43 mm from the top of the cylinder to 35.5 mm from the bottom of the cylinder after 43 mm from the top of the cylinder. An intermediate layer having a bump-shaped region controlled to 0.1 μm and a region from 23.5 mm to 37 mm from the top of the cylinder and a region from 29.5 mm to 16 mm from the bottom of the cylinder controlled to 1.0 ± 0.1 μm. Formed.
[0061]
The dielectric breakdown voltage of this intermediate layer is 60 ± 30 V in a region from 43 mm from the upper end of the cylinder to 35.5 mm from the lower end of the cylinder, a region from 23.5 mm to 37 mm from the upper end of the cylinder and 29.5 mm to 16 mm from the lower end of the cylinder. 180 ± 60V in the region up to
[0062]
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Comparative Example 2 except that the intermediate layer was formed. The oxygen atom content on the surface of the photosensitive layer in the non-image forming area was 12.1 atom% after printing 3000 sheets and after printing 10,000 sheets, which was 11.9 atom% before use, and increased by 1.7%. Met.
[0063]
Table 1 shows the results.
[0064]
[Example 5]
A 30 mmφ × 357.5 mm Al cylinder is used as a support, and the area from the top of the cylinder to 37 mm and the area from the bottom of the cylinder to 29.5 mm to the bottom of the cylinder are anodized in a sulfuric acid electrolyte to obtain an average film thickness of 4 μm. Was formed. Then, after being immersed in a sealing agent containing nickel nitrate as a main component, a hot water bath treatment is performed, and an anodic oxide coating is applied only to a region from the cylinder upper end to 37 mm and a region from the cylinder lower end to 29.5 mm to the cylinder lower end. Was formed.
[0065]
The dielectric breakdown voltage of the region where the anodized film was formed was 200 ± 120V.
[0066]
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Comparative Example 1 except that the Al cylinder having the anodic oxide film formed thereon was used as a support in place of the Al cylinder having a diameter of 30 mm x 357.5 mm in Comparative Example 1. Was. The oxygen atom content on the surface of the photosensitive layer in the non-image forming area is 12.2 atom% after printing 3000 sheets and after printing 10,000 sheets, which is 11.9 atom% before use, an increase of 2.5%. Met.
[0067]
Table 1 shows the results.
[0068]
[Example 6]
A 30mmφ × 357.5mm Al cylinder whose surface was roughened by honing was used as a support, and the area from the cylinder top to 37mm and the area from the cylinder bottom to 29.5mm to the cylinder bottom were anodized in sulfuric acid electrolyte. By performing the treatment, an anodic oxide film having an average film thickness of 4 μm was formed. Then, after being immersed in a sealing agent containing nickel nitrate as a main component, a hot water bath treatment is performed, and an anodic oxide coating is applied only to a region from the cylinder upper end to 37 mm and a region from the cylinder lower end to 29.5 mm to the cylinder lower end. Was formed.
[0069]
The dielectric breakdown voltage of the region where the anodized film was formed was 200 ± 120V.
[0070]
In the same manner as in Comparative Example 2 except that the Al cylinder of 30 mmφ × 357.5 mm whose surface was roughened by the honing treatment in Comparative Example 2 was used instead of the Al cylinder on which the anodized film was formed after the honing treatment, was used. To prepare an electrophotographic photosensitive member and evaluated. The oxygen atom content on the surface of the photosensitive layer in the non-image forming area is 12.2 atom% after printing 3000 sheets and after printing 10,000 sheets, which is 11.9 atom% before use, an increase of 2.5%. Met.
[0071]
Table 1 shows the results.
[0072]
[Example 7]
A modified machine (process speed 235.5 mm / sec) of a Canon LBP “Image Class 4000” was used as an evaluation device. Modifications were made by changing the high voltage setting, turning the drive motor faster, increasing the primary AC frequency, changing the laser from a single beam to a double beam, changing the laser light intensity, changing the scanner rotation speed, and reviewing the paper feed sequence. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that a modified machine of Canon LBP "Image Class 4000" was used as an evaluation device. The oxygen atom content of the photosensitive layer surface in the non-image forming area is 12.3 atom% after printing 3000 sheets and after printing 10,000 sheets, which is 11.9 atom% before use, an increase of 3.4%. Met.
[0073]
Table 1 shows the results.
[0074]
[Comparative Example 3]
To form the charge transport layer, a paint for the charge transport layer was prepared. 90 parts of a bisphenol Z type silicone-modified polycarbonate (viscosity average molecular weight 65,000), 10 parts of a bisphenol Z type polycarbonate (viscosity average molecular weight 42,000), 90 parts of an amine compound having the following structural formula,
[0075]
Embedded image

10 parts of an amine compound having the following structural formula
[0076]
Embedded image

Was dissolved in 500 parts of monochlorobenzene and 500 parts of dichloromethane to obtain a paint for a charge transport layer.
[0077]
Apply this paint to the area from the top of the cylinder 3mm to the bottom of the cylinder by the dipping method, dry at 120 ° C for 50 minutes, and control it to 25 ± 1μm in the area from 15mm from the top of the cylinder to 12.5mm from the bottom of the cylinder. The same operation as in Comparative Example 1 was performed except that the formed charge transport layer was formed. The oxygen atom content on the surface of the photosensitive layer in the non-image forming area was 15.9 atom% before use, 13.4 atom% after printing 3000 sheets, and 11.7 atom% after printing 10,000 sheets. Was done.
[0078]
As a result of the potential evaluation, the dark portion potential, the bright portion potential, the residual potential, the potential after printing 3000 sheets, and the photo memory were all good. The solvent cracking property and the pot life were all good. However, the scraping due to durability was severe, and 50,000 sheets could not be durable.
[0079]
[Table 1]

As a result of the potential evaluation, all of the initial dark portion potential, light portion potential, residual potential, these potentials after printing 3000 sheets, and the photo memory were good. In addition, there were no cracks, gelled or undissolved ones, and the solvent cracking properties and pot life were all good.
[0080]
In Examples 1 to 7, good results were obtained for all evaluation items. However, in all of Comparative Examples 1 and 2, the cleaning blade was turned under high temperature and high humidity, and it was not possible to endure 50,000 sheets. In Comparative Example 3, the photosensitive layer was severely scraped, and it was not possible to withstand 50,000 sheets.
[0081]
As described above, the electrophotographic photoreceptor of the present invention can have both excellent mechanical strength and surface lubricity until after durability, and further, has excellent electrophotographic properties, excellent durability, and general properties. No turning over with cleaning blade.
[0082]
The embodiments of the present invention have been described above. Preferred embodiments of the present invention are listed below.
[Embodiment 1]
In an electrophotographic photoreceptor having a photosensitive layer on a conductive support, an image is output by performing image output in which the oxygen atom content on the surface of the photosensitive layer is 3000 sheets in a non-image forming area of the electrophotographic photoreceptor. An electrophotographic photoreceptor having a region which increases in a range from 0.8% to 3.4% before.
[0083]
[Embodiment 2]
At least one of a charging unit for charging the electrophotographic photosensitive member and a transfer unit for transferring a latent image or a visualized toner image from the electrophotographic photosensitive member to a transfer medium is directly applied to the electrophotographic photosensitive member. 2. The electrophotographic photoconductor according to embodiment 1, wherein the electrophotographic photoconductor is in contact with the electrophotographic photoconductor.
[0084]
[Embodiment 3]
3. The electrophotographic photosensitive member according to claim 2, wherein the charging unit has a roller shape, and applies a voltage obtained by superimposing an AC voltage on a DC voltage.
[0085]
[Embodiment 4]
The electrophotographic photosensitive member according to any one of the first to third embodiments is integrally supported together with at least one unit selected from a charging unit, a developing unit, and a cleaning unit, and is detachable from an electrophotographic apparatus main body. And process cartridge.
[0086]
[Embodiment 5]
An electrophotographic apparatus comprising a process cartridge integrally supporting the electrophotographic photosensitive member according to any one of the first to third embodiments together with at least one unit selected from a charging unit, a developing unit and a cleaning unit.
[0087]
【The invention's effect】
As described above, the electrophotographic photoreceptor of the present invention has both excellent mechanical strength and surface lubricity until after durability, and has good electrophotographic properties. In particular, it has become possible to provide an electrophotographic photoreceptor that is excellent in durability and does not cause turning of the cleaning blade. Further, the range of choice of materials (constituent units) has been expanded, and it has become possible to provide an electrophotographic photosensitive member according to the purpose of use. Further, it has become possible to provide a process cartridge and an electrophotographic apparatus having the above electrophotographic photosensitive member.
[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 axes
3 Primary charging means
4 Image exposure light
5 Developing means
6 transfer means
7 Transfer material
8 Image fixing means
9 Cleaning blade
10 Pre-exposure light
11 Process cartridge
12 rails

Claims (1)

In an electrophotographic photoreceptor having a photosensitive layer on a conductive support, an image is output by performing image output in which the oxygen atom content on the surface of the photosensitive layer is 3000 sheets in a non-image forming area of the electrophotographic photoreceptor. An electrophotographic photoreceptor having a region which increases in a range from 0.8% to 3.4% before.

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