JP4110053B2 - Electrophotographic photoreceptor manufacturing method, electrophotographic photoreceptor, and electrophotographic apparatus using the same - Google Patents

Description

【０１１６】
次いで、搬送チャンバーを用いて真空状態で、基体を図５で示す第２の成膜炉に移し、表２に示した条件で第２の層である上部阻止層と表面層を堆積した。
【０１１７】
【表２】

【０１１８】
以上の手順で得られた感光体は負帯電で用いられる感光体であり、次のように評価した。
【０１１９】
（球状突起数）
得られた感光体の表面を光学顕微鏡で観察した。そして、２０μｍ以上の大きさの球状突起の数を数え、１０ｃｍ²当たりの個数を調べた。得られた結果は、比較例２での値を１００％とした場合の相対比較でランク付けを行った。
【０１２０】
◎・・・ ３５％以上６５％未満
○・・・ ６５％以上９５％未満
△・・・ ９５％以上１０５％未満
×・・・ １０５％以上。
【０１２１】
（画像欠陥）
一次帯電器としてコロナ放電を採用し、また、クリーナーにクリーニングブレードを具える電子写真装置に、本実施例で作製した電子写真用感光体を装着して画像形成を行った。具体的には、キヤノン製ＧＰ６０５（プロセススピード３００ｍｍ／ｓｅｃ、イメージ露光）をベースに負帯電が可能なように改造し、トナーをネガトナーに変更した複写機を試験用電子写真装置として用い、Ａ３サイズの白紙原稿を複写した。こうして得られた画像を観察し、直径０．３ｍｍ以上の球状突起に起因する黒ポチの個数を数えた。得られた結果は、比較例２での値を１００％とした場合の相対比較でランク付けを行った。
【０１２２】
◎・・・ ３５％以上６５％未満
○・・・ ６５％以上８５％未満
△・・・ ８５％以上９５％未満
×・・・ ９５％以上１０５％未満。
【０１２３】
（帯電能）
電子写真感光体を電子写真装置に設置し、正帯電用電子写真感光体の場合は帯電器に＋６ｋＶの高電圧を印加し、負帯電用電子写真感光体の場合は帯電器に−６ｋＶの高電圧を印加しコロナ帯電を行い、現像器位置に設置した表面電位計により電子写真感光体の暗部表面電位を測定する。得られた結果は、比較例３での値を１００％とした場合の相対評価でランク付けを行った。
【０１２４】
◎・・・ １１５％以上
○・・・ １０５％以上、１１５％未満
△・・・ ９５％以上、１０５％未満
×・・・ ９５％未満。
【０１２５】
（残留電位）
電子写真感光体を、一定の暗部表面電位（例えば４５０Ｖ）に帯電させる。そして直ちに一定光量の比較的強い光（例えば１．５Ｌｘ・ｓｅｃ）を照射する。この時、現像器位置に設置した表面電位計により電子写真用光感光体の残留電位を測定する。得られた結果は、比較例３での値を１００％とした場合の相対評価でランク付けを行った。
【０１２６】
◎・・・ ８５％未満
○・・・ ８５％以上、９５％未満
△・・・ ９５％以上、１０５％未満
×・・・ １０５％以上。
【０１２７】
（電位均一性）
電子写真感光体を、一定の暗部表面電位（例えば４５０Ｖ）に帯電させる。そして直ちに一定光量の光（例えば０．５Ｌｘ・ｓｅｃ）を照射する。この時、現像器位置に設置した表面電位計により電子写真用光感光体のドラム軸方向中央部の表面電位をおよそ２００Ｖになるように光量を調節する。そして、周方向の電位分布及びドラム軸方向の電位分布を測定し、最大値−最小値の値を計算する。得られた結果は、比較例３での値を１００％とした場合の相対評価でランク付けを行った。
【０１２８】
◎・・・ ９５％未満
○・・・ ９５％以上、１０５％未満
△・・・ １０５％以上、１１０％未満
×・・・ １１０％以上。
【０１２９】
（コスト）
１本の感光体当たりの生産時間を計算して各々のコストとした。図６に示したＶＨＦ方式の堆積装置は１回に８本の電子写真感光体が生産できる。また図５に示したＲＦ方式の堆積装置は１回に１本とした。比較例４での値を１００％とした場合の相対評価でランク付けを行った。
【０１３０】
◎・・・ ８５％未満
○・・・ ８５％以上、９５％未満
△・・・ ９５％以上、１０５％未満
×・・・ １０５％以上
以上の方法で総合評価を行った。結果を比較例１、２、３、４と共に表５に示す。
【０１３１】
［比較例１］
図６に示す第１の成膜炉を用いて、直径１０８ｍｍのＡｌ基体に、表１に示す条件で第１の層である光導電層を堆積し、そのまま続けて表３に示す条件で第２の層である上部阻止層と表面層を堆積した。このようにして作製した負帯電用感光体は実施例１と同様に評価し、結果を表５に示す。
【０１３２】
［比較例２］
図５に示すａ−Ｓｉ感光体成膜装置を用いて、表４に示す条件で直径１０８ｍｍのＡｌ基体に第１の層である光導電層を積層し、そのまま続けて表２に示す条件で第２の層である上部阻止層と表面層を堆積した。このように作製した負帯電用感光体は実施例１と同様に評価し、結果を表５に示す。
【０１３３】
［比較例３］
図６に示すａ−Ｓｉ感光体成膜装置を用いて、表１に示す条件で直径１０８ｍｍのＡｌ基体に第１の層である光導電層を堆積し、搬送チャンバーを用いて真空状態で図５に示す第２の成膜炉に移し、本比較例では表２に示す第２の層の上部阻止層を設けずに表面層のみを積層した。このように作製した負帯電用感光体は実施例１と同様に評価し、結果を表５に示す。
【０１３４】
［比較例４］
図５に示すａ−Ｓｉ感光体成膜装置を用いて、表４に示す条件で直径１０８ｍｍのＡｌ基体に第１の層である光導電層を積層し、搬送チャンバーを用いて真空状態で図５に示す第２の成膜炉に移し、表２に示した条件で第２の層である上部阻止層と表面層を堆積した。このように作製した負帯電用感光体は実施例１と同様に評価し、結果を表５に示す。
【０１３５】
【表３】

【０１３６】
【表４】

【０１３７】
【表５】

【０１３８】
表５から、本発明の感光体は球状突起数が比較例１〜３と同等レベルであっても、画像欠陥であるポチの数は非常に改善することが分かる。
【０１３９】
比較例１では、第２の層の積層にも続けてＶＨＦ方式を採用すると、成長機構が同じでありほとんど画像欠陥が減少しない。そのためにポチの低減効果が小さく現れている。比較例２では、第１の層の積層と第２の層の積層とを続けてＲＦ方式を採用した結果、成長機構が同じでありほとんど画像欠陥が減少しない。
【０１４０】
また、実施例１および比較例１〜２に示すように、上部阻止層を設けることで帯電能、残留電位は改善し、画像欠陥が減少していることがわかる。
【０１４１】
［実施例２］
図６に示す第１の成膜炉を用いて、表６に示す条件で直径１０８ｍｍのＡｌ基体に、第１の層として光導電層まで堆積した。
【０１４２】
【表６】

【０１４３】
次いで、その状態で搬送チャンバーを用いて真空状態で、図５に示す第２の成膜炉に移し、表７に示す条件で第２の層である上部阻止層を堆積した。
【０１４４】
以上の手順で作製した感光体は正帯電で用いられる感光体であり、評価にはキヤノン製ＧＰ６０５をベースにした複写機を試験用電子写真装置として用い、実施例１と同様の手順で評価し、結果を表８に示す。
【０１４５】
【表７】

【０１４６】
［実施例３］
第１の成膜炉から基体を取り出し大気に晒した以外は、実施例２の場合と同様にして感光体を作製した。実施例１と同様の手順で評価し、結果を表８に示す。
【０１４７】
【表８】

【０１４８】
表８から分かるように、本発明の効果は、高真空成膜方式の第１の成膜炉から感光ドラムを移してＲＦ方式の第２の成膜炉で成膜することで得られる。また第１の成膜炉から第２の成膜炉に基体を移す際に、真空中で移しても良いし、大気に晒しても良い。
【０１４９】
［実施例４］
図６に示した第１の成膜炉を用いて、表９に示す条件で直径１０８ｍｍのＡｌ基体に、第１の層として下部阻止層と光導電層まで堆積した。
【０１５０】
【表９】

【０１５１】
次いで、堆積済みの基体を一旦成膜炉から大気中に取り出し、その後に基体を図５に示す第２の成膜炉に戻し、表１０に示す条件で第２の層である上部阻止層と表面層を堆積した。
【０１５２】
【表１０】

【０１５３】
以上の手順で作製した負帯電用感光体は実施例１と同様に評価した。結果を表１１に示す。
【０１５４】
［実施例５］
図６に示す第１の成膜炉を用いて、表９に示す条件で直径１０８ｍｍのＡｌ基体に、第１の層として下部阻止層と光導電層まで堆積した。
【０１５５】
次いで堆積済みの基体を一旦成膜炉から大気中に取り出した。本実施例では、このとき、図７に示す研磨装置を用いて表面を研磨し、球状突起の突起部分の平坦化を行った。この平坦化は研磨前の表面の突起の高さをレーザー顕微鏡で測定したときに、約１０μｍであった突起が、０．５μｍ以下に減少するように平坦化研磨を行った。
【０１５６】
次に図８に示す水洗浄装置により基体を洗浄した。その後基体を図５に示した第２の成膜炉に移し、表１０に示した条件で第２の層である上部阻止層と表面層を堆積した。
【０１５７】
以上の手順で作製した負帯電用感光体は実施例１と同様に評価した。結果を表１１に示す。
【０１５８】
【表１１】

【０１５９】
表１１から、下部阻止層を設けても本発明の効果は同様に得られることが分かる。また、球状突起の突起部分を平坦化した後に第２の層を積層する方がより画像欠陥低減効果が高まることが判明した。
【０１６０】
［実施例６］
図６に示す第１の成膜炉を用いて、表１２に示す条件で直径１０８ｍｍのＡｌ基体に、第１の層として下部阻止層と光導電層まで堆積した。
【０１６１】
【表１２】

【０１６２】
次いで、堆積済みの基体を一旦成膜炉から大気中に取り出し、図８に示す水洗浄装置により基体を洗浄した。その後、基体を図５に示した第２の成膜炉に戻し、表１３に示す条件で第２の層である上部阻止層と表面層を堆積した。本実施例においては、上部阻止層の膜厚を変化させた感光体Ａ〜Ｆを作成した。
【０１６３】
【表１３】

【０１６４】
以上の手順で得られた負帯電用感光体は実施例１と同様の手順で評価すると共に、更に球状突起の大きさの評価を行った。得られた感光体の表面全体を光学顕微鏡で観察し、最も大きい球状突起のおおよその直径を調べた。その結果、本実施例の製造条件においては、いずれの感光体においてもほぼ１００μｍであることが判明した。こうして得られた最大球状突起の直径に対して、上部阻止層の膜厚の比を求めた。
【０１６５】
評価結果を表１４に示す。表１４から、本発明の画像欠陥低減効果を得るためには、上部阻止層の膜厚は、最大球状突起の直径の１０^-4倍以上の膜厚が好適であることが分かる。また、感光体Ｆについては画像欠陥低減効果が充分に得られたが、上部阻止層が厚くなりすぎたために感度低下が見られた。従って、膜厚の上限は１μｍ以下に抑えることが望ましい。また、第２の層を堆積する前に水洗浄装置により洗浄を行うことにより、より密着性が向上した。
【０１６６】
【表１４】

【０１６７】
［実施例７］
図６に示す第１の成膜炉を用いて、表１５に示す条件で直径１０８ｍｍのＡｌ基体に、第１の層として下部阻止層と光導電層まで堆積した。
【０１６８】
【表１５】

【０１６９】
次いで、基体を成膜炉から大気中に取り出し、図８に示す水洗浄装置で基体の洗浄を行った。図５に示す第２の成膜炉に基体を戻した後に成膜炉を真空引きし、引き続いて、表１６に示した条件で第２の層である上部阻止層と表面層を堆積した。本実施例においては、上部阻止層に含有される第１３族原子であるＢ（ボロン）の含有量を変化させた感光体Ｇ〜Ｌを作製した。
【０１７０】
【表１６】

【０１７１】
以上の手順で得られた負帯電感光体を実施例１と同様の手順で評価した。
【０１７２】
評価後、それぞれの感光体を切り出し、ＳＩＭＳ分析（２次イオン質量分析）を行い上部阻止層中のＢ（ボロン）含有量を調べた。
【０１７３】
評価結果を表１７に示す。表１７から分かるように、上部阻止層のＢ（ボロン）含有量は１００原子ｐｐｍから３００００原子ｐｐｍが適している。また、第２の層を堆積する前に水洗浄装置により洗浄を行うことで、より密着性が向上した。
【０１７４】
【表１７】

【０１７５】
[実施例８]
図６に示した第１の成膜炉を用いて、表１８に示した条件で直径１０８ｍｍのＡｌ基体に、第１の層として下部阻止層と光導電層の領域１、領域２まで堆積した感光体を製造した。
【０１７６】
【表１８】

【０１７７】
次いで、感光体を成膜炉から大気中に取り出し、図８に示した水洗浄装置で感光体の洗浄を行った。図５に示した第２の成膜炉に感光体を戻した後に成膜炉を真空引きし、引き続いて、表１９に示した条件で第２の層である上部阻止層と表面層を堆積した。本実施例においては、光導電層を領域１及び領域２からなるように感光体を作製した。評価は、実施例１と同様に実施した。
【０１７８】
【表１９】

【０１７９】
[実施例９]
図６に示した第１の成膜炉を用いて、表２０に示した条件で直径１０８ｍｍのＡｌ基体に、第１の層として下部阻止層と光導電層の領域１まで堆積した感光体を製造した。
【０１８０】
【表２０】

【０１８１】
次いで、感光体を成膜炉から大気中に取り出し、図８に示した水洗浄装置で感光体の洗浄を行った。図５に示した第２の成膜炉に感光体を戻した後に成膜炉を真空引きし、引き続いて、表２１に示した条件で第２の層である光導電層の領域２、上部阻止層と表面層とを堆積した。本実施例においては、光導電層を領域１までを第１の成膜炉において作製し、光導電層の領域２からを第２の成膜炉において感光体を作製した。
【０１８２】
【表２１】

【０１８３】
以上の手順で得られた負帯電感光体は実施例１と同様の手順で評価した。
評価結果を表２２に示す。表２２から分かるように、光導電層を領域１及び領域２に分けても、またさらに光導電層の領域１と領域２の間で高真空成膜方式の第１の成膜炉から感光ドラムを移してＲＦ方式の第２の成膜炉で成膜を行っても、本発明の効果が得られることが分かる。
【０１８４】
【表２２】

【０１８５】
[実施例１０]
図６に示す第１の成膜炉を用いて、表２３に示す条件で直径１０８ｍｍのＡｌ基体に、第１の層として下部阻止層と光導電層まで堆積した。
【０１８６】
【表２３】

【０１８７】
次いで、堆積済みの基体を一旦成膜炉から大気中に取り出した。本実施例では、このとき、図７に示した研磨装置を用いて表面を研磨し、球状突起の突起部分の平坦化を行った。その後、図８に示す水洗浄装置により基体を洗浄した。そして基体を図５に示した第２の成膜炉に戻し、表２４に示す条件で第２の層である上部阻止層と表面層を堆積した。本実施例においては、成膜時間を変えることで上部阻止層の膜厚を変化させた感光体Ｍ〜Ｒを作成した。
【０１８８】
【表２４】

【０１８９】
以上の手順で得られた負帯電用感光体について、球状突起の大きさの評価を行った。球状突起の大きさの評価は、表面層、上部阻止層を通して見える第１の層の表面を光学顕微鏡で観察し、最も大きい球状突起のおおよその直径を調べた。その結果、本実施例の製造条件においては、Ｍ〜Ｒのいずれの感光体においてもほぼ８０μｍであることが判明した。こうして得られた最大球状突起の直径に対して、上部阻止層の膜厚の比を求めた。
【０１９０】
得られた負帯電用感光体は実施例１と同様の手順で評価すると共に、更に耐久後の画像欠陥の評価を行った。
【０１９１】
（耐久後の画像欠陥）
得られた電子写真感光体を電子写真装置に装着して、Ａ４用紙横送りで１０万枚の連続通紙耐久を行った。１０万枚の通紙後、Ａ３サイズの白紙原稿を複写した。こうして得られた画像を観察し、直径０．３ｍｍ以上の球状突起に起因する黒ポチの個数を数えた。
【０１９２】
得られた結果は、通紙耐久前の画像の黒ポチの個数と比較してランク付けを行った。
【０１９３】
◎・・・耐久後においても画像欠陥の悪化は見られず、非常に良好
○・・・わずかに画像欠陥は悪化したが１０％未満の増加であり、良好
△・・・１０％以上２０％未満の増加が見られたが実用上、支障なし
×・・・２０％以上の増加が見られた。
【０１９４】
評価結果を表２５に示す。表２５から、本発明の画像欠陥低減効果を得るためには、第１の層の表面に存在する球状突起の突起部を平坦化し、さらに上部阻止層の膜厚を最大球状突起の直径の１０^-4倍以上の膜厚にすることがより好適であることが判明した。また、上部阻止層を１．５μｍとした感光体Ｒについては画像欠陥低減効果は充分に得られたが、若干の感度低下が見られた。従って、上部阻止層の膜厚の上限は１μｍ以下に抑えることが望ましいことが分かる。
【０１９５】
【表２５】

【０１９６】
【発明の効果】
以上述べたように、第１ステップとして、排気手段と原料ガス供給手段を備えた真空気密可能な第１の成膜炉内に円筒状基体を設置し、少なくとも原料ガスを高周波電力により分解し、該基体上に少なくとも非単結晶材料からなる第１の層を堆積する工程と、第２ステップとして、第１の層を堆積した円筒状基体を第１の成膜炉から取り出し第２の成膜炉に移す工程と、第３ステップとして、第２の成膜炉内で少なくとも原料ガスを高周波電力により分解し、該第１の層上に少なくとも非単結晶材料から成る上部阻止層を含む第２の層を再び堆積させる工程とを行うことにより、感光体表面に存在する球状突起が画像上に現れなくなる。その結果、画像欠陥を大幅に改善させることができる電子写真感光体製造方法を提供することが可能となった。
【０１９７】
第１のステップにおいて用いる第１の成膜炉が高真空成膜であるＶＨＦ方式の感光体製造装置であり、第３ステップにおいて用いる第２の成膜炉がＲＦ方式の感光体製造装置であると、さらに画像欠陥を減少させることができる。
【０１９８】
更に第２ステップにおいて、球状突起の突起部を研磨することにより平坦化した後に第２の層を積層することで、より一層、球状突起を画像に現れにくくすることができ、その結果画像欠陥を減少させることができる。
【０１９９】
さらに第２ステップと第３ステップの間に感光体を水と接触させるとさらに良い。具体的には、水洗浄を行うことにより、その後表面保護層を堆積した際の密着性が向上し、膜ハガレに対するラチチュードが非常に広くなる。
【０２００】
また、必要に応じて第２ステップで感光体の検査を行うことで、品質不良の感光体については後の工程を省略することができ、全体としてコストの低減を図ることができる。
【図面の簡単な説明】
【図１】電子写真感光体の球状突起の一例を示す模式的断面図である。
【図２】本発明の電子写真感光体の球状突起の一例を示す模式的断面図である。
【図３】第２のステップで表面を研磨した本発明の電子写真感光体の球状突起の一例を示す模式的断面図である。
【図４】本発明の電子写真感光体の一例を示す模式的断面図である。
【図５】ＲＦを用いたａ−Ｓｉ感光体成膜装置の模式的断面図である。
【図６】ＶＨＦを用いたａ−Ｓｉ感光体成膜装置の模式的断面図である。
【図７】本発明に用いた表面研磨装置の模式的断面図である。
【図８】本発明に用いた水洗浄装置の模式的断面図である。
【図９】本発明の電子写真装置の一例の模式的断面図である。
【符号の説明】
１０１、２０１、３０１ 導電性の表面を有する基体
１０２、２０２、３０２ 第１の層
１０３、２０３、３０３ 球状突起
１０４、２０４、３０４ ダスト
１０５、２０５、３０５ 上部阻止層
１０６、２０６、３０６ 球状突起正常堆積部分の境界
４０１ 基体
４０２ 第１の層
４０３ 第２の層
４０４ 下部阻止層
４０５ 光導電層
４０６ 上部阻止層
４０７ 表面層
４０８ 球状突起
５１００、６１００ 成膜装置
５１１０、６１１０ 反応容器、成膜炉
５１１１、６１１１ カソード電極
５１１２、６１１２ 導電性の表面を有する基体
５１１３、６１１３ 基体加熱用ヒーター
５１１４、６１１４ ガス導入管
５１１５、６１１５ 高周波マッチングボックス
５１１６、６１１６ ガス配管
５１１７ リークバルブ
５１１８、６１１８ メインバルブ
５１１９、６１１９ 真空計
５１２０、６１２０ 高周波電源
５１２１ 絶縁材料
５１２３ 受け台
５２００ ガス供給装置
５２１１〜５２１６ マスフローコントローラー
５２２１〜５２２６ ボンベ
５２３１〜５２３６ バルブ
５２４１〜５２４６ 流入バルブ
５２５１〜５２５６ 流出バルブ
５２６０，６２６０ 補助バルブ
５２６１〜５２６６ 圧力調整器
６１２０ 回転モーター
６１３０ 放電空間
７００ 基体
７２０ 弾性支持機構
７３０ 加圧弾性ローラ
７３１ 研磨テープ
７３２ 送り出しロール
７３３ 巻き取りロール
７３４ 定量送り出しロール
７３５ キャプスタンローラ
８０１ 導電性の表面を有する基体
８０２ 処理部
８０３ 被処理部材搬送機構
８１１ 被処理部材投入台
８２１ 被処理部材洗浄槽
８２２ 洗浄液
８３１ 純水接触槽
８３２ ノズル
８４１ 乾燥槽
８４２ ノズル
８５１ 被処理部材搬出台
８６１ 搬送アーム
８６２ 移動機構
８６３ チャッキング機構
８６４ エアーシリンダー
８６５ 搬送レール
９０４ 電子写真感光体
９０５ 一次帯電器
９０６ 現像器
９０６ａ 現像剤（トナー）
９０７ 転写帯電器
９０８ クリーナー
９０８−１ 弾性ローラー
９０８−２ クリーニングブレード
９０９ ＡＣ除電器
９１０ 除電ランプ
９１３ 転写材
９１４ 送りローラー
Ａ 画像露光（アナログ光、或いはデジタル光）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for inexpensively producing an amorphous silicon electrophotographic photoreceptor capable of maintaining good image formation for a long period of time, having a high chargeability and a high density with few image defects, and the electrophotographic photoreceptor, The present invention relates to an electrophotographic apparatus.
[0002]
[Prior art]
As a material for forming a photoconductive layer in a solid-state imaging device or an electrophotographic photosensitive member for electrophotography and an original reading device in the field of image formation, it has a high sensitivity and a high SN ratio [photocurrent (Ip) / (Id)] and irradiation. It has absorption spectral characteristics that match the spectral characteristics of the electromagnetic waves that it emits, has fast photoresponsiveness, has a desired dark resistance value, is non-polluting to the human body during use, and in solid-state imaging devices, afterimages Is required to be easily processed within a predetermined time. Particularly in the case of an electrophotographic photoreceptor used in an office as an office machine, the above-mentioned pollution-free property is an important point.
[0003]
A material that has been attracting attention based on such a viewpoint is amorphous silicon in which a dangling bond is modified with a monovalent element such as hydrogen or a halogen atom (hereinafter referred to as “a-Si”). For example, there is application to an electrophotographic photoreceptor for electrophotography (see, for example, Patent Document 1).
[0004]
Conventionally, as a method of forming an electrophotographic photosensitive member made of a-Si on a conductive support, a sputtering method, a method of decomposing a source gas by heat (thermal CVD method), and a method of decomposing a source gas by light (light There are many known methods such as a CVD method and a method of decomposing a source gas by plasma (plasma CVD method). Among them, the plasma CVD method, that is, a method of decomposing a source gas by glow discharge such as direct current, high frequency, or microwave, and forming a deposited film on a conductive substrate is currently put into practical use, such as a method for forming an electrophotographic photosensitive member. Very advanced.
[0005]
As a layer structure of such a deposited film, a so-called surface layer having a blocking ability on the surface side in addition to a conventional electrophotographic photoreceptor using a-Si as a base and appropriately adding a modifying element. In addition, a structure in which an upper blocking layer is laminated has also been proposed.
[0006]
For example, a photoconductor is disclosed in which an intermediate layer (upper blocking layer) containing atoms for controlling conductivity is reduced between the photoconductive layer and the surface layer by reducing the carbon atom content from the surface layer. (For example, refer to Patent Document 2).
[0007]
[Patent Document 1]
JP 54-86341 A
[Patent Document 2]
JP-A-8-15882
[0008]
[Problems to be solved by the invention]
By such a conventional electrophotographic photosensitive member forming method, an electrophotographic photosensitive member having practical characteristics and uniformity to some extent can be obtained. Further, if the inside of the vacuum reaction vessel is strictly cleaned, it is possible to obtain an electrophotographic photosensitive member with a certain number of defects. However, in these conventional methods for producing an electrophotographic photosensitive member, for example, for an electrophotographic photosensitive member for electrophotography, a product requiring a relatively large deposited film with a large area has a uniform film quality and various optical and electrical characteristics. There is a problem that it is difficult to obtain a deposited film that satisfies the requirements for characteristics and has few image defects at the time of image formation by an electrophotographic process in a high yield.
[0009]
In particular, the a-Si film has the property that when dust of the order of several μm adheres to the surface of the substrate, abnormal growth, that is, so-called “spherical protrusions” grow with the dust as a nucleus during film formation. . The spherical protrusion has a shape that is a reverse of the conical shape with dust as the starting point.There are very many localized levels at the interface between the normal deposition part and the spherical protrusion part, so the resistance decreases, and the charged charge passes through the interface. Therefore, it has the property of coming out to the support side. For this reason, the part with the spherical protrusion appears as a white point in the solid black image on the image (in the case of reversal development, it appears as a black point in the solid white image). The so-called “pochi” image defect has a stricter standard every year, and depending on the size, even if there are several A3 sheets, they may be treated as defective. Furthermore, the standard becomes more stringent when mounted on a color copier, and even if one is present on A3 paper, it may be defective.
[0010]
Since these spherical protrusions start from dust, the support to be used is precisely cleaned before film formation, and all the steps to be installed in the film formation apparatus are performed in a clean room or under vacuum. In this way, efforts have been made to reduce the amount of dust adhering to the support as much as possible before the start of film formation, which has been effective. However, the cause of the occurrence of the spherical protrusion is not only the dust adhering to the support. That is, when an a-Si photosensitive member is manufactured, the required film thickness is very large, from several μm to several tens of μm, and therefore the film formation time ranges from several hours to several tens of hours. During this time, the a-Si film is deposited not only on the support but also on the film forming furnace wall and the structure in the film forming furnace. Since these furnace walls and structures do not have a controlled surface like a support, the adhesion is weak in some cases, and film peeling may occur during film formation over a long period of time. If even a slight peeling occurs during the film formation, it becomes dust and adheres to the surface of the photoconductor being deposited, and this causes the abnormal growth of the spherical projections. Therefore, in order to maintain a high yield, careful management is required not only for the management of the support before film formation but also for the prevention of film peeling in the film formation furnace during film formation. The manufacture of the Si photoreceptor was difficult.
[0011]
The object of the present invention is to solve such problems in the conventional electrophotographic photosensitive member without sacrificing electrical characteristics, and to stably manufacture at a low cost and with a high yield. It is an object to provide an easy-to-use method for producing an electrophotographic photoreceptor, an electrophotographic photoreceptor thereof, and an electrophotographic apparatus.
[0012]
[Means for Solving the Problems]
The present invention provides a method of manufacturing an electrophotographic photosensitive member including a layer made of a non-single crystal material. As a first step, a cylinder is placed in a vacuum film-tight first film forming furnace including an exhaust unit and a source gas supply unit. A step of manufacturing a substrate in which at least a source gas is decomposed by high-frequency power and a first layer made of at least a non-single crystal material is deposited on the conductivity of the substrate; In the step of transferring the substrate on which the first layer is deposited to the second film forming furnace, and as the third step, at least the source gas is decomposed by high-frequency power in the second film forming furnace, and further on the first layer. And re-depositing a second layer including an upper blocking layer made of at least a non-single crystal material.
[0013]
In the first step, the plasma CVD method (VHF-PCVD method) using the VHF band, which has a high deposition rate and excellent film quality uniformity, is used, and in the third step, the RF band, which has a low rate and good adhesion, is used. It is more preferable to adopt the plasma CVD method (RF-PCVD method) that has been performed in terms of both image defect reduction and photoreceptor characteristics.
[0014]
In the second step, the substrate on which the first layer is laminated may be once taken out from the film formation furnace to the atmosphere, and the surface of the substrate on which the first layer is laminated is processed such as polishing. It is more preferable that the process of performing is included. Further, the set temperature of the substrate having the conductive surface may be changed between the second step and the third step, and it is further preferable to inspect the substrate during that time. Specifically, an appearance inspection, an image inspection, a potential inspection, and the like. Further, after the inspection, washing with water improves the adhesion when the upper blocking layer is formed thereafter, and the latitude for film peeling becomes very wide.
[0015]
The present inventors have studied improvement of image defects caused by spherical protrusions in a photoreceptor made of a non-single crystal material, particularly an a-Si photoreceptor. In particular, efforts have been made to prevent image defects caused by spherical protrusions generated by film peeling from the film forming furnace wall and structures in the furnace during film formation.
[0016]
As described above, spherical projections become image defects such as spots, because there are many localized levels at the interface between the normal deposition part and the spherical projection part of the deposited film, which lowers the resistance, and the charged electric charge passes through the interface. This is because they pass through to the support side. However, since the spherical projections generated by the dust adhering to the middle of the film grows from the middle of the deposited film, not from the substrate, if a blocking layer is provided on the surface side to prevent charging charge injection, The presence of protrusions may not cause image defects.
[0017]
Therefore, the present inventors conducted an experiment in which a film formation condition for growing spherical protrusions was selected from the middle of the deposited film, and an upper blocking layer was provided on the surface of the substrate formed under this condition. However, contrary to expectation, it has been found that the injection of charges from the spherical projections cannot be prevented, and an image defect occurs.
[0018]
In order to investigate this cause, the cross section of the spherical protrusion was cut out and observed in detail with an SEM (scanning electron microscope). This is shown in FIG. In the figure, 101 is a conductive substrate, 102 is a normal deposition portion of the first layer, 103 is a spherical projection, 104 is dust adhered during film formation, 105 is an upper blocking layer, 106 is a spherical projection portion and a normal deposition portion. Is the boundary. As can be seen from FIG. 1, the spherical protrusion 103 grows from the middle of the normal deposition portion of the first layer 102 with the dust 104 as a starting point, and there is a boundary 106 between the spherical protrusion 103 and the normal deposition portion. ing. The charged electric charge passes through this boundary to the support side, causing a spot on the image. Even if the upper blocking layer 105 is deposited on the spherical protrusion 103, the upper blocking layer 105 is deposited while maintaining the growth pattern of the spherical protrusion 103 grown so far. I can do it. As a result, the charged charge passes through this boundary and the function as the upper blocking layer is lost.
[0019]
Therefore, the present inventors have intensively studied to prevent the growth of the boundary 106 when the upper blocking layer 105 is laminated, and as a result, different film formation is performed for the deposition of the first layer and the deposition of the second layer. It was discovered that the growth of this boundary 106 can be suppressed by depositing by the method.
[0020]
That is, if the substrate is once taken out from the first film-forming furnace before the upper blocking layer is formed, transferred to the second film-forming furnace and then deposited on the upper blocking layer, the growth of this boundary can be suppressed. It is. In particular, it is more preferable to adopt a high vacuum film forming method such as VHF-PCVD method for the first film forming furnace and a low rate film forming method based on RF-PCVD method to the second film forming furnace. I understood that.
[0021]
In order to investigate this situation, the cross section of the spherical protrusion was cut out again, and the cross section was observed with an SEM (scanning electron microscope). The result is shown in FIG. The spherical protrusion 203 starts growing from the dust 204 attached during the film formation of the normal deposition portion of the first layer 202 as the starting point. However, the difference between the photoconductors of this time is that when the upper blocking layer 205 is deposited, the boundary portion 205 is disconnected from the boundary portion of the spherical protrusion 203 so far. That is, the first layer 202 is formed in the first film formation furnace of the VHF-PCVD method, is once taken out from the first film formation furnace, and then returned to the second film formation furnace of the RF-PCVD method. When the upper blocking layer 205 is formed, it is estimated that the growth surface is discontinuous. As a result, the boundary between the low-resistance spherical projection portion 203 and the normal deposition portion is sealed with the upper blocking layer 205, and it becomes difficult for the charged charges to pass through and image defects are suppressed.
[0022]
Although the details of the change that occurs on the surface of the first layer 202 are currently unknown, the deposition pressure differs greatly between the high vacuum deposition method such as the VHF-PCVD method and the RF-PCVD method. Can do. Therefore, it is considered that a difference occurs in the growth mechanism of the deposited film, and as a result, the growth of the boundary 106 is suppressed. In particular, by reducing the rate in the RF-PCVD method, the coverage is improved, and the deposited film is also formed in a place where the shadow is likely to be a shadow such as the boundary of the protrusion, so that it is considered that image defects can be suppressed. .
[0023]
Further, in order to prevent the charged charges from slipping out of the spherical protrusion 203, it has been found effective to polish and flatten the top of the spherical protrusion 203 after forming the first layer 202.
[0024]
FIG. 3 shows an example of an electrophotographic photoreceptor in which, after the first layer 302 is formed, the top of the spherical protrusion 303 is flattened by polishing and a discontinuous laminated interface is formed. The spherical protrusion 303 starts growing from the dust 304 attached during the film formation of the normal deposition portion of the first layer 302 as a starting point. However, the top of the spherical protrusion 303 is polished and flattened by a polishing means before the upper blocking layer 305 is deposited. For this reason, the upper blocking layer 305 formed thereafter does not inherit the boundary portion 306 at all, and is uniformly deposited on the flattened surface. As described above, it is more complete when the upper blocking layer 305 is laminated after the first layer 202 is planarized by the polishing means so that the lamination interface is flattened and the lamination interface becomes a clear discontinuous interface. Since the boundary 306 between the spherical protrusion portion 303 and the normal deposition portion of the first layer 302 is sealed, the charged charges are less likely to pass through, and the effect of suppressing image defects is further enhanced.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail with reference to the drawings as necessary.
[0026]
<A-Si Photosensitive Member According to the Present Invention>
FIG. 4 shows an example of an electrophotographic photoreceptor according to the present invention.
[0027]
In the electrophotographic photosensitive member of the present invention, a first layer 402 is laminated in a first film forming furnace as a first step on a substrate 401 made of a conductive material such as Al or stainless steel, and a second step as a second step. The substrate on which the first layer is laminated is taken out from the first film forming furnace and transferred to the second film forming furnace, and as the third step, the second layer 403 including the upper blocking layer 406 is stacked in the second film forming furnace. It is a thing. By manufacturing in this way, the upper blocking layer 406 can be deposited so as to cover the spherical protrusion 408 generated in the first layer, and even if the spherical protrusion 408 is present, it does not appear in the image. It is possible to maintain good image quality. In the present invention, the first layer 402 includes a photoconductive layer 405. As a material of the photoconductive layer 405, a-Si is used. In addition, as a material for the upper blocking layer 406, a layer containing a-Si as a base material and containing carbon, nitrogen, and oxygen as needed is used.
[0028]
Note that a lower blocking layer 404 may be further provided on the first layer 402 as necessary. By providing the lower blocking layer 404 and selecting and containing a group 13 element, a group 15 element, or the like as a dopant, the charge polarity such as positive charge and negative charge can be controlled.
[0029]
Specific examples of group 13 atoms that serve as dopants include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). B and Al are particularly preferred. is there. Specific examples of Group 15 atoms include phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi). P is particularly preferred.
[0030]
The second layer 403 may further include a surface layer 407 on the upper blocking layer 406 as necessary. The surface layer 407 is based on a-Si, and if necessary, a layer containing a relatively large amount of at least one of carbon, nitrogen, and oxygen is used to improve environmental resistance, wear resistance, and scratch resistance. Can do.
[0031]
In addition, at least a first region of the photoconductive layer 405 may be deposited as the first layer 402, and then at least a second region of the photoconductive layer and an upper blocking layer 406 may be deposited as the second layer.
[0032]
<Shape and material of substrate according to the present invention>
The shape of the substrate 401 may be a desired one according to the driving method of the electrophotographic photosensitive member. For example, it can be a cylindrical or plate-like endless belt with a smooth surface or an uneven surface, and its thickness is appropriately determined so that a desired electrophotographic photoreceptor can be formed. When flexibility as a body is required, it can be made as thin as possible within a range in which the function as a cylinder can be sufficiently exhibited. However, the cylinder is usually preferably 10 μm or more from the standpoints of mechanical strength and the like in manufacturing and handling.
[0033]
As the base material, conductive materials such as Al and stainless steel are generally used. For example, various conductive materials such as various plastics, glass, and ceramics, especially those having no conductivity, are formed with at least a light receiving layer. A material imparted with conductivity, for example, by vapor deposition on the surface to be used can be used.
[0034]
In addition to the above, examples of the conductive material include metals such as Cr, Mo, Au, In, Nb, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof.
[0035]
Examples of the plastic include films or sheets of polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, and the like.
[0036]
<First layer according to the present invention>
The first layer 402 is composed of an amorphous material (abbreviated as “a-Si (H, X)”) containing a silicon atom as a base and further containing a hydrogen atom and / or a halogen atom in the present invention. .
[0037]
The a-Si film can be formed by a plasma CVD method, a sputtering method, an ion plating method, or the like, but a film produced by using the plasma CVD method is preferable because a high quality film can be obtained.
[0038]
In particular, since the first layer is required to have the thickest layer thickness among the electrophotographic photosensitive members and the uniformity of the film quality is required, the VHF band capable of plasma in a high vacuum is used. A plasma CVD method is used.
[0039]
The raw material is SiH _Four , Si ₂ H ₆ , Si _Three H ₈ , Si _Four H _Ten It can be produced by using silicon hydride (silanes) in a gas state or the like which can be gasified as a raw material gas and decomposing with high frequency power. Furthermore, SiH is easy to handle at the time of layer preparation and has good Si supply efficiency. _Four , Si ₂ H ₆ Is preferable.
[0040]
At this time, the temperature of the substrate is preferably 200 to 450 ° C., more preferably about 250 to 350 ° C. in view of characteristics. This is for accelerating the surface reaction on the substrate surface and sufficiently relaxing the structure.
[0041]
Similarly, the optimum range of the pressure in the reaction vessel is appropriately selected according to the layer design. ^-2 ~ 1x10 ^Three Pa, preferably 5 × 10 ^-2 ~ 5x10 ² Pa, optimally 1 × 10 ^-1 ~ 1x10 ² Pa is preferable.
[0042]
In addition, H ₂ Alternatively, it is also preferable from the viewpoint of improving characteristics to form a layer by mixing a desired amount of a gas containing halogen atoms. An effective source gas for supplying halogen atoms is fluorine gas (F ₂ ), BrF, ClF, ClF _Three , BrF _Three , BrF _Five , IF _Five , IF ₇ And interhalogen compounds. Specific examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include SiF _Four , Si ₂ F ₆ And the like. Preferred examples thereof include silicon fluoride. In addition, these carbon supply source gases can be replaced with H as required. ₂ , He, Ar, Ne or the like may be used after being diluted.
[0043]
The layer thickness of the first layer 402 is not particularly limited, but about 15 to 50 μm is appropriate in consideration of the manufacturing cost.
[0044]
Further, the first layer 402 may have a plurality of layer structures in order to improve characteristics. For example, by disposing a layer with a narrower band gap on the surface side and a layer with a wider band gap on the substrate side, the photosensitivity and charging characteristics can be improved at the same time. In particular, for a light source having a relatively long wavelength and almost no variation in wavelength, such as a semiconductor laser, an epoch-making effect appears by such a layer structure.
[0045]
The lower blocking layer 404 provided as necessary is generally based on a-Si (H, X), and has a conductivity type controlled by containing a dopant such as a group 13 element or a group 15 element, and from the substrate. It is possible to have the ability to prevent the injection of carriers. In this case, if necessary, the stress can be adjusted by adding at least one element selected from C, N, and O to have a function of improving the adhesion of the photosensitive layer.
[0046]
As the group 13 element and the group 15 element used as the dopant of the lower blocking layer 404, those described above are used. Further, as a source material for introducing a group 13 atom, specifically, for introducing a boron atom, B ₂ H ₆ , B _Four H _Ten , B _Five H ₉ , B _Five H ₁₁ , B ₆ H _Ten , B ₆ H ₁₂ , B ₆ H ₁₄ Boron hydride such as BF _Three , BCl _Three , BBr _Three And boron halides. In addition, AlCl _Three , GaCl _Three , Ga (CH _Three ) _Three , InCl _Three , TlCl _Three Etc. can also be mentioned. B ₂ H ₆ Is one of the preferred raw materials from the viewpoint of handling.
[0047]
Effectively used as a raw material for introducing Group 15 atoms is PH for introducing phosphorus atoms. _Three , P ₂ H _Four Phosphorus hydride such as PF _Three , PF _Five , PCl _Three , PCl _Five , PBr _Three , PI _Three Phosphorus halides such as PH _Four I etc. are mentioned. In addition, AsH _Three , AsF _Three , AsCl _Three , AsBr _Three , AsF _Five , SbH _Three , SbF _Three , SbF _Five , SbCl _Three , SbCl _Five , BiH _Three , BiCl _Three , BiBr _Three Are effective starting materials for introducing Group 15 atoms.
[0048]
The content of dopant atoms is preferably 1 × 10 ^-2 ~ 1x10 ^Four Atomic ppm, more preferably 5 × 10 ^-2 ~ 5x10 ^Three Atomic ppm, optimally 1 × 10 ^-1 ~ 1x10 ^Three The atomic ppm is desirable.
[0049]
<Second layer according to the present invention>
After the first layer 402 is formed, the second layer 403 according to the present invention is deposited after the discharge is stopped once and transferred from the first film forming furnace to the second film forming furnace.
[0050]
For the formation of the second layer, it is preferable to use a plasma CVD method using an RF band with a low rate and good adhesion.
[0051]
The film forming furnace may be transferred by removing the substrate from the film forming furnace while maintaining the vacuum after forming the first layer 402, or by removing the substrate from the film forming furnace and bringing it into contact with a gas containing oxygen and water vapor. May be. As the gas containing oxygen and water vapor, air that is air in a normal environment can be used. That is, the gas to be contacted contains at least oxygen and water vapor and, if necessary, an inert gas such as nitrogen gas. For example, oxygen is preferably contained in the total gas in an amount of about 5% by volume or more. Pure oxygen with water vapor added may be used, but an oxygen content of about air is usually sufficient. The water vapor may be added so that the relative humidity at room temperature of 25 ° C. is, for example, 1% or more, preferably about 10% or more. Under normal conditions, it is preferable to use air, which is air in the environment, because the process is simple. At this time, it is preferable that the top of the spherical protrusion on the surface is polished by a polishing means to be flat. Such processing can be performed by a surface polishing apparatus described later. By flattening the spherical protrusion, it is possible to more effectively prevent the slipping of electric charges, to prevent the cleaning blade from being chipped or poorly cleaned due to the spherical protrusion, and also to prevent the occurrence of fusion starting from the spherical protrusion. Can do.
[0052]
It is also meaningful to perform an appearance inspection and characteristic evaluation of the substrate as necessary when the substrate on which the first layer is formed is taken out from the film forming furnace. By performing the inspection at this point, a subsequent process can be omitted for a defective substrate, and the cost can be reduced as a whole.
[0053]
Further, it is desirable to clean the substrate on which the first layer is formed before setting it again in the film forming furnace in order to improve the adhesion of the second layer 403 and reduce dust adhesion. As a specific cleaning method, it is preferable to clean the surface with a clean cloth or paper, and preferably to perform precision cleaning by organic cleaning or water cleaning. In particular, in view of environmental considerations in recent years, water washing with a water washing apparatus described later is more preferable.
[0054]
The second layer 403 of the present invention includes an upper blocking layer 406. The upper blocking layer 406 has a function of blocking charge injection from the surface side to the first layer side when the photosensitive member is subjected to a charging process with a constant polarity on its free surface. Such a function is not exhibited when the charging process is performed. In order to provide such a function, it is necessary for the upper blocking layer 406 to appropriately contain atoms that control conductivity. As the atoms used for such purposes, in the present invention, group 13 atoms that give p-type conduction characteristics or group 15 atoms that give n-type conduction characteristics can be used. Specific examples of such group 13 atoms include boron (B), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), and boron is particularly preferable. Specific examples of Group 15 atoms include phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and the like, with phosphorus being particularly preferred.
[0055]
The necessary content of the atoms for controlling the conductivity contained in the upper blocking layer 406 is preferably changed as appropriate in consideration of the composition of the upper blocking layer 406 and the manufacturing method. On the other hand, it is set to 100 atom ppm or more and 30000 atom ppm or less, and more preferably 500 atom ppm or more and 10,000 atom ppm or less.
[0056]
The atoms that control the conductivity contained in the upper blocking layer 406 may be distributed uniformly in the upper blocking layer 406 or may be included in a non-uniform distribution in the layer thickness direction. May be. However, in any case, in the in-plane direction parallel to the surface of the substrate, it is necessary to uniformly contain the material in a uniform distribution from the viewpoint of uniform characteristics in the in-plane direction.
[0057]
The upper blocking layer 406 can be made of any material as long as it is an a-Si-based material, but is preferably made of the same material as the surface layer 407 described later. That is, materials such as “a-SiC: H, X”, “a-SiO: H, X”, “a-SiN: H, X”, “a-SiCON: H, X” are preferably used. The carbon atoms, nitrogen atoms, or oxygen atoms contained in the upper blocking layer 406 may be uniformly distributed in the layer, or may be contained in a non-uniformly distributed state in the layer thickness direction. Also good. However, in any case, in the in-plane direction parallel to the surface of the substrate, it is necessary to uniformly contain the material in a uniform distribution from the viewpoint of uniform characteristics in the in-plane direction.
[0058]
The content of carbon atoms and / or nitrogen atoms and / or oxygen atoms contained in the entire layer region of the upper blocking layer 406 in the present invention is appropriately determined so that the object of the present invention is effectively achieved. In the case of one type, the amount is preferably 10% to 70% of the total amount with silicon as the total amount when there are two or more types.
[0059]
In the present invention, it is necessary that the upper blocking layer 406 contains hydrogen atoms and / or halogen atoms. This compensates for dangling bonds of silicon atoms and improves layer quality, particularly photoconductivity. Indispensable for improving the characteristics and charge retention characteristics. The hydrogen content is usually 30 to 70 atomic%, preferably 35 to 65 atomic%, and most preferably 40 to 60 atomic% with respect to the total amount of constituent atoms. The halogen atom content is usually 0.01 to 15 atom%, preferably 0.1 to 10 atom%, and most preferably 0.5 to 5 atom%.
[0060]
The film thickness of the upper blocking layer 406 is adjusted to a film thickness that can effectively prevent image defects due to the spherical protrusions 408. There are various sizes when the spherical protrusion 408 is viewed from the surface side, but the larger the diameter, the greater the degree of charge injection and the more likely it is to appear in an image. Accordingly, it is effective to increase the thickness of the upper blocking layer 406 as the spherical protrusion increases. Specifically, the diameter of the largest spherical protrusion existing on the substrate after the second layer is deposited is 10. ^-Four It is desirable that the thickness be twice or more. By setting the thickness within this range, it is possible to effectively prevent charges from slipping out of the spherical protrusion 408. The upper limit of the film thickness is preferably 1 μm or less from the viewpoint of minimizing sensitivity reduction.
[0061]
In order to improve the adhesion between the first layer 402 and the second layer 403, it is effective to provide a layer equivalent to the composition of the first layer 402 between the upper blocking layer 406.
[0062]
Further, it is preferable that the composition of the upper blocking layer 406 is continuously changed from the first layer 402 side toward the surface layer 407, which is effective in not only improving adhesion but also preventing interference.
[0063]
In order to form the upper blocking layer 406 having characteristics capable of achieving the object of the present invention, the mixing ratio of the gas for supplying Si and the gas for supplying C and / or N and / or O, the gas in the reaction vessel It is necessary to appropriately set the pressure, discharge power, and substrate temperature.
[0064]
A substance that can be a gas for supplying silicon (Si) used in forming the upper blocking layer includes SiH. _Four , Si ₂ H ₆ , Si _Three H ₈ , Si _Four H _Ten It is mentioned that silicon hydrides (silanes) that are in a gas state or can be gasified are effectively used. Further, in terms of easy handling at the time of layer formation, good Si supply efficiency, etc. _Four , Si ₂ H ₆ Is preferable. In addition, these source gases for supplying Si are supplied with H as required. ₂ , He, Ar, Ne or the like may be used after being diluted.
[0065]
Examples of substances that can serve as carbon supply gas include CH _Four , C ₂ H ₂ , C ₂ H ₆ , C _Three H ₈ , C _Four H _Ten It is mentioned that hydrocarbons that are in the gas state or can be gasified are used effectively, and further, in terms of ease of handling at the time of layer formation, good C supply efficiency, etc. _Four , C ₂ H ₂ , C ₂ H ₆ Is preferable. Also, these source gases for C supply can be replaced with H as required. ₂ , He, Ar, Ne or the like may be used after being diluted.
[0066]
Examples of substances that can serve as nitrogen or oxygen supply gas include NH _Three , NO, N ₂ O, NO ₂ , O ₂ , CO, CO ₂ , N ₂ The compounds in the gaseous state such as those that can be gasified are effective. In addition, the source gas for supplying nitrogen and oxygen can be replaced with H if necessary. ₂ , He, Ar, Ne, etc.
[0067]
Similarly, the optimum range of the pressure in the reaction vessel is appropriately selected according to the layer design. ^-2 ~ 1x10 ^Three Pa, preferably 5 × 10 ^-2 ~ 5x10 ² Pa, optimally 1 × 10 ^-1 ~ 1x10 ² Pa is preferable.
[0068]
Furthermore, the optimum range of the substrate temperature is appropriately selected according to the layer design, but in the usual case, it is preferably 150 to 350 ° C., more preferably 180 to 330 ° C., and most preferably 200 to 300 ° C.
[0069]
In the present invention, the layer formation factors such as the mixing ratio of the dilution gas, the gas pressure, the discharge power, the substrate temperature, etc. for forming the upper blocking layer 406 are not normally determined separately, but the desired characteristics. It is desirable to determine an optimum value of each layer creation factor based on mutual and organic relations in order to form a photoconductor having the above.
[0070]
In the present invention, the second layer 403 may further be provided with a surface layer 407 formed of a non-single crystal material, particularly an a-Si material, on the upper blocking layer 406 as necessary. The surface layer 407 has a free surface, and is effective mainly in improving moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability.
[0071]
The a-Si-based surface layer 407 has a common component in which each of the amorphous materials forming the photoconductive layer 405, the upper blocking layer 406, and the surface layer 407 constituting the first layer is a silicon atom. Therefore, chemical stability is sufficiently ensured at the laminated interface. When an a-Si-based material is used as the material of the surface layer 407, a compound with a silicon atom containing at least one element selected from carbon, nitrogen, and oxygen is preferable, and in particular, a main component is a-SiC. Is preferred.
[0072]
When the surface layer 407 contains one or more of carbon, nitrogen, and oxygen, the content of these atoms is preferably in the range of 30 to 90% with respect to all atoms constituting the network.
[0073]
The surface layer 407 contains at least hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms and improves layer quality, in particular, photoconductivity and charge retention characteristics. Indispensable for. The hydrogen content is usually 30 to 70 atomic%, preferably 35 to 65 atomic%, and most preferably 40 to 60 atomic% with respect to the total amount of constituent atoms. The fluorine atom content is usually 0.01 to 15 atom%, preferably 0.1 to 10 atom%, and most preferably 0.5 to 5 atom%.
[0074]
A photoreceptor formed within these hydrogen and / or fluorine content ranges can be satisfactorily applied as being excellent in practice. That is, it is known that defects existing in the surface layer 407 (mainly dangling bonds of silicon atoms and carbon atoms) adversely affect the characteristics of the electrophotographic photosensitive member. For example, deterioration of charging characteristics due to charge injection from the free surface, fluctuations in charging characteristics due to changes in the surface structure under the usage environment, for example, high humidity, and further from the photoconductive layer to the surface layer during corona charging or light irradiation Such adverse effects include the occurrence of an afterimage phenomenon during repeated use due to charge injection and charge trapping in defects in the surface layer.
[0075]
However, by controlling the hydrogen content in the surface layer 407 to 30 atomic% or more, defects in the surface layer are greatly reduced. As a result, the electrical characteristics and high-speed continuous usability are improved compared to the conventional case. Can be planned. On the other hand, if the hydrogen content in the surface layer 407 exceeds 70 atomic%, the hardness of the surface layer is lowered, so that it cannot withstand repeated use. Therefore, controlling the hydrogen content within the above range is one of important factors for obtaining excellent desired electrophotographic characteristics. The hydrogen content in the surface layer 407 can be controlled by the flow rate (ratio) of the source gas, the substrate temperature, the discharge power, the gas pressure, and the like.
[0076]
In addition, by controlling the fluorine content in the surface layer 407 within a range of 0.01 atomic% or more, it is possible to more effectively achieve the generation of bonds between silicon atoms and carbon atoms in the surface layer. Become. Furthermore, as a function of fluorine atoms, it is possible to effectively prevent the breakage of the bond between silicon atoms and carbon atoms due to damage such as corona.
[0077]
On the other hand, if the fluorine content in the surface layer 407 exceeds 15 atomic%, the effect of generating bonds between silicon atoms and carbon atoms in the surface layer and the breaking of bonds between silicon atoms and carbon atoms due to damage such as corona. The effect which prevents is hardly recognized. Furthermore, residual potential and image memory are remarkably recognized because excess fluorine atoms impede carrier mobility in the surface layer. Therefore, controlling the fluorine content within the above range is one of important factors for obtaining desired electrophotographic characteristics. The fluorine content in the surface layer 407 can be controlled by the flow rate (ratio) of the source gas, the substrate temperature, the discharge power, the gas pressure, and the like, similarly to the hydrogen content.
[0078]
Further, in the present invention, the surface layer 407 may contain atoms for controlling conductivity as required. The atoms for controlling conductivity may be contained in the surface layer in a uniformly distributed state, or there may be a portion containing in a non-uniformly distributed state in the layer thickness direction. .
[0079]
Examples of the atoms that control conductivity include so-called impurities in the semiconductor field, and group 13 atoms that give p-type conduction characteristics or group 15 atoms that give n-type conduction characteristics can be used. .
[0080]
The layer thickness of the surface layer 407 is usually 0.01 to 3 μm, preferably 0.05 to 2 μm, and most preferably 0.1 to 1 μm from the viewpoints of wear of the surface layer and an increase in residual potential. It is desirable to be done.
[0081]
In order to form the surface layer 407 having characteristics capable of achieving the object of the present invention, it is necessary to appropriately set the temperature of the substrate and the gas pressure in the reaction vessel as desired. The optimum range of the substrate temperature (Ts) is appropriately selected according to the layer design. In normal cases, it is preferably 150 to 350 ° C., more preferably 180 to 330 ° C., and most preferably 200 to 300 ° C. desirable.
[0082]
Similarly, the optimum range of the pressure in the reaction vessel is appropriately selected according to the layer design. ^-2 ~ 1x10 ^Three Pa, preferably 5 × 10 ^-2 ~ 5x10 ² Pa, optimally 1 × 10 ^-1 ~ 1x10 ² Pa is preferable.
[0083]
As the source gas used for forming the surface layer, the source gas used for forming the upper blocking layer can be used.
[0084]
Although the above-mentioned ranges can be mentioned as the desirable numerical ranges of the substrate temperature and gas pressure for forming the surface layer 407, the conditions are not usually determined separately, and a photoreceptor having desired characteristics is formed. It is desirable to determine an optimum value based on mutual and organic relations.
[0085]
<A-Si Photoreceptor Film Forming Apparatus According to the Present Invention>
FIG. 5 is a diagram schematically showing an example of an apparatus for depositing a photoreceptor by RF plasma CVD using an RF band high-frequency power source for forming the second layer, and FIG. 6 shows the formation of the first layer. It is the figure which showed typically an example of the deposition apparatus of the photoreceptor by VHF plasma CVD method using the VHF power supply which performs.
[0086]
These apparatuses are roughly classified into a deposition apparatus 5100 (6100), a source gas supply apparatus 5200, and an exhaust apparatus (not shown) for decompressing the inside of the film forming furnace 5110. This apparatus is configured by replacing the deposition apparatus 5100 shown in FIG. 5 with the deposition apparatus 6100 of FIG.
[0087]
The first layer is formed by a photoreceptor deposition apparatus (first film-forming furnace) by the VHF plasma CVD method shown in FIG. However, the high-frequency power to be applied is 50 V to 450 MHz, for example, a VHF power source having a frequency of 105 MHz, and the pressure is kept about 13.3 mPa to 1330 Pa, lower than the RF plasma CVD method.
[0088]
In the film forming furnace 6110 of the film forming apparatus 6100, a base 6112 connected to the ground, a heater 6113 for heating the base, and a source gas introduction pipe 6114 are installed, and a high frequency power source 6120 is connected via a high frequency matching box 6115. ing. The source gas supply device 5200 is made of SiH. _Four , H ₂ , CH _Four , NO, B ₂ H ₆ , CF _Four Material gas cylinders 5221 to 5226, valves 5231 to 5236, 5241 to 5246, 5251 to 5256, and mass flow controllers 5211 to 5216, and gas cylinders of the respective constituent gases are gas introduction pipes in the film forming furnace 6110 through the valve 5260. 6114.
[0089]
The base 6112 is connected to the ground by being placed on the conductive cradle 6123.
[0090]
Hereinafter, an example of a procedure of a method for forming a photoreceptor using the apparatus of FIG. 6 will be described.
[0091]
A substrate 6112 is installed in the film forming furnace 6110, and the film forming furnace 6110 is evacuated by an unillustrated exhaust device (for example, a vacuum pump). Subsequently, the temperature of the substrate 6112 is controlled to a desired temperature of 200 to 450 ° C., more preferably 250 to 350 ° C. by the substrate heating heater 6113. Next, it is confirmed that the gas cylinder valve 5231 to 5236 and the leak valve (not shown) of the film forming furnace are closed in order to flow the material gas for forming the photoconductor into the film forming furnace 5110. After confirming that 5241 to 5246, the outflow valves 5251 to 5256, and the auxiliary valve 6260 are opened, the main valve 6118 is opened and the film forming furnace 6110 and the gas supply pipe 6116 are exhausted.
[0092]
Thereafter, when the reading of the vacuum gauge 6119 reaches 0.5 mPa, the auxiliary valve 6260 and the outflow valves 5251 to 5256 are closed. Thereafter, each gas is introduced from the gas cylinders 5221 to 5226 by opening the valves 5231 to 5236, and each gas pressure is adjusted to 0.2 MPa by the pressure regulators 5261 to 5266. Next, the inflow valves 5241 to 5246 are gradually opened to introduce each gas into the mass flow controllers 5211 to 5216.
[0093]
After completing the film formation preparation by the above procedure, a first layer, for example, a photoconductive layer is first formed on the base 6112.
[0094]
That is, when the substrate 6112 reaches a desired temperature, necessary ones of the outflow valves 5251 to 5256 and the auxiliary valve 6260 are gradually opened, and a desired source gas is supplied from the gas cylinders 5221 to 5226 to the gas introduction pipe 6114. Into the film forming furnace 6110. Next, it adjusts so that each source gas may become a desired flow volume by each mass flow controller 5211-5216. At that time, the opening of the main valve 6118 is adjusted while looking at the vacuum gauge 6119 so that the inside of the film forming furnace 6110 has a desired pressure of 13.3 mPa to 1330 Pa. When the internal pressure is stabilized, the high-frequency power source 5120 is set to a desired power and, for example, a high-frequency power is supplied to the cathode electrode 6111 through the high-frequency matching box 6115 using a VHF power source having a frequency of 50 to 450 MHz, for example, 105 MHz. Raise it. Each material gas introduced into the film formation furnace 6110 is decomposed by this discharge energy, and a first layer containing a desired silicon atom as a main component is deposited on the substrate 6112.
[0095]
In this apparatus, in the discharge space 6130 surrounded by the support 6112, the introduced source gas is excited and dissociated by the discharge energy, and a predetermined deposited film is formed on the support 6112. At this time, in order to make the layer formation uniform, the support rotating motor 6120 is rotated at a desired rotation speed.
[0096]
After the formation of the desired film thickness, the supply of high-frequency power is stopped, the outflow valves 5251 to 5256 are closed, the inflow of each source gas into the film formation furnace 6110 is stopped, and the formation of the first layer is completed. . Known compositions and film thicknesses of the first layer can be used. When the lower blocking layer is formed between the first layer and the substrate, basically, the above operation may be performed in advance.
[0097]
It is important that the substrate on which the first layer is formed by the above procedure is once taken out from the first film forming furnace shown in FIG. 6 and transferred to the second film forming furnace shown in FIG. In the case of taking out from the film forming furnace, appearance inspection such as peeling of the substrate and spherical protrusions may be performed at the same time. In addition, image inspection and potential characteristic inspection can be performed as necessary.
[0098]
When the photoconductor is in contact with ozone, such as image inspection or electric potential characteristic inspection, it is preferable to perform water washing or organic washing before forming the second layer. Water washing is more preferable. The method of washing with water will be described later. Thus, the adhesiveness can be further improved by washing with water before forming the second layer.
[0099]
The substrate exposed to the atmosphere is returned to the photoconductor deposition apparatus (second film forming furnace) by the RF plasma CVD method using the RF band high-frequency power source for forming the second layer, and includes the upper blocking layer. The second layer is formed. The second layer is formed by using CH as the source gas. _Four , C ₂ H ₆ Hydrocarbon gas such as H if necessary ₂ Except for the additional use of a dilution gas, etc., this is basically the same as the formation of the first layer.
[0100]
However, the high frequency power to be applied is supplied to the cathode electrode 5111 through the high frequency matching box 5115 to generate a high frequency glow discharge. Each material gas introduced into the film forming furnace 5110 is decomposed by this discharge energy, and a second layer containing a desired silicon atom as a main component is deposited on the substrate 5112. At that time, the pressure is maintained at about 13.3 Pa to 1330 Pa and higher than the VHF plasma CVD method.
[0101]
Known compositions and film thicknesses of the second layer can be used. In order to improve the adhesion between the second layer and the first layer, the above operation is basically performed also when the second layer is laminated after laminating the same layer as the first layer. This can be done in advance.
[0102]
Furthermore, a SiC-based surface layer is stacked on the outermost surface using a Si-containing gas and a carbon-containing gas. In this case, basically, the above operation may be performed.
[0103]
<Surface polishing apparatus according to the present invention>
FIG. 7 shows an example of a surface processing apparatus used for surface processing in the manufacturing process of the electrophotographic photoreceptor of the present invention, specifically, an example of a surface polishing apparatus used for polishing as surface processing. Indicates. In the configuration example of the surface polishing apparatus shown in FIG. 7, a workpiece (deposited film surface on a cylindrical substrate) 700 is a cylindrical substrate having a first layer made of a-Si deposited on its surface. Yes, attached to the elastic support mechanism 720. In the apparatus shown in FIG. 7, for example, a pneumatic holder is used as the elastic support mechanism 720, and specifically, a pneumatic holder (trade name: air pick, model number: PO45TCA * 820) manufactured by Bridgestone Corporation is used. The pressure elastic roller 730 winds the polishing tape 731 and presses the surface of the a-Si photoconductive layer or intermediate layer of the workpiece 700. The polishing tape 731 is supplied from the feed roll 732 and collected by the take-up roll 733. The feed speed is adjusted by a fixed feed roll 734 and a capstan roller 735, and the tension is also adjusted. As the polishing tape 731, what is usually called a wrapping tape is preferably used. When processing the surface of the first layer such as the photoconductive layer of non-single crystal material such as a-Si or the intermediate layer such as the upper blocking layer, the lapping tape has SiC, Al as the abrasive grains. ₂ O _Three , Fe ₂ O _Three Etc. are used. Specifically, Fuji Film Lapping Tape LT-C2000 was used. The roller portion of the pressure elastic roller 730 is made of a material such as neoprene rubber or silicone rubber, and has a JIS rubber hardness of 20 to 80, more preferably a JIS rubber hardness of 30 to 60. Further, the shape of the roller part is preferably such that the diameter of the central part in the longitudinal direction is slightly larger than the diameters of both end parts, for example, the diameter difference between the two is 0.0 to 0.6 mm, more preferably 0.2 to 0. A shape in the range of 4 mm is preferred. The pressure elastic roller 730 presses the rotating workpiece (deposition film surface on the cylindrical substrate) 700 in a pressure pressure range of 0.05 MPa to 0.2 MPa, and applies the polishing tape 731 such as the above-described one. The lapping tape is fed to polish the surface of the deposited film.
[0104]
For surface polishing performed in the atmosphere, wet polishing means such as buff polishing can be used in addition to the means using the polishing tape. Further, when using a wet polishing means, a step of washing and removing the liquid used for polishing is provided after the polishing process, and at that time, the surface is brought into contact with water and cleaned. be able to.
[0105]
In this way, for example, by flattening the laminated interface including amorphous silicon as described above and making the laminated interface a discontinuous interface, the spherical projection portion 303 and the normal deposition portion of the first layer 302 are more completely separated. Since the boundary 306 is sealed, it is possible to obtain a photoreceptor in which charged charges are less likely to pass through and the effect of suppressing image defects is further increased.
[0106]
<Water cleaning apparatus according to the present invention>
For example, Japanese Patent No. 2786756 discloses water washing. An example of the water washing apparatus which can be used for this invention is shown in FIG.
[0107]
The processing apparatus shown in FIG. 8 includes a processing unit 802 and a processing target member transport mechanism 803. The processing unit 802 includes a processing target input base 811, a processing target cleaning tank 821, a pure water contact tank 831, a drying tank 841, and a processing target carry-out base 851. Both the cleaning tank 821 and the pure water contact tank 831 are provided with a temperature adjusting device (not shown) for keeping the temperature of the liquid constant. The transport mechanism 803 includes a transport rail 865 and a transport arm 861, and the transport arm 861 moves air on the rail 865, a chucking mechanism 863 that holds the base 801, and air for moving the chucking mechanism 863 up and down. It consists of a cylinder 864. The substrate 801 placed on the input table 811 is transported to the cleaning tank 821 by the transport mechanism 803. The oil and powder adhering to the surface are cleaned by ultrasonic treatment in the cleaning liquid 822 made of the surfactant aqueous solution in the cleaning tank 821. Next, the substrate 801 is transported to the pure water contact tank 831 by the transport mechanism 803, and pure water having a resistivity of 175 kΩ · m (17.5 MΩ · cm) maintained at a temperature of 25 ° C. is supplied from the nozzle 832 to 4.9 MPa. Sprayed with pressure. After the pure water contact step, the substrate 801 is moved to the drying tank 841 by the transport mechanism 803, and is dried by blowing high-temperature high-pressure air from the nozzle 842. The substrate 801 after the drying process is carried to the carry-out table 851 by the transport mechanism 803.
[0108]
<Electrophotographic apparatus according to the present invention>
An example of an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention is shown in FIG. The apparatus of this example is suitable when a cylindrical electrophotographic photosensitive member is used, but the electrophotographic apparatus of the present invention is not limited to this example, and the shape of the photosensitive member is an endless belt or the like. May be desired.
[0109]
In FIG. 9, reference numeral 904 denotes an electrophotographic photosensitive member according to the present invention, and reference numeral 905 denotes a primary charger that charges the photosensitive member 904 for forming an electrostatic latent image. Although a corona charger is shown in the figure, a contact charger as described in JP-A-63-210864 may be used. Reference numeral 906 denotes a developing device for supplying a developer (toner) 906a to the photosensitive member 904 on which the electrostatic latent image is formed, and reference numeral 907 denotes a transfer charger for transferring the toner on the surface of the photosensitive member to the transfer material. . In the figure, a corona charger is described, but a roller electrode as described in JP-A-62-157881 may be used. A cleaner 908 cleans the surface of the photoreceptor. In this example, in order to effectively perform uniform cleaning of the surface of the photoreceptor, the surface of the photoreceptor is cleaned using the elastic roller 908-1 and the cleaning blade 908-2, but only one of them or the cleaner 908 itself. It is also possible to design a configuration that does not include Reference numerals 909 and 910 denote an AC static eliminator and a static eliminator lamp, respectively, for neutralizing the surface of the photosensitive member in preparation for the next copying operation, but it is possible to design a configuration without either or both. Reference numeral 913 denotes a transfer material such as paper, and reference numeral 914 denotes a transfer roller for the transfer material. As the light source for exposure A, a halogen light source, or a light source such as a laser or LED mainly having a single wavelength is used.
[0110]
Using such an apparatus, a copy image is formed as follows, for example.
[0111]
First, the electrophotographic photosensitive member 904 is rotated at a predetermined speed in the direction of the arrow, and the surface of the photosensitive member 904 is uniformly charged using the primary charger 905. Next, image exposure A is performed on the surface of the charged photoconductor 904, and an electrostatic latent image of the image is formed on the surface of the photoconductor 904. Then, when the portion where the electrostatic latent image is formed on the surface of the photoreceptor 904 passes through the installation portion of the developing device 906, the toner is supplied to the surface of the photoreceptor 904 by the developing device 906, and the electrostatic latent image is converted into the toner. The toner image is developed (developed) as an image by 906a, and further, the toner image reaches the installation portion of the transfer charger 907 as the photoconductor 904 rotates, and is transferred to the transfer material 913 sent by the feed roller 914. It is.
[0112]
After the transfer is completed, residual toner is removed from the surface of the electrophotographic photosensitive member 904 by the cleaner 908 to prepare for the next copying process, and further, the static eliminator 909 and the static elimination lamp 910 so that the potential of the surface becomes zero or almost zero. The charge is eliminated, and one copy process is completed.
[0113]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited at all by these.
[0114]
[Example 1]
Using the a-Si photosensitive film forming apparatus (first film forming furnace) shown in FIG. 6, the photoconductive layer is deposited as the first layer on the Al substrate having a diameter of 108 mm under the conditions shown in Table 1. did.
[0115]
[Table 1]

[0116]
Next, the substrate was transferred to the second film forming furnace shown in FIG. 5 in a vacuum state using the transfer chamber, and the upper blocking layer and the surface layer as the second layer were deposited under the conditions shown in Table 2.
[0117]
[Table 2]

[0118]
The photoreceptor obtained by the above procedure is a photoreceptor used for negative charging, and was evaluated as follows.
[0119]
(Number of spherical protrusions)
The surface of the obtained photoreceptor was observed with an optical microscope. Then, the number of spherical protrusions having a size of 20 μm or more is counted, and 10 cm ² The number of hits was examined. The obtained results were ranked by relative comparison when the value in Comparative Example 2 was 100%.
[0120]
◎ 35% or more and less than 65%
○ ... 65% or more and less than 95%
△ ... 95% or more and less than 105%
X: 105% or more.
[0121]
(Image defect)
Corona discharge was adopted as the primary charger, and the electrophotographic photosensitive member produced in this example was mounted on an electrophotographic apparatus having a cleaner with a cleaning blade to form an image. Specifically, based on Canon's GP605 (process speed 300mm / sec, image exposure), modified to be negatively chargeable and using a copier with toner changed to negative toner, A3 size A blank manuscript was copied. The images thus obtained were observed, and the number of black spots caused by spherical protrusions having a diameter of 0.3 mm or more was counted. The obtained results were ranked by relative comparison when the value in Comparative Example 2 was 100%.
[0122]
◎ 35% or more and less than 65%
○ ... 65% or more and less than 85%
△ ... 85% or more and less than 95%
X: 95% or more and less than 105%.
[0123]
(Chargeability)
The electrophotographic photosensitive member is installed in an electrophotographic apparatus. In the case of an electrophotographic photosensitive member for positive charging, a high voltage of +6 kV is applied to the charger, and in the case of an electrophotographic photosensitive member for negative charging, a high voltage of -6 kV is applied to the charging device. A voltage is applied to perform corona charging, and the surface potential of the dark part of the electrophotographic photosensitive member is measured with a surface potential meter installed at the position of the developing device. The obtained results were ranked by relative evaluation when the value in Comparative Example 3 was 100%.
[0124]
◎ ... 115% or more
○ ... 105% or more, less than 115%
Δ: 95% or more, less than 105%
X: Less than 95%.
[0125]
(Residual potential)
The electrophotographic photosensitive member is charged to a constant dark portion surface potential (for example, 450 V). Immediately thereafter, a relatively strong light having a constant light quantity (for example, 1.5 Lx · sec) is irradiated. At this time, the residual potential of the electrophotographic photosensitive member is measured by a surface potential meter installed at the position of the developing device. The obtained results were ranked by relative evaluation when the value in Comparative Example 3 was 100%.
[0126]
◎ ... Less than 85%
○ ... 85% or more, less than 95%
Δ: 95% or more, less than 105%
X: 105% or more.
[0127]
(Potential uniformity)
The electrophotographic photosensitive member is charged to a constant dark portion surface potential (for example, 450 V). Immediately after that, a certain amount of light (for example, 0.5 Lx · sec) is irradiated. At this time, the amount of light is adjusted by a surface potential meter installed at the position of the developing unit so that the surface potential at the center in the drum axial direction of the electrophotographic photoconductor is about 200V. Then, the potential distribution in the circumferential direction and the potential distribution in the drum axis direction are measured, and the maximum value-minimum value is calculated. The obtained results were ranked by relative evaluation when the value in Comparative Example 3 was 100%.
[0128]
◎ ... Less than 95%
○ ... 95% or more, less than 105%
△ ... 105% or more, less than 110%
X: 110% or more.
[0129]
(cost)
The production time per photoconductor was calculated and used as each cost. The VHF deposition apparatus shown in FIG. 6 can produce eight electrophotographic photosensitive members at a time. Further, the number of RF deposition apparatuses shown in FIG. 5 is one at a time. Ranking was performed by relative evaluation when the value in Comparative Example 4 was 100%.
[0130]
◎ ... Less than 85%
○ ... 85% or more, less than 95%
Δ: 95% or more, less than 105%
× ... 105% or more
Overall evaluation was performed by the above method. The results are shown in Table 5 together with Comparative Examples 1, 2, 3, and 4.
[0131]
[Comparative Example 1]
Using the first film-forming furnace shown in FIG. 6, a photoconductive layer, which is the first layer, is deposited on an Al substrate having a diameter of 108 mm under the conditions shown in Table 1. Two layers, an upper blocking layer and a surface layer, were deposited. The negatively charged photoreceptor thus prepared was evaluated in the same manner as in Example 1, and the results are shown in Table 5.
[0132]
[Comparative Example 2]
Using the a-Si photosensitive film forming apparatus shown in FIG. 5, a photoconductive layer as the first layer was laminated on an Al substrate having a diameter of 108 mm under the conditions shown in Table 4, and the conditions shown in Table 2 were continued as they were. A second layer, an upper blocking layer and a surface layer, were deposited. The negatively charged photoreceptor thus prepared was evaluated in the same manner as in Example 1, and the results are shown in Table 5.
[0133]
[Comparative Example 3]
A photoconductive layer as the first layer is deposited on an Al substrate having a diameter of 108 mm under the conditions shown in Table 1 using the a-Si photosensitive film forming apparatus shown in FIG. In this comparative example, only the surface layer was laminated without providing the upper blocking layer of the second layer shown in Table 2. The negatively charged photoreceptor thus prepared was evaluated in the same manner as in Example 1, and the results are shown in Table 5.
[0134]
[Comparative Example 4]
Using the a-Si photosensitive film forming apparatus shown in FIG. 5, a photoconductive layer as the first layer is laminated on an Al substrate having a diameter of 108 mm under the conditions shown in Table 4, and the film is shown in a vacuum state using a transfer chamber. Then, the upper blocking layer and the surface layer as the second layer were deposited under the conditions shown in Table 2. The negatively charged photoreceptor thus prepared was evaluated in the same manner as in Example 1, and the results are shown in Table 5.
[0135]
[Table 3]

[0136]
[Table 4]

[0137]
[Table 5]

[0138]
From Table 5, it can be seen that the photoreceptor of the present invention greatly improves the number of spots that are image defects even when the number of spherical protrusions is the same level as in Comparative Examples 1 to 3.
[0139]
In Comparative Example 1, when the VHF method is employed for the second layer, the growth mechanism is the same and image defects are hardly reduced. For this reason, the effect of reducing the spots appears small. In Comparative Example 2, as a result of adopting the RF system by continuing the stacking of the first layer and the stacking of the second layer, the growth mechanism is the same and the image defects are hardly reduced.
[0140]
Further, as shown in Example 1 and Comparative Examples 1 and 2, it can be seen that by providing the upper blocking layer, the charging ability and the residual potential are improved, and the image defects are reduced.
[0141]
[Example 2]
A first film forming furnace shown in FIG. 6 was used to deposit a photoconductive layer as a first layer on an Al substrate having a diameter of 108 mm under the conditions shown in Table 6.
[0142]
[Table 6]

[0143]
Next, in this state, the transfer chamber was used to transfer to a second film forming furnace shown in FIG. 5 in a vacuum state, and an upper blocking layer as a second layer was deposited under the conditions shown in Table 7.
[0144]
The photoconductor produced by the above procedure is a photoconductor used for positive charging. For evaluation, a copying machine based on Canon GP605 was used as a test electrophotographic apparatus, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 8.
[0145]
[Table 7]

[0146]
[Example 3]
A photoconductor was prepared in the same manner as in Example 2 except that the substrate was taken out from the first film forming furnace and exposed to the atmosphere. Evaluation was performed in the same procedure as in Example 1, and the results are shown in Table 8.
[0147]
[Table 8]

[0148]
As can be seen from Table 8, the effect of the present invention can be obtained by transferring the photosensitive drum from the first film forming furnace of the high vacuum film forming method and forming the film in the second film forming furnace of the RF method. Further, when transferring the substrate from the first film forming furnace to the second film forming furnace, it may be transferred in a vacuum or exposed to the atmosphere.
[0149]
[Example 4]
Using the first film forming furnace shown in FIG. 6, a lower blocking layer and a photoconductive layer were deposited as a first layer on an Al substrate having a diameter of 108 mm under the conditions shown in Table 9.
[0150]
[Table 9]

[0151]
Then, the deposited substrate is once taken out from the film formation furnace to the atmosphere, and then the substrate is returned to the second film formation furnace shown in FIG. 5, and the upper blocking layer which is the second layer under the conditions shown in Table 10 A surface layer was deposited.
[0152]
[Table 10]

[0153]
The negatively charged photoreceptor prepared by the above procedure was evaluated in the same manner as in Example 1. The results are shown in Table 11.
[0154]
[Example 5]
Using the first film-forming furnace shown in FIG. 6, a lower blocking layer and a photoconductive layer were deposited as a first layer on an Al base having a diameter of 108 mm under the conditions shown in Table 9.
[0155]
Next, the deposited substrate was once taken out from the film forming furnace into the atmosphere. In this example, at this time, the surface was polished by using the polishing apparatus shown in FIG. 7, and the protrusions of the spherical protrusions were flattened. This flattening was performed so that the protrusions, which were about 10 μm, were reduced to 0.5 μm or less when the height of the protrusions on the surface before polishing was measured with a laser microscope.
[0156]
Next, the substrate was cleaned by a water cleaning apparatus shown in FIG. Thereafter, the substrate was transferred to the second film forming furnace shown in FIG. 5, and the upper blocking layer and the surface layer, which were the second layer, were deposited under the conditions shown in Table 10.
[0157]
The negatively charged photoreceptor prepared by the above procedure was evaluated in the same manner as in Example 1. The results are shown in Table 11.
[0158]
[Table 11]

[0159]
From Table 11, it can be seen that the effect of the present invention can be obtained similarly even if the lower blocking layer is provided. It has also been found that the effect of reducing the image defect is further enhanced by laminating the second layer after flattening the protruding portion of the spherical protrusion.
[0160]
[Example 6]
Using the first film forming furnace shown in FIG. 6, a lower blocking layer and a photoconductive layer were deposited as a first layer on an Al substrate having a diameter of 108 mm under the conditions shown in Table 12.
[0161]
[Table 12]

[0162]
Next, the deposited substrate was once taken out from the film forming furnace into the atmosphere, and the substrate was cleaned by the water cleaning apparatus shown in FIG. Thereafter, the substrate was returned to the second film forming furnace shown in FIG. 5, and an upper blocking layer and a surface layer as the second layer were deposited under the conditions shown in Table 13. In this example, photoconductors A to F having different thicknesses of the upper blocking layer were prepared.
[0163]
[Table 13]

[0164]
The negatively charged photoreceptor obtained by the above procedure was evaluated by the same procedure as in Example 1, and the size of the spherical protrusion was further evaluated. The entire surface of the obtained photoreceptor was observed with an optical microscope, and the approximate diameter of the largest spherical protrusion was examined. As a result, it was found that in any of the photoconductors, the manufacturing conditions of this example were about 100 μm. The ratio of the thickness of the upper blocking layer to the diameter of the maximum spherical protrusion thus obtained was determined.
[0165]
The evaluation results are shown in Table 14. From Table 14, in order to obtain the image defect reduction effect of the present invention, the thickness of the upper blocking layer is 10 times the diameter of the largest spherical protrusion. ^-Four It can be seen that a film thickness of twice or more is suitable. Further, although the image defect reduction effect was sufficiently obtained for the photoreceptor F, the sensitivity was lowered because the upper blocking layer became too thick. Therefore, it is desirable to keep the upper limit of the film thickness to 1 μm or less. Further, the adhesion was further improved by washing with a water washing device before depositing the second layer.
[0166]
[Table 14]

[0167]
[Example 7]
Using the first film forming furnace shown in FIG. 6, a lower blocking layer and a photoconductive layer were deposited as a first layer on an Al substrate having a diameter of 108 mm under the conditions shown in Table 15.
[0168]
[Table 15]

[0169]
Next, the substrate was taken out from the film forming furnace into the atmosphere, and the substrate was cleaned with a water cleaning apparatus shown in FIG. After returning the substrate to the second film forming furnace shown in FIG. 5, the film forming furnace was evacuated, and subsequently, an upper blocking layer and a surface layer as the second layer were deposited under the conditions shown in Table 16. In this example, photoconductors G to L were produced in which the content of B (boron) which is a Group 13 atom contained in the upper blocking layer was changed.
[0170]
[Table 16]

[0171]
The negatively charged photoreceptor obtained by the above procedure was evaluated by the same procedure as in Example 1.
[0172]
After the evaluation, each photoconductor was cut out and subjected to SIMS analysis (secondary ion mass spectrometry) to examine the B (boron) content in the upper blocking layer.
[0173]
The evaluation results are shown in Table 17. As can be seen from Table 17, the B (boron) content of the upper blocking layer is suitably from 100 atomic ppm to 30000 atomic ppm. Further, the adhesion was further improved by washing with a water washing device before depositing the second layer.
[0174]
[Table 17]

[0175]
[Example 8]
Using the first film-forming furnace shown in FIG. 6, the first blocking layer and photoconductive layer regions 1 and 2 were deposited on an Al substrate having a diameter of 108 mm under the conditions shown in Table 18. A photoreceptor was manufactured.
[0176]
[Table 18]

[0177]
Next, the photoconductor was taken out from the film forming furnace to the atmosphere, and the photoconductor was cleaned with a water cleaning apparatus shown in FIG. After the photosensitive member is returned to the second film forming furnace shown in FIG. 5, the film forming furnace is evacuated, and subsequently, an upper blocking layer and a surface layer as the second layer are deposited under the conditions shown in Table 19. did. In this example, the photoconductor was prepared so that the photoconductive layer was composed of regions 1 and 2. Evaluation was carried out in the same manner as in Example 1.
[0178]
[Table 19]

[0179]
[Example 9]
Using the first film-forming furnace shown in FIG. 6, a photoconductor deposited as a first layer up to region 1 of the lower blocking layer and the photoconductive layer on an Al substrate having a diameter of 108 mm under the conditions shown in Table 20 is used. Manufactured.
[0180]
[Table 20]

[0181]
Next, the photoconductor was taken out from the film forming furnace to the atmosphere, and the photoconductor was cleaned with a water cleaning apparatus shown in FIG. After the photosensitive member is returned to the second film forming furnace shown in FIG. 5, the film forming furnace is evacuated, and subsequently, the region 2 and the upper part of the photoconductive layer as the second layer under the conditions shown in Table 21. A blocking layer and a surface layer were deposited. In this example, the photoconductive layer up to region 1 was produced in the first film forming furnace, and the photoconductor was produced from the photoconductive layer region 2 in the second film forming furnace.
[0182]
[Table 21]

[0183]
The negatively charged photoreceptor obtained by the above procedure was evaluated by the same procedure as in Example 1.
The evaluation results are shown in Table 22. As can be seen from Table 22, even if the photoconductive layer is divided into region 1 and region 2, the photosensitive drum is also moved from the first film forming furnace of the high vacuum film forming system between the region 1 and the region 2 of the photoconductive layer. It can be seen that the effects of the present invention can be obtained even if the film is formed in the second RF film forming furnace.
[0184]
[Table 22]

[0185]
[Example 10]
Using the first film forming furnace shown in FIG. 6, a lower blocking layer and a photoconductive layer were deposited as a first layer on an Al substrate having a diameter of 108 mm under the conditions shown in Table 23.
[0186]
[Table 23]

[0187]
Next, the deposited substrate was once taken out from the film forming furnace into the atmosphere. In this example, at this time, the surface was polished by using the polishing apparatus shown in FIG. 7, and the protrusions of the spherical protrusions were flattened. Thereafter, the substrate was cleaned by the water cleaning apparatus shown in FIG. Then, the substrate was returned to the second film forming furnace shown in FIG. 5, and the upper blocking layer and the surface layer as the second layer were deposited under the conditions shown in Table 24. In this example, photoconductors M to R in which the film thickness of the upper blocking layer was changed by changing the film formation time were prepared.
[0188]
[Table 24]

[0189]
The size of the spherical protrusion was evaluated for the negatively charged photoreceptor obtained by the above procedure. The size of the spherical protrusion was evaluated by observing the surface of the first layer visible through the surface layer and the upper blocking layer with an optical microscope and examining the approximate diameter of the largest spherical protrusion. As a result, it was found that the manufacturing conditions of this example were approximately 80 μm for any of the photoconductors M to R. The ratio of the thickness of the upper blocking layer to the diameter of the maximum spherical protrusion thus obtained was determined.
[0190]
The obtained negatively charged photoconductor was evaluated in the same procedure as in Example 1, and image defects after durability were further evaluated.
[0191]
(Image defects after endurance)
The obtained electrophotographic photosensitive member was mounted on an electrophotographic apparatus, and 100,000 sheets of continuous paper passing durability was performed by A4 paper lateral feeding. After passing 100,000 sheets, an A3 size blank original was copied. The images thus obtained were observed, and the number of black spots caused by spherical protrusions having a diameter of 0.3 mm or more was counted.
[0192]
The obtained results were ranked in comparison with the number of black spots in the image before endurance for passing paper.
[0193]
◎ ・ ・ ・ No deterioration of image defects even after endurance, very good
○ ・ ・ ・ Slightly worsened image defects, but increased by less than 10%, good
Δ: An increase of 10% or more but less than 20% was observed, but there was no practical problem.
X: An increase of 20% or more was observed.
[0194]
The evaluation results are shown in Table 25. From Table 25, in order to obtain the image defect reduction effect of the present invention, the protrusions of the spherical protrusions present on the surface of the first layer are flattened, and the film thickness of the upper blocking layer is 10 times the diameter of the maximum spherical protrusion. ^-Four It has been found that it is more preferable to make the film thickness twice or more. Further, with respect to the photoreceptor R having an upper blocking layer of 1.5 μm, a sufficient image defect reduction effect was obtained, but a slight decrease in sensitivity was observed. Therefore, it can be seen that the upper limit of the thickness of the upper blocking layer is desirably 1 μm or less.
[0195]
[Table 25]

[0196]
【The invention's effect】
As described above, as a first step, a cylindrical substrate is installed in a vacuum-tight first film forming furnace equipped with an evacuation unit and a source gas supply unit, and at least the source gas is decomposed with high-frequency power, A step of depositing at least a first layer made of a non-single-crystal material on the substrate, and a second step of removing the cylindrical substrate on which the first layer has been deposited from the first film formation furnace as a second step A step of transferring to a furnace, and a third step, wherein at least a source gas is decomposed by high-frequency power in a second film-forming furnace, and a second blocking layer comprising at least a non-single-crystal material is formed on the first layer. In this case, the spherical protrusions existing on the surface of the photosensitive member do not appear on the image. As a result, it has become possible to provide an electrophotographic photoreceptor manufacturing method capable of greatly improving image defects.
[0197]
The first film forming furnace used in the first step is a VHF type photoconductor manufacturing apparatus in which high-vacuum film forming is performed, and the second film forming furnace used in the third step is an RF type photoconductor manufacturing apparatus. Further, image defects can be reduced.
[0198]
Further, in the second step, the second layer is laminated after polishing the projections of the spherical projections, and the spherical projections can be made more difficult to appear in the image. Can be reduced.
[0199]
It is even better if the photoreceptor is brought into contact with water between the second step and the third step. Specifically, by performing water cleaning, the adhesion when the surface protective layer is deposited thereafter is improved, and the latitude with respect to film peeling is very wide.
[0200]
Further, by performing the inspection of the photoconductor in the second step as necessary, the subsequent process can be omitted for the photoconductor of poor quality, and the cost can be reduced as a whole.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an example of a spherical protrusion of an electrophotographic photosensitive member.
FIG. 2 is a schematic cross-sectional view showing an example of a spherical protrusion of the electrophotographic photosensitive member of the present invention.
FIG. 3 is a schematic cross-sectional view showing an example of a spherical protrusion of the electrophotographic photosensitive member of the present invention whose surface is polished in the second step.
FIG. 4 is a schematic cross-sectional view showing an example of the electrophotographic photosensitive member of the present invention.
FIG. 5 is a schematic cross-sectional view of an a-Si photosensitive film forming apparatus using RF.
FIG. 6 is a schematic cross-sectional view of an a-Si photosensitive film forming apparatus using VHF.
FIG. 7 is a schematic cross-sectional view of a surface polishing apparatus used in the present invention.
FIG. 8 is a schematic cross-sectional view of a water cleaning apparatus used in the present invention.
FIG. 9 is a schematic cross-sectional view of an example of the electrophotographic apparatus of the present invention.
[Explanation of symbols]
101, 201, 301 Substrate having a conductive surface
102, 202, 302 First layer
103, 203, 303 Spherical protrusion
104, 204, 304 dust
105, 205, 305 Upper blocking layer
106, 206, 306 Boundary of spherical deposit normal accumulation part
401 substrate
402 First layer
403 Second layer
404 Lower blocking layer
405 photoconductive layer
406 Upper blocking layer
407 Surface layer
408 Spherical protrusion
5100, 6100 Film forming apparatus
5110, 6110 Reaction vessel, film forming furnace
5111, 6111 Cathode electrode
5112, 6112 Substrate having a conductive surface
5113, 6113 Substrate heating heater
5114, 6114 Gas introduction pipe
5115, 6115 high frequency matching box
5116, 6116 Gas piping
5117 Leak valve
5118, 6118 Main valve
5119, 6119 Vacuum gauge
5120, 6120 High frequency power supply
5121 Insulating materials
5123 cradle
5200 Gas supply device
5211-5216 Mass Flow Controller
5221-5226 cylinder
5231-5236 Valve
5241-5246 Inflow valve
5251-5256 Outflow valve
5260, 6260 Auxiliary valve
5261-5266 Pressure regulator
6120 rotary motor
6130 Discharge space
700 base
720 Elastic support mechanism
730 Pressure elastic roller
731 Abrasive tape
732 Delivery roll
733 Winding roll
734 Constant delivery roll
735 Capstan Roller
801 Substrate having a conductive surface
802 Processing unit
803 To-be-processed member conveyance mechanism
811 Workpiece input table
821 Cleaning tank to be processed
822 Cleaning solution
831 Pure water contact tank
832 nozzle
841 Drying tank
842 nozzle
851 Untreated table
861 Transfer arm
862 Movement mechanism
863 Chucking Mechanism
864 Air cylinder
865 transport rail
904 Electrophotographic photosensitive member
905 Primary charger
906 Developer
906a Developer (toner)
907 Transfer charger
908 cleaner
908-1 Elastic Roller
908-2 Cleaning blade
909 AC static eliminator
910 Static elimination lamp
913 Transfer material
914 Feed roller
A Image exposure (analog light or digital light)

Claims (24)

In a method for producing an electrophotographic photoreceptor including a layer made of a non-single crystal material,
As a first step, a cylindrical substrate having a conductive surface is installed in a vacuum-tight first film forming furnace equipped with an exhaust means and a source gas supply means, and at least the source gas is decomposed by high-frequency power, Depositing at least a first layer of a non-single crystalline material on the cylindrical substrate;
As a second step, a step of removing the cylindrical substrate on which the first layer is deposited from the first film forming furnace;
As a third step, a cylindrical substrate on which the first layer is deposited is placed in a vacuum-tight second film-forming furnace equipped with an exhaust unit and a source gas supply unit, and at least the source gas is decomposed by high-frequency power. And depositing a second layer including an upper blocking layer made of a non-single crystal material on the first layer. 2. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the first layer is a non-single-crystal material containing at least silicon atoms as a base material and containing hydrogen atoms and / or halogen atoms. 3. The electrophotographic photosensitive material according to claim 1, wherein the upper blocking layer is a non-single crystal material containing at least a silicon atom as a base material and further containing at least one of carbon, oxygen, and nitrogen atoms. Body manufacturing method. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the upper blocking layer is a non-single-crystal material further containing an atom for controlling conductivity. 5. The method for producing an electrophotographic photosensitive member according to claim 4, wherein the atoms controlling the conductivity contained in the upper blocking layer are Group 13 or Group 15 elements of the Periodic Table. The electrophotography according to claim 4 or 5, wherein the content of the Group 13 or Group 15 element in the upper blocking layer is 100 atom ppm or more and 30000 atom ppm or less. A method for producing a photoreceptor. The upper blocking layer has a thickness of 10 ⁻⁴ times or more of the diameter of the largest spherical projection among the spherical projections present on the surface of the electrophotographic photosensitive member after depositing the second layer, and The method for producing an electrophotographic photosensitive member according to claim 1, wherein the upper blocking layer is formed to have a thickness of 1 μm or less. 8. The electrophotographic photosensitive member according to claim 1, wherein in the second step, the cylindrical gas on which the first layer is deposited is once taken out from the film forming furnace while maintaining a vacuum state. Body manufacturing method. 8. The method according to claim 1, wherein in the second step, the cylindrical substrate on which the first layer is deposited is once taken out of the film forming furnace and exposed to a gas containing oxygen and water vapor. A method for producing an electrophotographic photoreceptor. The method for producing an electrophotographic photosensitive member according to claim 9, wherein the gas containing oxygen and water vapor is air. The method of manufacturing an electrophotographic photosensitive member according to claim 1, wherein the third step includes a step of further laminating a surface layer on the upper blocking layer. 12. The electrophotographic photosensitive member according to claim 11, wherein the surface layer is made of a non-single crystal material containing at least silicon atoms as a base material and further containing at least one of carbon, oxygen, and nitrogen atoms. Method. The method of manufacturing an electrophotographic photosensitive member according to claim 1, wherein the first film forming furnace is a plasma CVD method using a VHF band for a high frequency. The method of manufacturing an electrophotographic photosensitive member according to claim 1, wherein the second film forming furnace is a plasma CVD method using an RF band for a high frequency. Depositing at least a first region of the photoconductive layer as the first layer, and then depositing at least a second region of the photoconductive layer and the upper blocking layer as a second layer. The method for producing an electrophotographic photosensitive member according to claim 1. 16. The method for producing an electrophotographic photoreceptor according to claim 1, wherein the second step further includes a step of processing the surface of the first layer. The step of processing the surface of the first layer is a step of removing at least the top of the protrusions present on the surface of the first layer deposited in the first step. Manufacturing method for electrophotographic photoreceptors. 18. The method for producing an electrophotographic photoreceptor according to claim 16, wherein the step of processing the surface of the first layer is a polishing process. 19. The electrophotographic photoreceptor according to claim 18, wherein the polishing process comprises polishing the protrusions on the surface of the first layer deposited in the first step to flatten the surface. Manufacturing method. In the polishing process, a polishing tape is brought into contact with the surface of the first layer deposited in the first step by using an elastic rubber roller, and the first layer surface is rotated together with the cylindrical substrate. 20. The electrophotographic photosensitive member according to claim 18, wherein a relative speed difference is provided between the speed and the rotational movement speed of the elastic rubber roller for contacting the polishing tape. Manufacturing method. 21. The method of manufacturing an electrophotographic photosensitive member according to claim 1, wherein the second step further includes a step of inspecting a photosensitive member in which the first layer is laminated. The electrophotographic photosensitive member according to any one of claims 1 to 21, wherein in the second step, the surface of the first layer is brought into contact with water and washed before proceeding to the third step. Body manufacturing method. An electrophotographic photosensitive member produced by the production method according to claim 1. An electrophotographic apparatus using the electrophotographic photosensitive member according to claim 23.

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