JP3831672B2 - Electrophotographic photosensitive member and electrophotographic apparatus - Google Patents

Description

式中、Ｃｐ_１，Ｃｐ_２はカップラー残基を表し、同一でも異なっていても良い。Ｒ_２０１，Ｒ_２０２はそれぞれ、水素原子、ハロゲン原子、アルキル基、アルコキシ基、シアノ基のいずれかを表し、同一でも異なっていても良い。またＣｐ_１，Ｃｐ_２は下記（II）式で表され、
【化２】

式中、Ｒ_２０３は、水素原子、メチル基、エチル基などのアルキル基、フェニル基などのアリール基を表す。Ｒ_２０４，Ｒ_２０５，Ｒ_２０６，Ｒ_２０７，Ｒ_２０８はそれぞれ、水素原子、ニトロ基、シアノ基、フッ素、塩素、臭素、ヨウ素などのハロゲン原子、トリフルオロメチル基、メチル基、エチル基などのアルキル基、メトキシ基、エトキシ基などのアルコキシ基、ジアルキルアミノ基、水酸基を表し、Ｚは置換もしくは無置換の芳香族炭素環または置換もしくは無置換の芳香族複素環を構成するのに必要な原子群を表す。
【００４５】
特に、前記Ｃｐ_１とＣｐ_２が異なる構造の非対称アゾ顔料は、Ｃｐ_１とＣｐ_２が同一構造である対象型のアゾ顔料よりも、光感度が良好な場合が多く、感光体の小径化、使用プロセスの高速化に対応できるものであり、有効に使用される。また、ブラッグ角２θの回折ピーク（±０．２゜）として２７．２゜に最大回折ピークを有するチタニルフタロシアニンの中でも、最低角として７．３゜にピークを有するチタニルフタロシアニン（特開２００１−１９８７１号公報に記載）が、高感度であり、繰り返し使用における帯電性の低下が小さく、特に有効に使用できる。
【００４６】
電荷発生層４は、必要に応じて結着樹脂とともに適当な溶剤中にボールミル、アトライター、サンドミル、超音波などを用いて分散し、これを導電性支持体上に塗布し、乾燥することにより形成される。
【００４７】
必要に応じて電荷発生層４に用いられる結着樹脂としては、ポリアミド、ポリウレタン、エポキシ樹脂、ポリケトン、ポリカーボネート、シリコーン樹脂、アクリル樹脂、ポリビニルブチラール、ポリビニルホルマール、ポリビニルケトン、ポリスチレン、ポリスルホン、ポリ−Ｎ−ビニルカルバゾール、ポリアクリルアミド、ポリビニルベンザール、ポリエステル、フェノキシ樹脂、塩化ビニル−酢酸ビニル共重合体、ポリ酢酸ビニル、ポリフェニレンオキシド、ポリアミド、ポリビニルピリジン、セルロース系樹脂、カゼイン、ポリビニルアルコール、ポリビニルピロリドン等が挙げられる。結着樹脂の量は、電荷発生物質１００重量部に対し０〜５００重量部、好ましくは１０〜３００重量部が適当である。
【００４８】
ここで用いられる溶剤としては、イソプロパノール、アセトン、メチルエチルケトン、シクロヘキサノン、テトラヒドロフラン、ジオキサン、エチルセルソルブ、酢酸エチル、酢酸メチル、ジクロロメタン、ジクロロエタン、モノクロロベンゼン、シクロヘキサン、トルエン、キシレン、リグロイン等が挙げられるが、特にケトン系溶媒、エステル系溶媒、エーテル系溶媒が良好に使用される。塗布液の塗工法としては、浸漬塗工法、スプレーコート、ビートコート、ノズルコート、スピナーコート、リングコート等の方法を用いることができる。
【００４９】
電荷発生層４の膜厚は、０．０１〜５μｍ程度が適当であり、好ましくは０．１〜２μｍである。
【００５０】
電荷輸送層５は、電荷輸送物質および結着樹脂を適当な溶剤に溶解ないし分散し、これを電荷発生層上に塗布、乾燥することにより形成できる。また、必要により可塑剤、レベリング剤、酸化防止剤等を添加することもできる。
【００５１】
電荷輸送物質には、正孔輸送物質と電子輸送物質とがある。電荷輸送物質としては、例えばクロルアニル、ブロムアニル、テトラシアノエチレン、テトラシアノキノジメタン、２，４，７−トリニトロ−９−フルオレノン、２，４，５，７−テトラニトロ−９−フルオレノン、２，４，５，７−テトラニトロキサントン、２，４，８−トリニトロチオキサントン、２，６，８−トリニトロ−４Ｈ−インデノ〔１，２−ｂ〕チオフェン−４−オン、１，３，７−トリニトロジベンゾチオフェン−５，５−ジオキサイド、ベンゾキノン誘導体等の電子受容性物質が挙げられる。
【００５２】
正孔輸送物質としては、ポリ−Ｎ−ビニルカルバゾールおよびその誘導体、ポリ−γ−カルバゾリルエチルグルタメートおよびその誘導体、ピレン−ホルムアルデヒド縮合物およびその誘導体、ポリビニルピレン、ポリビニルフェナントレン、ポリシラン、オキサゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、モノアリールアミン誘導体、ジアリールアミン誘導体、トリアリールアミン誘導体、スチルベン誘導体、α−フェニルスチルベン誘導体、ベンジジン誘導体、ジアリールメタン誘導体、トリアリールメタン誘導体、９−スチリルアントラセン誘導体、ピラゾリン誘導体、ジビニルベンゼン誘導体、ヒドラゾン誘導体、インデン誘導体、ブタジェン誘導体、ピレン誘導体等、ビススチルベン誘導体、エナミン誘導体等その他公知の材料が挙げられる。これらの電荷輸送物質は単独、または２種以上混合して用いられる。
【００５３】
結着樹脂としては、ポリスチレン、スチレン−アクリロニトリル共重合体、スチレン−ブタジエン共重合体、スチレン−無水マレイン酸共重合体、ポリエステル、ポリ塩化ビニル、塩化ビニル−酢酸ビニル共重合体、ポリ酢酸ビニル、ポリ塩化ビニリデン、ポリアレート、フェノキシ樹脂、ポリカーボネート、酢酸セルロース樹脂、エチルセルロース樹脂、ポリビニルブチラール、ポリビニルホルマール、ポリビニルトルエン、ポリ−Ｎ−ビニルカルバゾール、アクリル樹脂、シリコーン樹脂、エポキシ樹脂、メラミン樹脂、ウレタン樹脂、フェノール樹脂、アルキッド樹脂等の熱可塑性または熱硬化性樹脂が挙げられる。
【００５４】
電荷輸送物質の量は結着樹脂１００重量部に対し、２０〜３００重量部、好ましくは４０〜１５０重量部が適当である。また、電荷輸送層の膜厚は解像度・応答性の点から、２５μｍ以下とすることが好ましい。下限値に関しては、使用するシステム（特に帯電電位等）に異なるが、５μｍ以上が好ましい。
【００５５】
ここで用いられる溶剤としては、テトラヒドロフラン、ジオキサン、トルエン、ジクロロメタン、モノクロロベンゼン、ジクロロエタン、シクロヘキサノン、メチルエチルケトン、アセトンなどが用いられる。
【００５６】
本発明の感光体において電荷輸送層５中に可塑剤やレベリング剤を添加してもよい。可塑剤としては、ジブチルフタレート、ジオクチルフタレートなど一般の樹脂の可塑剤として使用されているものがそのまま使用でき、その使用量は、結着樹脂に対して０〜３０重量％程度が適当である。レベリング剤としては、ジメチルシリコーンオイル、メチルフェニルシリコーンオイルなどのシリコーンオイル類や、側鎖にパーフルオロアルキル基を有するポリマーあるいは、オリゴマーが使用され、その使用量は結着樹脂に対して、０〜１重量％が適当である。
【００５７】
次に単層構成の感光層２の場合について述べる。上述した電荷発生物質を結着樹脂中に分散した感光体が使用できる。単層感光層は、電荷発生物質および電荷輸送物質および結着樹脂を適当な溶剤に溶解ないし分散し、これを塗布、乾燥することによって形成できる。さらに、この感光層には上述した電荷輸送材料を添加した機能分離タイプとしても良く、良好に使用できる。また、必要により、可塑剤やレベリング剤、酸化防止剤等を添加することもできる。
【００５８】
結着樹脂としては、先に電荷輸送層５で挙げた結着樹脂をそのまま用いるほかに、電荷発生層４で挙げた結着樹脂を混合して用いてもよい。もちろん、先に挙げた高分子電荷輸送物質も良好に使用できる。結着樹脂１００重量部に対する電荷発生物質の量は５〜４０重量部が好ましく、電荷輸送物質の量は０〜１９０重量部が好ましくさらに好ましくは５０〜１５０重量部である。単層感光層は、電荷発生物質、結着樹脂を必要ならば電荷輸送物質とともにテトラヒドロフラン、ジオキサン、ジクロロエタン、シクロヘキサン等の溶媒を用いて分散機等で分散した塗工液を、浸漬塗工法やスプレーコート、ビードコートなどで塗工して形成できる。単層感光層の膜厚は、５〜２５μｍ程度が適当である。
【００５９】
本発明の感光体においては、導電性支持体１ と感光層との間に下引き層を設けることができる。下引き層は一般には樹脂を主成分とするが、これらの樹脂はその上に感光層を溶剤で塗布することを考えると、一般の有機溶剤に対して耐溶剤性の高い樹脂であることが望ましい。このような樹脂としては、ポリビニルアルコール、カゼイン、ポリアクリル酸ナトリウム等の水溶性樹脂、共重合ナイロン、メトキシメチル化ナイロン等のアルコール可溶性樹脂、ポリウレタン、メラミン樹脂、フェノール樹脂、アルキッド−メラミン樹脂、エポキシ樹脂等、三次元網目構造を形成する硬化型樹脂等が挙げられる。また、下引き層にはモアレ防止、残留電位の低減等のために酸化チタン、シリカ、アルミナ、酸化ジルコニウム、酸化スズ、酸化インジウム等で例示できる金属酸化物の微粉末顔料を加えてもよい。
【００６０】
これらの下引き層は前述の感光層の如く適当な溶媒、塗工法を用いて形成することができる。更に本発明の下引き層として、シランカップリング剤、チタンカップリング剤、クロムカップリング剤等を使用することもできる。この他、本発明の下引き層には、Ａｌ_２Ｏ_３を陽極酸化にて設けたものや、ポリパラキシリレン（パリレン）等の有機物やＳｉＯ_２、ＳｎＯ_２、ＴｉＯ_２、ＩＴＯ、ＣｅＯ_２等の無機物を真空薄膜作成法にて設けたものも良好に使用できる。このほかにも公知のものを用いることができる。下引き層の膜厚は０〜５μｍが適当である。
【００６１】
本発明の感光体においては、感光層保護の目的で、保護層３が感光層の上に設けられる。保護層３は、比抵抗が異なる２種類のフィラーが含有され、支持体側の層から表面側の層に向かい、全フィラーに対する比抵抗の高いフィラーの割合が順次大きくなるように構成される。或いは、全フィラーに対する比抵抗の高いフィラーの割合が連続的に大きくなるように構成される。これにより、感光体表面の耐摩耗性向上と残留電位低減、透明性、画像ボケの低減の両立を図ることが可能になる。
【００６２】
保護層中のフィラー濃度は使用するフィラー種により、また感光体を使用する電子写真プロセス条件によっても異なるが、保護層の最表層側において全固形分に対するフィラーの比で５０重量％以下、好ましくは３０重量％以下程度が良好である。保護層の最感光層側においては３０重量％以下、好ましくは１０重量％以下程度が良好である。
【００６３】
また、使用するフィラーのうち、比抵抗の大きい方のフィラーの体積平均粒径は、０．１μｍ〜 ２μｍの範囲が良好に使用され、好ましくは０．３μｍ〜１μｍの範囲である。この場合、平均粒径が小さすぎると耐摩耗性が十分に発揮されず、大きすぎると塗膜の表面性が悪くなったり、塗膜そのものが形成できなかったりするからである。尚、本発明におけるフィラーの平均粒径とは、特別な記載のない限り体積平均粒径であり、超遠心式自動粒度分布測定装置：ＣＡＰＡ−７００（堀場製作所製）により求めたものである。この際、累積分布の５０％に相当する粒子径（Ｍｅｄｉａｎ径）として算出されたものである。また、同時に測定される各々の粒子の標準偏差が１μｍ以下であることが重要である。これ以上の標準偏差の値である場合には、粒度分布が広すぎて、本発明の効果が顕著に得られなくなってしまう場合がある。
【００６４】
比抵抗の異なるフィラーの混合割合については、特別な制限はあまりないが、表面層の最外層において、比抵抗の大きいフィラーの割合が全フィラーのうち５０％以上、好ましくは７０％以上存在していることが望ましい。
【００６５】
保護層３に使用される材料としてはＡＢＳ樹脂、ＡＣＳ樹脂、オレフィン−ビニルモノマー共重合体、塩素化ポリエーテル、アリル樹脂、フェノール樹脂、ポリアセタール、ポリアミド、ポリアミドイミド、ポリアクリレート、ポリアリルスルホン、ポリブチレン、ポリブチレンテレフタレート、ポリカーボネート、ポリアリレート、ポリエーテルスルホン、ポリエチレン、ポリエチレンテレフタレート、ポリイミド、アクリル樹脂、ポリメチルベンテン、ポリプロピレン、ポリフェニレンオキシド、ポリスルホン、ポリスチレン、ＡＳ樹脂、ブタジエン−スチレン共重合体、ポリウレタン、ポリ塩化ビニル、ポリ塩化ビニリデン、エポキシ樹脂等の樹脂が挙げられる。中でも、ポリカーボネートもしくはポリアリレートが最も良好に使用できる。
【００６６】
また、感光体の保護層に添加されるフィラー材料のうち、有機性フィラー材料としては、ポリテトラフルオロエチレンのようなフッ素樹脂粉末、シリコーン樹脂粉末、ａ−カーボン粉末等が挙げられ、無機性フィラー材料としては、銅、スズ、アルミニウム、インジウムなどの金属粉末、シリカ、酸化錫、酸化亜鉛、酸化チタン、酸化インジウム、酸化アンチモン、酸化ビスマス、アンチモンをドープした酸化錫、錫をドープした酸化インジウム等の金属酸化物、チタン酸カリウムなどの無機材料が挙げられる。特に、フィラーの硬度の点からは、この中でも無機材料を用いることが有利である。特に、シリカ、酸化チタン、アルミナが有効に使用できる。
【００６７】
また、本発明の構成要件の一つであるフィラーのｐＨも解像度やフィラーの分散性に大きく影響する。その理由の一つとしては、フィラー、特に金属酸化物は製造時に塩酸等が残存することが考えられる。その残存量が多い場合には、画像ボケの発生は避けられず、またそれは残存量によってはフィラーの分散性にも影響を及ぼす場合がある。もう一つの理由としては、フィラー、特に金属酸化物の表面における帯電性の違いによるものである。通常、液体中に分散している粒子はプラスあるいはマイナスに帯電しており、それを電気的に中性に保とうとして反対の電荷を持つイオンが集まり、そこで電気二重層が形成されることによって粒子の分散状態は安定化している。粒子から遠ざかるに従いその電位（ゼータ電位）は徐々に低くなり、粒子から十分に離れて電気的に中性である領域の電位はゼロとなる。従って、ゼータ電位の絶対値の増加によって粒子の反発力が高くなることによって安定性は高くなり、ゼロに近づくに従い凝集しやすく不安定になる。一方、系のｐＨ値によってゼータ電位は大きく変動し、ある ｐＨ値において電位はゼロとなり等電点を持つことになる。従って、系の等電点からできるだけ遠ざけて、ゼータ電位の絶対値を高めることによって分散系の安定化が図られることになる。
【００６８】
本発明の構成においては、フィラーとしては前述の等電点におけるｐＨが、少なくとも５以上を示すものが画像ボケ抑制の点から好ましく、より塩基性を示すフィラーであるほどその効果が高くなる傾向があることが確認された。等電点におけるｐＨが高い塩基性を示すフィラーは、系が酸性であった方がゼータ電位はより高くなることにより、分散性及びその安定性は向上することになる。
【００６９】
ここで、本発明におけるフィラーのｐＨは、ゼータ電位から等電点におけるｐＨ値を記載した。この際、ゼータ電位の測定は、大塚電子（株）製レーザーゼータ電位計にて測定した。
【００７０】
更に、画像ボケが発生しにくいフィラーとしては、電気絶縁性が高いフィラー（比抵抗が１０^１０Ω・ｃｍ以上）が好ましく、フィラーのｐＨが５以上を示すものやフィラーの誘電率が５以上を示すものが特に有効に使用できる。また、ｐＨが５以上のフィラーあるいは誘電率が５以上のフィラーを単独で使用することはもちろん、ｐＨが５以下のフィラーとｐＨが５以上のフィラーとを２種類以上を混合したり、誘電率が５以下のフィラーと誘電率が５以上のフィラーとを２種類以上混合したりして用いることも可能である。また、これらのフィラーの中でも高い絶縁性を有し、熱安定性が高い上に、耐摩耗性が高い六方細密構造であるα型アルミナは、画像ボケの抑制や耐摩耗性の向上の点から特に有用である。
【００７１】
本発明において使用するフィラーの比抵抗は以下のように定義される。フィラーのような粉体は、充填率によりその比抵抗値が異なるので、一定の条件下で測定する必要がある。本発明においては、特開平５−９４０４９号公報（特にその第１図）、及び、特開平５−１１３６８８号公報（特にその第１図）に示された測定装置と同様の構成の装置を用いて、フィラーの比抵抗値を測定し、この値を用いた。測定装置において、電極面積は４．０ｃｍ^２である。測定前に片側の電極に４ｋｇの荷重を１分間かけ、電極間距離が４ｍｍになるように試料量を調節する。測定の際は、上部電極の重量（１ｋｇ）の荷重状態で測定を行い、印加電圧は１００Ｖにて測定する。１０^６Ω・ｃｍ以上の領域は、ＨＩＧＨ ＲＥＳＩＳＴＡＮＣＥ ＭＥＴＥＲ（横河ヒューレットパッカード）、それ以下の領域についてはデジタルマルチメーター（フルーク）により測定した。これにより得られた比抵抗値を本発明の言うところの比抵抗値と定義するものである。
【００７２】
フィラーの誘電率は以下のように測定した。上述のような比抵抗の測定と同様なセルを用い、荷重をかけた後に、静電容量を測定し、これより誘電率を求めた。静電容量の測定は、誘電体損測定器（安藤電気）を使用した。
【００７３】
更に、これらのフィラーは少なくとも一種の表面処理剤で表面処理させることが可能であり、そうすることがフィラーの分散性の面から好ましい。フィラーの分散性の低下は残留電位の上昇だけでなく、塗膜の透明性の低下や塗膜欠陥の発生、さらには耐摩耗性の低下をも引き起こすため、高耐久化あるいは高画質化を妨げる大きな問題に発展する可能性がある。表面処理剤としては、従来用いられている表面処理剤すべてを使用することができるが、フィラーの絶縁性を維持できる表面処理剤が好ましい。例えば、チタネート系カップリング剤、アルミニウム系カップリング剤、ジルコアルミネート系カップリング剤、高級脂肪酸等、あるいはこれらとシランカップリング剤との混合処理や、Ａｌ_２Ｏ_３、ＴｉＯ_２、ＺｒＯ_２、シリコーン、ステアリン酸アルミニウム等、あるいはそれらの混合処理がフィラーの分散性及び画像ボケの点からより好ましい。シランカップリング剤による処理は、画像ボケの影響が強くなるが、上記の表面処理剤とシランカップリング剤との混合処理を施すことによりその影響を抑制できる場合がある。表面処理量については、用いるフィラーの平均一次粒径によって異なるが、３〜３０ｗｔ％が適しており、５〜２０ｗｔ％がより好ましい。表面処理量がこれよりも少ないとフィラーの分散効果が得られず、また多すぎると残留電位の著しい上昇を引き起こす。これらフィラ−材料は単独もしくは２種類以上混合して用いられる。フィラーの表面処理量に関しては、上述のようにフィラー量に対する使用する表面処理剤の重量比で定義される。
【００７４】
尚、保護層の厚さは０．１〜１０μｍ程度が適当である。これらフィラ−材料は、適当な分散機を用いることにより分散できる。また、保護層の透過率の点から使用するフィラーは１次粒子レベルまで分散され、凝集体が少ない方が好ましい。
【００７５】
保護層の形成法としては通常の塗布法が採用される。中でも、スプレー工法は有効な手段であり、最適な方法としては次の方法が挙げられる。１つは複数のフィラー比率の異なる保護層用塗工液を、下層が乾かないうちに順次スプレー法で積層していく方法である。この場合、塗工液の数だけスプレーヘッドを用意し、塗工を連続的に行うことが望ましい。別の１つは複数のフィラー比率の異なる保護層用塗工液を、下層の指触乾燥が終了したら順次スプレー法で積層していく方法である。この場合、塗工液の数だけスプレーヘッドを用意し、塗工を連続的に行うことが望ましい。さらに別の方法は、使用するフィラーの数だけスプレーヘッドを用意し、各々フィラー単独の分散液を作製し、感光層側から保護側に向かい、それぞれの吐出量を変化させ、各々のフィラーの存在比率分布を設ける方法が挙げられる。
【００７６】
また、保護層３には残留電位低減、応答性改良のため、電荷輸送物質を含有しても良い。電荷輸送物質は、電荷輸送層の説明のところに記載した材料を用いることができる。電荷輸送物質として、低分子電荷輸送物質を用いる場合には、保護層中における濃度傾斜を設けても構わない。耐摩耗性向上のため、表面側を低濃度にすることは有効な手段である。ここで言う濃度とは、保護層を構成する全材料の総重量に対する低分子電荷輸送物質の重量の比を表し、濃度傾斜とは上記重量比において表面側において濃度が低くなるような傾斜を設けることを示す。
【００７７】
また、保護層には電荷輸送物質としての機能とバインダー樹脂の機能を持った高分子電荷輸送物質も良好に使用される。これら高分子電荷輸送物質から構成される保護層は耐摩耗性に優れたものである。高分子電荷輸送物質としては、公知の材料が使用できるが、特に、トリアリールアミン構造を主鎖および／または側鎖に含むポリカーボネートが良好に用いられる。中でも、（ＩＩＩ）〜（ＸＩＩ）式で表される高分子電荷輸送物質が良好に用いられ、これらを以下に例示し、具体例を示す。
【００７８】
（ＩＩＩ）式
【化３】

式中、Ｒ_１，Ｒ_２，Ｒ_３はそれぞれ独立して置換もしくは無置換のアルキル基又はハロゲン原子、Ｒ_４は水素原子又は置換もしくは無置換のアルキル基、Ｒ_５，Ｒ_６は置換もしくは無置換のアリール基、ｏ，ｐ，ｑはそれぞれ独立して０〜４の整数、ｋ，ｊは組成を表し、０．１≦ｋ≦１、０≦ｊ≦０．９、ｎは繰り返し単位数を表し５〜５０００の整数である。Ｘは脂肪族の２価基、環状脂肪族の２価基、または下記一般式で表される２価基を表す。
【化４】

式中、Ｒ_１０１，Ｒ_１０２は各々独立して置換もしくは無置換のアルキル基、アリール基またはハロゲン原子を表す。ｌ、ｍは０〜４の整数、Ｙは単結合、炭素原子数１〜１２の直鎖状、分岐状もしくは環状のアルキレン基、−Ｏ−，−Ｓ−，−ＳＯ−，−ＳＯ_２−，−ＣＯ−，−ＣＯ−Ｏ−Ｚ−Ｏ−ＣＯ−（式中Ｚは脂肪族の２価基を表す。）または、
【化５】

（式中、ａ は１〜２０の整数、ｂは１〜２０００の整数、Ｒ_１０３、Ｒ_１０４は置換または無置換のアルキル基又はアリール基を表す。）を表す。ここで、Ｒ_１０１とＲ_１０２，Ｒ_１０３とＲ_１０４は、それぞれ同一でも異なってもよい。
【００７９】
（IV）式
【化６】

式中、Ｒ_７、Ｒ_８は置換もしくは無置換のアリール基、Ａｒ_１、Ａｒ_２、Ａｒ_３は同一又は異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、（III）式の場合と同じである。
【００８０】
（Ｖ）式
【化７】

式中、Ｒ_９、Ｒ_１０は置換もしくは無置換のアリール基、Ａｒ_４，Ａｒ_５，Ａｒ_６は同一又は異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、（III）式の場合と同じである。
【００８１】
（VI）式
【化８】

式中、Ｒ_１１、Ｒ_１２は置換もしくは無置換のアリール基、Ａｒ_７、Ａｒ_８、Ａｒ_９は同一又は異なるアリレン基、ｐは１〜５の整数を表す。Ｘ，ｋ，ｊおよびｎは、（III）式の場合と同じである。
【００８２】
（VII）式
【化９】

式中、Ｒ_１３，Ｒ_１４は置換もしくは無置換のアリール基、Ａｒ_１０，Ａｒ_１１，Ａｒ_１２は同一又は異なるアリレン基、Ｘ_１，Ｘ_２は置換もしくは無置換のエチレン基、又は置換もしくは無置換のビニレン基を表す。Ｘ，ｋ，ｊおよびｎは、（III）式の場合と同じである。
【００８３】
（VIII）式
【化１０】

式中、Ｒ_１５，Ｒ_１６，Ｒ_１７，Ｒ_１８は置換もしくは無置換のアリール基、Ａｒ_１３，Ａｒ_１４，Ａｒ_１５，Ａｒ_１６は同一又は異なるアリレン基、Ｙ_１，Ｙ_２，Ｙ_３は単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル基、酸素原子、硫黄原子、ビニレン基を表し同一であっても異なってもよい。Ｘ，ｋ，ｊおよびｎは、（III）式の場合と同じである。
【００８４】
（ＩＸ）式
【化１１】

式中、Ｒ_１９，Ｒ_２０は水素原子、置換もしくは無置換のアリール基を表し，Ｒ_１９とＲ_２０は環を形成していてもよい。Ａｒ_１７，Ａｒ_１８，Ａｒ_１９は同一又は異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、（III）式の場合と同じである。
【００８５】
（Ｘ）式
【化１２】

式中、Ｒ_２１は置換もしくは無置換のアリール基、Ａｒ_２０，Ａｒ_２１，Ａｒ_２２，Ａｒ_２３は同一又は異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、（III）式の場合と同じである。
【００８６】
（ＸＩ）式
【化１３】

式中、Ｒ_２２，Ｒ_２３，Ｒ_２４，Ｒ_２５は置換もしくは無置換のアリール基、Ａｒ_２４，Ａｒ_２５，Ａｒ_２６，Ａｒ_２７，Ａｒ_２８は同一又は異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、（III）式の場合と同じである。
【００８７】
（XII）式
【化１４】

式中、Ｒ_２６，Ｒ_２７は置換もしくは無置換のアリール基、Ａｒ_２９，Ａｒ_３０，Ａｒ_３１は同一又は異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、（III）式の場合と同じである。
【００８８】
また、保護層に使用される高分子電荷輸送物質として、上述の高分子電荷輸送物質の他に、保護層の成膜時には電子供与性基を有するモノマーあるいはオリゴマーの状態で、成膜後に硬化反応あるいは架橋反応をさせることで、最終的に２次元あるいは３次元の架橋構造を有する重合体も含むものである。
【００８９】
これら電子供与性基を有する重合体から構成される保護層、あるいは架橋構造を有する重合体は耐摩耗性に優れたものである。通常、電子写真プロセスにおいては、帯電電位（未露光部電位）は一定であるため、繰り返し使用により感光体の表面層が摩耗すると、その分だけ感光体にかかる電界強度が高くなってしまう。この電界強度の上昇に伴い、地汚れの発生頻度が高くなるため、感光体の耐摩耗性が高いことは、地汚れに対して有利である。これら電子供与性基を有する重合体から構成される保護層は、自身が高分子化合物であるため成膜性に優れ、低分子分散型高分子からなる保護層に比べ、電荷輸送部位を高密度に構成することが可能で電荷輸送能に優れたものである。このため、高分子電荷輸送物質を用いた保護層を有する感光体には高速応答性が期待できる。
【００９０】
その他の電子供与性基を有する重合体としては、公知単量体の共重合体や、ブロック重合体、グラフト重合体、スターポリマーや、また、例えば特開平３−１０９４０６号公報、特開２００００−２０６７２３号公報、特開２００１−３４００１号公報等に開示されているような電子供与性基を有する架橋重合体などを用いることも可能である。
【００９１】
本発明の感光体においては感光層と保護層との間に中間層を設けることも可能である中間層には、一般にバインダー樹脂を主成分として用いる。これら樹脂としては、ポリアミド、アルコール可溶性ナイロン、水溶性ポリビニルブチラール、ポリビニルブチラール、ポリビニルアルコールなどが挙げられる。中間層の形成法としては、前述のごとく通常の塗布法が採用される。なお、中間層の厚さは０．０５〜２μｍ程度が適当である。
【００９２】
また、本発明においては、耐環境性の改善のため、とりわけ、感度低下、残留電位の上昇を防止する目的で、各層に酸化防止剤、可塑剤、滑剤、紫外線吸収剤、低分子電荷輸送物質およびレベリング剤を添加することが出来る。これらの化合物の代表的な材料を以下に記す。
【００９３】
各層に添加できる酸化防止剤として、例えば、フェノ−ル系化合物、パラフェニレンジアミン類、ハイドロキノン類、有機硫黄化合物類、有機燐化合物類などが挙げられる。
【００９４】
各層に添加できる可塑剤として、リン酸エステル系可塑剤、フタル酸エステル系可塑剤、芳香族カルボン酸エステル系可塑剤、脂肪族二塩基酸エステル系可塑剤、脂肪酸エステル誘導体、オキシ酸エステル系可塑剤、エポキシ可塑剤、二価アルコールエステル系可塑剤、含塩素可塑剤、ポリエステル系可塑剤、スルホン酸誘導体、クエン酸誘導体、ターフェニル、部分水添ターフェニル、ショウノウ、２−ニトロジフェニル、ジノニルナフタリン、アビエチン酸メチルなどが挙げられる。
【００９５】
各層に添加できる滑剤としては、例えば、炭化水素系化合物、脂肪酸系化合物、脂肪酸アミド系化合物、エステル系化合物、アルコール系化合物、金属石けん、天然ワックス、シリコーン化合物、フッ素化合物などが挙げられる。
【００９６】
各層に添加できる紫外線吸収剤として、例えば、ベンゾフェノン系、サルシレート系、ベンゾトリアゾール系、シアノアクリレート系、クエンチャー（金属錯塩系）、ＨＡＬＳ （ヒンダードアミン）の各化合物が挙げられる。
【００９７】
次に図面を用いて本発明の電子写真方法ならびに電子写真装置を詳しく説明する。第５図は、本発明の電子写真プロセスおよび電子写真装置を説明するための概略図であり、下記するような変形例も本発明の範疇に属するものである。
【００９８】
第５図において、感光体６は導電性支持体上に、少なくとも感光層と比抵抗の異なる２種類のフィラーの混合比率の異なる複数層の保護層が設けられてなる。或いは、感光体１は導電性支持体上に、少なくとも感光層と比抵抗の異なるフィラーの混合比率傾斜を持った保護層が設けられてなる。感光体６はドラム状の形状を示しているが、シート状、エンドレスベルト状のものであっても良い。帯電部材８、転写前チャージャー１２、クリーニング前チャージャー１７には、コロトロン、スコロトロン、固体帯電器（ソリッド・ステート・チャージャー）、帯電ローラーを始めとする公知の手段が用いられる。帯電部材は、感光体に対し接触もしくは近接配置したものが良好に用いられる。
【００９９】
ここでいう接触方式の帯電部材とは、感光体表面に帯電部材の表面が接触するタイプのものであり、帯電ローラー、帯電ブレード、帯電ブラシの形状がある。中でも帯電ローラーや帯電ブラシが良好に使用される。
【０１００】
また、近接配置した帯電部材とは、感光体表面と帯電部材表面の間に２００μｍ以下の空隙（ギャップ）を有するように非接触状態で近接配置したタイプのものである。空隙の距離から、コロトロン、スコロトロンに代表される公知の帯電器とは区別されるものである。本発明において使用される近接配置された帯電部材は、感光体表面との空隙を適切に制御できる機構のものであればいかなる形状のものでも良い。例えば、感光体の回転軸と帯電部材の回転軸を機械的に固定して、適正ギャップを有するような配置にすればよい。中でも、帯電ローラーの形状の帯電部材を用い、帯電部材の非画像形成部両端にギャップ形成部材を配置して、この部分のみを感光体表面に当接させ、画像形成領域を非接触配置させる、あるいは感光体非画像形成部両端ギャップ形成部材を配置して、この部分のみを帯電部材表面に当接させ、画像形成領域を非接触配置させる様な方法が、簡便な方法でギャップを安定して維持できる方法である。特に特願平１３−２１１４４８号、特願平１３−２２６４３２号に記載された方法は良好に使用できる。帯電部材側にギャップ形成部材を配置した近接帯電機構の一例を第９図に示す。
【０１０１】
また、帯電用部材により感光体に帯電を施す際、帯電部材に直流成分に交流成分を重畳した電界により感光体に帯電を与えることにより、帯電ムラを低減することが可能で効果的である。
【０１０２】
転写手段には、一般に上記の帯電器が使用できるが、転写チャージャーと分離チャージャーを併用したものが効果的である。また、画像露光部１０、除電ランプ７等の光源には、蛍光灯、タングステンランプ、ハロゲンランプ、水銀灯、ナトリウム灯、発光ダイオード（ＬＥＤ）、半導体レーザー（ＬＤ）、エレクトロルミネッセンス（ＥＬ）などの発光物全般を用いることができる。そして、所望の波長域の光のみを照射するために、シャープカットフィルター、バンドパスフィルター、近赤外カットフィルター、ダイクロイックフィルター、干渉フィルター、色温度変換フィルターなどの各種フィルターを用いることもできる。
【０１０３】
かかる光源等は、第５図に示される工程の他に光照射を併用した転写工程、除電工程、クリーニング工程、あるいは前露光などの工程を設けることにより、感光体に光が照射される。
【０１０４】
さて、現像ユニット１１により感光体６上に現像されたトナーは、転写紙１４に転写されるが、全部が転写されるわけではなく、感光体６上に残存するトナーも生ずる。このようなトナーは、ファーブラシ１８およびブレードにより、感光体より除去される。クリーニングは、クリーニングブラシだけで行なわれることもあり、クリーニングブラシにはファーブラシ、マグファーブラシを始めとする公知のものが用いられる。
【０１０５】
電子写真感光体に正（負）帯電を施し、画像露光を行なうと、感光体表面上には正（負）の静電潜像が形成される。これを負（正）極性のトナー（検電微粒子）で現像すれば、ポジ画像が得られるし、また正（負）極性のトナーで現像すれば、ネガ画像が得られる。かかる現像手段には、公知の方法が適用されるし、また、除電手段にも公知の方法が用いられる。
【０１０６】
第６図には、本発明による電子写真プロセスの別の例を示す。感光体２１は導電性支持体上に、少なくとも感光層と少なくとも感光層と比抵抗の異なる２種類のフィラーの混合比率の異なる複数層の保護層、或いは比抵抗の異なるフィラーの混合比率傾斜を持った保護層が設けられてなる。駆動ローラー２２ａ，２２ｂにより駆動され、帯電ローラー（帯電器）２３による帯電、光源２４による像露光、現像（図示せず）、転写チャージャー（帯電器）２５を用いる転写、光源２６によるクリーニング前露光、ブラシ２７によるクリーニング、光源２８による除電が繰返し行なわれる。第６図においては、感光体２１（勿論この場合は支持体が透光性である）に支持体側よりクリーニング前露光の光照射が行なわれる。
【０１０７】
以上の図示した電子写真プロセスは、本発明における実施形態を例示するものであって、もちろん他の実施形態も可能である。例えば、第６図において支持体側よりクリーニング前露光を行っているが、これは感光層側から行ってもよいし、また、像露光、除電光の照射を支持体側から行ってもよい。一方、光照射工程は、像露光、クリーニング前露光、除電露光が図示されているが、他に転写前露光、像露光のプレ露光、およびその他公知の光照射工程を設けて、感光体に光照射を行なうこともできる。
【０１０８】
以上に示すような画像形成手段は、複写装置、ファクシミリ、プリンター内に固定して組み込まれていてもよいが、プロセスカートリッジの形でそれら装置内に組み込まれてもよい。プロセスカートリッジとは、感光体を内蔵し、他に帯電手段、露光手段、現像手段、転写手段、クリーニング手段、除電手段を含んだ１つの装置（部品）である。プロセスカートリッジの形状等は多く挙げられるが、一般的な例として、第７図に示すものが挙げられる。ここで内蔵される感光体33は、導電性支持体上に、少なくとも感光層と少なくとも感光層と比抵抗の異なる２種類のフィラーの混合比率の異なる複数層の保護層或いは比抵抗の異なるフィラーの混合比率傾斜を持った保護層が設けられてなるものである。
【０１０９】
第１０図は、本発明のタンデム方式のフルカラー電子写真装置を説明するための概略図であり、下記するような変形例も本発明の範疇に属するものである。第１０図において、符号１０１Ｃ，１０１Ｍ，１０１Ｙ，１０１Ｋはドラム状の感光体であり、この感光体１０１Ｃ，１０１Ｍ，１０１Ｙ，１０１Ｋは図中の矢印方向に回転し、その周りに少なくとも回転順に帯電部材１０２Ｃ，１０２Ｍ，１０２Ｙ，１０２Ｋ、現像部材１０４Ｃ，１０４Ｍ，１０４Ｙ，１０４Ｋ、クリーニング部材１０５Ｃ，１０５Ｍ，１０５Ｙ，１０５Ｋが配置されている。帯電部材１０２Ｃ，１０２Ｍ，１０２Ｙ，１０２Ｋは、感光体表面を均一に帯電するための帯電装置を構成する帯電部材である。この帯電部材１０２Ｃ，１０２Ｍ，１０２Ｙ，１０２Ｋと現像部材１０４Ｃ，１０４Ｍ，１０４Ｙ，１０４Ｋの間の感光体表面に図示しない露光部材からのレーザー光１０３Ｃ，１０３Ｍ，１０３Ｙ，１０３Ｋが照射され、感光体１０１Ｃ，１０１Ｍ，１０１Ｙ，１０１Ｋに静電潜像が形成されるようになっている。そして、このような感光体１０１Ｃ，１０１Ｍ，１０１Ｙ，１０１Ｋを中心とした４つの画像形成要素１０６Ｃ，１０６Ｍ，１０６Ｙ，１０６Ｋが、転写材搬送手段である転写搬送ベルト１１０に沿って並置されている。転写搬送ベルト１１０は各画像形成ユニット１０６Ｃ，１０６Ｍ，１０６Ｙ，１０６Ｋの現像部材１０４Ｃ，１０４Ｍ，１０４Ｙ，１０４Ｋとクリーニング部材１０５Ｃ，１０５Ｍ，１０５Ｙ，１０５Ｋの間で感光体１０１Ｃ，１０１Ｍ，１０１Ｙ，１０１Ｋに当接しており、転写搬送ベルト１１０の感光体側の裏側に当たる面（裏面）には転写バイアスを印加するための転写ブラシ１１１Ｃ，１１１Ｍ，１１１Ｙ，１１１Ｋが配置されている。各画像形成要素１０６Ｃ，１０６Ｍ，１０６Ｙ，１０６Ｋは現像装置内部のトナーの色が異なるのと、本発明に係わる黒色トナー像形成用帯電部材１０２ＫにＤＣ成分のみを印可し、黒色以外のトナー像用帯電部材１０２Ｃ、１０２Ｍ、１０２ＹにＤＣ成分にＡＣ成分を重畳した交番電界を印可するものであり、その他は全て同様の構成となっている。
【０１１０】
第１０図に示す構成のカラー電子写真装置において、画像形成動作は次のようにして行われる。まず、各画像形成要素１０６Ｃ，１０６Ｍ，１０６Ｙ，１０６Ｋにおいて、感光体１０１Ｃ，１０１Ｍ，１０１Ｙ，１０１Ｋが矢印方向（感光体と連れ周り方向）に回転する帯電部材１０２Ｃ，１０２Ｍ，１０２Ｙ，１０２Ｋにより帯電され、次に露光部でレーザー光１０３Ｃ，１０３Ｍ，１０３Ｙ，１０３Ｋにより、作成する各色の画像に対応した静電潜像が形成される。次に現像部材１０４Ｃ，１０４Ｍ，１０４Ｙ，１０４Ｋにより潜像を現像してトナー像が形成される。現像部材１０４Ｃ，１０４Ｍ，１０４Ｙ，１０４Ｋは、それぞれＣ（シアン），Ｍ（マゼンタ），Ｙ（イエロー），Ｋ（ブラック）のトナーで現像を行う現像部材で、４つの感光体１０１Ｃ，１０１Ｍ，１０１Ｙ，１０１Ｋ上で作られた各色のトナー像は転写紙上で重ねられる。転写紙１０７は給紙コロ１０８によりトレイから送り出され、一対のレジストローラ１０９で一旦停止し、上記感光体上への画像形成とタイミングを合わせて転写搬送ベルト１１０に送られる。転写搬送ベルト１１０上に保持された転写紙１０７は搬送されて、各感光体１０１Ｃ，１０１Ｍ，１０１Ｙ，１０１Ｋとの当接位置（転写部）で各色トナー像の転写が行われる。感光体上のトナー像は、転写ブラシ１１１Ｃ，１１１Ｍ，１１１Ｙ，１１１Ｋに印加された転写バイアスと感光体１０１Ｃ，１０１Ｍ，１０１Ｙ，１０１Ｋとの電位差から形成される電界により、転写紙１０７上に転写される。そして４つの転写部を通過して４色のトナー像が重ねられた転写紙１０７は定着装置１１２に搬送され、トナーが定着されて、図示しない排紙部に排紙される。また、転写部で転写されずに各感光体１０１Ｃ，１０１Ｍ，１０１Ｙ，１０１Ｋ上に残った残留トナーは、クリーニング装置１０５Ｃ，１０５Ｍ，１０５Ｙ，１０５Ｋで回収される。尚、第１図の例では画像形成要素は転写紙搬送方向上流側から下流側に向けてＣ（シアン），Ｍ（マゼンタ），Ｙ（イエロー），Ｋ（ブラック）の色の順で並んでいるが、この順番に限るものでは無く、色順は任意に設定されるものである。また、黒色のみの原稿を作成する際には、黒色以外の画像形成要素（１０６Ｃ，１０６Ｍ，１０６Ｙ）が停止するような機構を設けることは本発明に特に有効に利用できる。更に、図１０において帯電部材は感光体と当接しているが、両者の間に適当なギャップ（１０〜２００μｍ程度）を設けてやることにより、両者の摩耗量が低減できると共に、帯電部材へのトナーフィルミングが少なくて済み良好に使用できる。
【０１１１】
以上に示すような画像形成手段は、複写装置、ファクシミリ、プリンター内に固定して組み込まれていてもよいが、各々の電子写真要素はプロセスカートリッジの形でそれら装置内に組み込まれてもよい。プロセスカートリッジとは、感光体を内蔵し、他に帯電手段、露光手段、現像手段、転写手段、クリーニング手段、除電手段等を含んだ１つの装置（部品）である。
【０１１２】
【実施例】
以下、本発明を実施例を挙げて説明するが、本発明が実施例により制約を受けるものではない。なお、部はすべて重量部である。
【０１１３】
実施例１
アルミニウムシリンダー上に下記組成の下引き層塗工液、電荷発生層塗工液、および電荷輸送層塗工液を、順次塗布・乾燥し、３．５μｍの下引き層、０．２μｍの電荷発生層、２０μｍの電荷輸送層、５μｍの保護層からなる電子写真感光体を形成した。尚、下引き層、電荷発生層、電荷輸送層は浸漬塗工法で塗工し、保護層はスプレー法にて塗工を行った。
◎下引き層塗工液
二酸化チタン粉末 ４００部
メラミン樹脂 ６５部
アルキッド樹脂 １２０部
２−ブタノン ４００部
◎電荷発生層塗工液
下記構造のビスアゾ顔料 １２部
【化１５】

ポリビニルブチラール ５部
２−ブタノン ２００部
シクロヘキサノン ４００部
◎電荷輸送層塗工液
Ａ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ８部
【化１６】

テトラヒドロフラン ２００部
◎保護層塗工液１
Ｃ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ７部
【化１７】

酸化錫粉末
（比抵抗：１０^６Ω・ｃｍ、平均一次粒径：０．２μｍ） ５部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液２
Ｃ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ７部
【化１８】

酸化錫粉末（比抵抗：１０^６Ω・ｃｍ、平均一次粒径：０．２μｍ） ３部
アルミナ微粒子（比抵抗：２．５ｘ１０^１２Ω・ｃｍ、平均一次粒径：０．４μ
ｍ） ２部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液３
Ｃ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ７部
【化１９】

アルミナ微粒子
（比抵抗：２．５ｘ１０^１２Ω・ｃｍ、平均一次粒径：０．４ μｍ） ５部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
【０１１４】
上記保護層塗工液は、保護層塗工液１、２、３の順に３つのスプレーヘッドを用い、スプレー法により連続的に塗工した。この際連続的とは、下層を塗工後、指触乾燥しないうちに次の塗工液をスプレー法により積層する事を指す。尚、保護層塗工液１、２は２μｍ相当ずつ塗工し、保護層塗工液３は１μｍ相当塗工し、合計５μｍの保護層を形成した。
【０１１５】
実施例２
実施例１における保護層塗工液１、２、３をそれぞれ以下の組成のものに変更した以外は、実施例１と同様に感光体を作製した。
◎保護層塗工液１
下記構造式の高分子電荷輸送物質 ７部
【化２０】

酸化錫粉末（比抵抗：１０^６Ω・ｃｍ、平均一次粒径：０．２μｍ） ２部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液２
下記構造式の高分子電荷輸送物質 ７部
【化２１】

酸化錫粉末（比抵抗：１０^６Ω・ｃｍ、平均一次粒径：０．２μｍ） １部
アルミナ微粒子（比抵抗：２．５ｘ１０^１２Ω・ｃｍ、平均一次粒径：０．４μ
ｍ） １部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液３
下記構造式の高分子電荷輸送物質 ７部
【化２２】

アルミナ微粒子（比抵抗：２．５ｘ１０^１２Ω・ｃｍ、平均一次粒径：０．４μ
ｍ） ２部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
【０１１６】
比較例１
実施例１における保護層を保護層塗工液１のみを用い、５μｍの保護層を形成した以外は、実施例１と全く同様に感光体を作製した。
【０１１７】
比較例２
実施例１における保護層を保護層塗工液２のみを用い、５μｍの保護層を形成した以外は、実施例１と全く同様に感光体を作製した。
【０１１８】
比較例３
実施例１における保護層を保護層塗工液３のみを用い、５μｍの保護層を形成した以外は、実施例１と全く同様に感光体を作製した。
【０１１９】
比較例４
実施例２における保護層を保護層塗工液１のみを用い、５μｍの保護層を形成した以外は、実施例２と全く同様に感光体を作製した。
【０１２０】
比較例５
実施例２における保護層を保護層塗工液２のみを用い、５μｍの保護層を形成した以外は、実施例２と全く同様に感光体を作製した。
【０１２１】
比較例６
実施例２における保護層を保護層塗工液３のみを用い、５μｍの保護層を形成した以外は、実施例２と全く同様に感光体を作製した。
【０１２２】
試験例１
以上のように作製した実施例１、２および比較例１〜６の感光体を第５図に示す電子写真プロセス（ただし、クリーニング前露光は無し、帯電部材はスコロトロン方式チャージャー）に装着し、画像露光光源を６５５ｎｍの半導体レーザー（ポリゴン・ミラーによる画像書き込み）として、連続して２万枚の印刷を行い、その時の画像を初期と２万枚後に評価した。更に、２万枚おける感光体表面の摩耗量も併せて測定した。以上の結果は、表１に併せて示す。
【表１】

【０１２３】
実施例３
実施例１で使用した第３図に示す電子写真プロセスの帯電部材をスコロトロン・チャージャーから帯電ローラーに変更し、帯電ローラーが感光体に接触するように配置した。この装置に実施例１で作製した感光体を搭載し、下記の帯電条件で、実施例１と同様の評価を行った。
帯電条件：ＤＣ バイアス：−８００Ｖ
【０１２４】
初期及び２万枚目の画像はいずれも良好であったが、２万枚後の画像には帯電ローラー汚れ（トナーフィルミング）に基づく、ごく僅かな異常画像（地汚れ）が認められた。しかしながら、連続プリント時のオゾン臭は実施例１の場合に比べて、格段に少なかった。
【０１２５】
実施例４
実施例３で使用した帯電ローラーの両端部に厚さ５０μｍ、幅５ｍｍの絶縁テープを張り付け、帯電ローラー表面と感光体表面との間に空間的なギャップ（５０μｍ）を有するように配置した。その他の条件は実施例３と全く同様に評価を行った。その結果、実施例３で認められた帯電ローラー汚れは、全く認められず、初期及び２万枚目の画像はいずれも良好であった。しかしながら、２万枚後にハーフトーン画像を出力した際、ごく僅かではあるが、帯電ムラに基づく画像ムラが認められた。
【０１２６】
実施例５
実施例４の評価において、帯電条件を以下のように変更した以外は実施例４と同様の評価を行った。
帯電条件：ＤＣバイアス：−８００Ｖ
ＡＣバイアス：１．６ｋＶ（ｐｅａｋ ｔｏ ｐｅａｋ）、周波数１．６ｋＨｚ
【０１２７】
初期及び２万枚後の画像は良好であった。実施例３で認められた帯電ローラー汚れ、実施例４で認められたハーフトーン画像ムラは、全く認められなかった。
【０１２８】
実施例６
ニッケルベルト上に下記組成の下引き層塗工液、電荷発生層塗工液、および電荷輸送層塗工液を、順次塗布・乾燥し、３μｍの下引き層、０．３μｍの電荷発生層、２２μｍの電荷輸送層、３μｍの保護層からなる電子写真感光体を形成した。尚、下引き層、電荷発生層、電荷輸送層は浸漬塗工法で塗工し、保護層はスプレー法にて塗工を行った。
◎下引き層塗工液
二酸化チタン粉末 １００部
アルコール可溶性ナイロン １００部
メタノール ５００部
ブタノール ３００部
◎電荷発生層塗工液
下記構造のビスアゾ顔料 １０部
【化２３】

ポリビニルブチラール ２部
２−ブタノン ２００部
シクロヘキサノン ４００部
◎電荷輸送層塗工液
Ｚ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ７部
【化２４】

テトラヒドロフラン ２００部
◎保護層塗工液１
Ｚ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ６部
【化２５】

酸化錫−酸化アンチモン粉末
（比抵抗：１０^６Ω・ｃｍ、平均１次粒径０．４μｍ） ５部
トルエン ６００部
◎保護層塗工液２
Ｚ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ６部
【化２６】

酸化錫−酸化アンチモン粉末
（比抵抗：１０^６Ω・ｃｍ、平均１次粒径０．４μｍ） ３部
酸化チタン微粒子（比抵抗：１．５ｘ１０^１０Ω・ｃｍ、平均一次粒径：０．６
μｍ） ２部
トルエン ６００部
◎保護層塗工液３
Ｚ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ６部
【化２７】

酸化チタン微粒子（比抵抗：１．５ｘ１０^１０Ω・ｃｍ、平均一次粒径：０．６
μｍ） ５部
トルエン ６００部
【０１２９】
上記保護層塗工液は、保護層塗工液１、２、３の順にスプレー法により連続的に塗工した。この際連続的とは、下層を塗工後、指触乾燥しないうちに次の塗工液をスプレー法により積層する事を指す。尚、保護層塗工液１、２、３は１μｍ相当ずつ塗工し、合計３μｍの保護層を形成した。
【０１３０】
実施例７
実施例６における保護層塗工液１、２、３をそれぞれ以下の組成のものに変更した以外は、実施例６と同様に感光体を作製した。
◎保護層塗工液１
下記構造式の高分子電荷輸送物質 ７部
【化２８】

酸化錫−酸化アンチモン粉末（比抵抗：１０^６Ω・ｃｍ、平均１次粒径：０．６
μｍ） ２．５部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液２
下記構造式の高分子電荷輸送物質 ７部
【化２９】

酸化錫−酸化アンチモン粉末
（比抵抗：１０^６Ω・ｃｍ、平均１次粒径０．６μｍ） １．５部
シリカ微粒子（比抵抗：４ｘ１０^１３Ω・ｃｍ、平均一次粒径：０．５μｍ） １部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液３
下記構造式の高分子電荷輸送物質 ７部
【化３０】

シリカ微粒子（比抵抗：４ｘ１０^１３Ω・ｃｍ、平均一次粒径：０．５μｍ） ２．５部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
【０１３１】
比較例７
実施例６における保護層を保護層塗工液１のみを用い、３μｍの保護層を形成した以外は、実施例６と全く同様に感光体を作製した。
【０１３２】
比較例８
実施例６における保護層を保護層塗工液２のみを用い、３μｍの保護層を形成した以外は、実施例６と全く同様に感光体を作製した。
【０１３３】
比較例９
実施例６における保護層を保護層塗工液３のみを用い、３μｍの保護層を形成した以外は、実施例６と全く同様に感光体を作製した。
【０１３４】
比較例１０
実施例６における保護層を積層せず、電荷輸送層を２５μｍとした以外は、実施例６と同様に感光体を作製した。
【０１３５】
比較例１１
実施例７における保護層を保護層塗工液１のみを用い、３μｍの保護層を形成した以外は、実施例７と全く同様に感光体を作製した。
【０１３６】
比較例１２
実施例７における保護層を保護層塗工液２のみを用い、３μｍの保護層を形成した以外は、実施例７と全く同様に感光体を作製した。
【０１３７】
比較例１３
実施例７における保護層を保護層塗工液３のみを用い、３μｍの保護層を形成した以外は、実施例７と全く同様に感光体を作製した。
【０１３８】
試験例２
以上のように作製した実施例６、７および比較例７〜１３の感光体を第６図に示す電子写真プロセス（ただし、クリーニング前露光は無し）に装着し、画像露光光源を６５５ｎｍのＬＥＤとして、連続して３万枚の印刷を行い、その時の画像を初期と３万枚後に評価した。更に、３万枚おける感光体表面の摩耗量も併せて測定した。以上の結果は、表２に併せて示す。
【表２】

【０１３９】
実施例８
実施例６に使用したフィラーに処理量が２０％になるようにチタネート系カップリング剤による表面処理を行った。このフィラーを用いて、実施例６における保護層塗工液１、２、３を作製した。これらについて、塗工液中の平均粒径（堀場製作所：ＣＡＰＡ７００で測定）、塗工液の沈降性（試験管内で静置した塗工液粒子の沈降度合いを肉眼で確認）について評価した。結果を表３に示す。尚、表３に示される値は、それぞれの保護層塗工液３の測定結果である。
【０１４０】
実施例９
実施例６に使用したフィラーに処理量が２０％になるようにＡｌ_２Ｏ_３による表面処理を行った。このフィラーを用いて、実施例６における保護層塗工液１、２、３を作製した。これらについて、塗工液中の平均粒径（堀場製作所：ＣＡＰＡ７００で測定）、塗工液の沈降性（試験管内で静置した塗工液粒子の沈降度合いを肉眼で確認）について評価した。結果を表３に示す。尚、表３に示される値は、それぞれの保護層塗工液３の測定結果である。
【０１４１】
【表３】

【０１４２】
実施例１０
実施例８で作製した分散液を用い、実施例６と同様に感光体を作製した。また、透過率測定用サンプルとして、保護層のみをポリエステルフィルム上に形成した。感光体の外観結果、表面粗さＲｚと６５５ｎｍにおける透過率を表４に示す。
【０１４３】
実施例１１
実施例９で作製した分散液を用い、実施例６と同様に感光体を作製した。また、透過率測定用サンプルとして、保護層のみをポリエステルフィルム上に形成した。感光体の外観結果、表面粗さＲｚと６５５ｎｍにおける透過率を表４に示す。
【０１４４】
【表４】

【０１４５】
実施例１２
実施例１０で作製した感光体を先の実施例６の評価に用いた装置と同じものに搭載し、画像評価を行った。その結果、実施例６の分散液を用いた感光体より、実施例８の分散液を用いた感光体の解像度が勝っていた。
【０１４６】
実施例１３
実施例１１で作製した感光体を先の実施例６の評価に用いた装置と同じものに搭載し、画像評価を行った。その結果、実施例６の分散液を用いた感光体より、実施例９の分散液を用いた感光体の解像度が勝っていた。
【０１４７】
実施例１４
アルミニウムシリンダー上に下記組成の下引き層塗工液、電荷発生層塗工液、および電荷輸送層塗工液を、順次塗布・乾燥し、３．５μｍの下引き層、０．２μｍの電荷発生層、２１μｍの電荷輸送層および４μｍの保護層からなる電子写真感光体を形成した。
◎下引き層塗工液
二酸化チタン粉末 ４００部
メラミン樹脂 ６５部
アルキッド樹脂 １２０部
２−ブタノン ４００部
◎電荷発生層塗工液
図８のスペクトルを有するチタニルフタロシアニン ８部
（特開２００１−１９８７１号公報に記載のチタニルフタロシアニン）
ポリビニルブチラール ５部
２−ブタノン ４００部
◎電荷輸送層塗工液
Ｚ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ７部
【化３１】

塩化メチレン ８０部
◎保護層塗工液１
ポリアリレート １０部
下記構造式の電荷輸送物質 ８部
【化３２】

酸化錫粉末（比抵抗：１０^５Ω・ｃｍ、平均１次粒径０．４μｍ） ６部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液２
ポリアリレート １０部
下記構造式の電荷輸送物質 ８部
【化３３】

粉末（比抵抗：１０^５Ω・ｃｍ、平均１次粒径０．４μｍ） ３部
アルミナ微粒子（比抵抗：２．５ｘ１０^１２Ω・ｃｍ、平均１次粒径０．４μｍ
） ３部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液３
ポリアリレート １０部
下記構造式の電荷輸送物質 ８部
【化３４】

アルミナ微粒子（２．５ｘ１０^１２Ω・ｃｍ、平均１次粒径０．４μｍ） ６部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
【０１４８】
上記保護層塗工液は、保護層塗工液１、２、３の順にスプレー法により連続的に塗工した。この際連続的とは、下層を塗工後、指触乾燥しないうちに次の塗工液をスプレー法により積層する事を指す。尚、保護層塗工液１、２は１．５μｍ相当ずつ塗工し、保護層塗工液３は１μｍ相当塗工し、合計４μｍの保護層を形成した。
【０１４９】
比較例１４
実施例１４における保護層を保護層塗工液１のみを用い、４μｍの保護層を形成した以外は、実施例１４と全く同様に感光体を作製した。
【０１５０】
比較例１５
実施例１４における保護層を保護層塗工液２のみを用い、４μｍの保護層を形成した以外は、実施例１４と全く同様に感光体を作製した。
【０１５１】
比較例１６
実施例１４における保護層を保護層塗工液３のみを用い、４μｍの保護層を形成した以外は、実施例１４と全く同様に感光体を作製した。
【０１５２】
比較例１７
実施例１４における保護層を積層せず、電荷輸送層を２５μｍとした以外は、実施例１４と同様に感光体を作製した。
【０１５３】
試験例３
以上のように作製した実施例１４および比較例１４〜１７の感光体を第７図に示す電子写真プロセス用カートリッジに装着し、画像露光光源を７８０ｎｍの半導体レーザー（ポリゴン・ミラーによる画像書き込み）として、連続して２万枚の印刷を行い、その時の画像を初期と２万枚後に評価した。更に、２万枚おける感光体表面の摩耗量も併せて測定した。以上の結果は、表５に併せて示す。
【表５】

【０１５４】
実施例１５
アルミニウムシリンダー上に下記組成の下引き層塗工液、電荷発生層塗工液、および電荷輸送層塗工液を、順次塗布・乾燥し、３．５μｍの下引き層、０．２μｍの電荷発生層、２０μｍの電荷輸送層、５μｍの保護層からなる電子写真感光体を形成した。尚、下引き層、電荷発生層、電荷輸送層は浸漬塗工法で塗工し、保護層はスプレー法にて塗工を行った。
◎下引き層塗工液
二酸化チタン粉末 ４００部
メラミン樹脂 ６５部
アルキッド樹脂 １２０部
２−ブタノン ４００部
◎電荷発生層塗工液
下記構造のビスアゾ顔料 １２部
【化３５】

ポリビニルブチラール ５部
２−ブタノン ２００部
シクロヘキサノン ４００部
◎電荷輸送層塗工液
Ａ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ８部
【化３６】

テトラヒドロフラン ２００部
◎保護層塗工液１
Ｃ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ７部
【化３７】

酸化錫粉末
（比抵抗：１ｘ１０^５Ω・ｃｍ、平均一次粒径：０．２μｍ） ５部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液２
Ｃ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ７部
【化３８】

酸化錫粉末（比抵抗：１ｘ１０^５Ω・ｃｍ、平均一次粒径：０．２μｍ） ３部
アルミナ微粒子（比抵抗：２．５ｘ１０^１２Ω・ｃｍ、平均一次粒径：０．４μ
ｍ） ２部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液３
Ｃ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ７部
【化３９】

アルミナ微粒子
（比抵抗：２．５ｘ１０^１２Ω・ｃｍ、平均一次粒径：０．４μｍ） ５部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
【０１５５】
上記保護層塗工液は、保護層塗工液１、２、３の順に３つのスプレーヘッドを用い、スプレー法により順次塗工した。この順次塗工とは、下層を塗工後、指触乾燥が完了したら、次の塗工液をスプレー法により積層する事を指す。尚、保護層塗工液１、２は２μｍ相当ずつ塗工し、保護層塗工液３は１μｍ相当塗工し、合計５μｍの保護層を形成した。
【０１５６】
実施例１６
実施例１５における保護層塗工液１、２、３をそれぞれ以下の組成のものに変更した以外は、実施例１と同様に感光体を作製した。
◎保護層塗工液１
下記構造式の高分子電荷輸送物質 ７部
【化４０】

酸化錫粉末（比抵抗：１ｘ１０^６Ω・ｃｍ、平均一次粒径：０．４μｍ） ２部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液２
下記構造式の高分子電荷輸送物質 ７部
【化４１】

酸化錫粉末（比抵抗：１ｘ１０^６Ω・ｃｍ、平均一次粒径：０．４μｍ） １部
アルミナ微粒子（比抵抗：２．５ｘ１０^１２Ω・ｃｍ、平均一次粒径：０．４μ
ｍ） １部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液３
下記構造式の高分子電荷輸送物質 ７部
【化４２】

アルミナ微粒子（比抵抗：２．５ｘ１０^１２Ω・ｃｍ、平均一次粒径：０．４μ
ｍ） ２部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
【０１５７】
比較例１８
実施例１５における保護層を保護層塗工液１のみを用い、５μｍの保護層を形成した以外は、実施例１５ と全く同様に感光体を作製した。
【０１５８】
比較例１９
実施例１５における保護層を保護層塗工液２のみを用い、５μｍの保護層を形成した以外は、実施例１５と全く同様に感光体を作製した。
【０１５９】
比較例２０
実施例１５における保護層を保護層塗工液３のみを用い、５μｍの保護層を形成した以外は、実施例１５と全く同様に感光体を作製した。
【０１６０】
比較例２１
実施例１６における保護層を保護層塗工液１のみを用い、５μｍの保護層を形成した以外は、実施例１６と全く同様に感光体を作製した。
【０１６１】
比較例２２
実施例１６における保護層を保護層塗工液２のみを用い、５μｍの保護層を形成した以外は、実施例１６と全く同様に感光体を作製した。
【０１６２】
比較例２３
実施例１６における保護層を保護層塗工液３のみを用い、５μｍの保護層を形成した以外は、実施例１６と全く同様に感光体を作製した。
【０１６３】
比較例２４
以上のように作製した実施例１５、１６および比較例１８〜２３の感光体を第５図に示す電子写真プロセス（ただし、クリーニング前露光は無し、帯電部材はスコロトロン方式チャージャー）に装着し、画像露光光源を６５５ｎｍの半導体レーザー（ポリゴン・ミラーによる画像書き込み）として、連続して２万枚の印刷を行い、その時の画像を初期と２万枚後に評価した。更に、２万枚おける感光体表面の摩耗量も併せて測定した。以上の結果は、表６に併せて示す。
【表６】

【０１６４】
実施例１７
実施例１５で使用した第５図に示す電子写真プロセスの帯電部材をスコロトロン・チャージャーから帯電ローラーに変更し、帯電ローラーが感光体に接触するように配置した。この装置に実施例１５で作製した感光体を搭載し、下記の帯電条件で、実施例１５と同様の評価を行った。
帯電条件：ＤＣバイアス：−８５０Ｖ
【０１６５】
初期及び２万枚目の画像はいずれも良好であったが、２万枚後の画像には帯電ローラー汚れ（トナーフィルミング）に基づく、ごく僅かな異常画像（地汚れ）が認められた。しかしながら、連続プリント時のオゾン臭は実施例１５の場合に比べて、格段に少なかった。
【０１６６】
実施例１８
実施例１７で使用した帯電ローラーの両端部に厚さ５０μｍ、幅５ｍｍの絶縁テープを張り付け、帯電ローラー表面と感光体表面との間に空間的なギャップ（５０μｍ）を有するように配置した。その他の条件は実施例１７と全く同様に評価を行った。その結果、実施例１７で認められた帯電ローラー汚れは、全く認められず、初期及び２万枚目の画像はいずれも良好であった。しかしながら、２万枚後にハーフトーン画像を出力した際、ごく僅かではあるが、帯電ムラに基づく画像ムラが認められた。
【０１６７】
実施例１９
実施例１８の評価において、帯電条件を以下のように変更した以外は実施例１８と同様の評価を行った。
帯電条件：ＤＣバイアス：−８５０Ｖ
ＡＣバイアス：１．８ｋＶ（ｐｅａｋ ｔｏ ｐｅａｋ）、周波数１．５ｋＨｚ
【０１６８】
初期及び２万枚後の画像は良好であった。実施例１７で認められた帯電ローラー汚れ、実施例１８で認められたハーフトーン画像ムラは、全く認められなかった。
【０１６９】
実施例２０
ニッケルベルト上に下記組成の下引き層塗工液、電荷発生層塗工液、および電荷輸送層塗工液を、順次塗布・乾燥し、３μｍの下引き層、０．３μｍの電荷発生層、２２μｍの電荷輸送層、３μｍの保護層からなる電子写真感光体を形成した。尚、下引き層、電荷発生層、電荷輸送層は浸漬塗工法で塗工し、保護層はスプレー法にて塗工を行った。
◎下引き層塗工液
二酸化チタン粉末 １００部
アルコール可溶性ナイロン １００部
メタノール ５００部
ブタノール ３００部
◎電荷発生層塗工液
下記構造のビスアゾ顔料 １０部
【化４３】

ポリビニルブチラール ２部
２−ブタノン ２００部
シクロヘキサノン ４００部
◎電荷輸送層塗工液
Ｚ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ７部
【化４４】

テトラヒドロフラン ２００部
◎保護層塗工液１
Ｚ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ６部
【化４５】

酸化錫粉末（比抵抗：１ｘ１０^６Ω・ｃｍ、平均一次粒径：０．４μｍ） ５部
トルエン ６００部
◎保護層塗工液２
Ｚ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ６部
【化４６】

酸化錫粉末（比抵抗：１ｘ１０^６Ω・ｃｍ、平均一次粒径：０．４μｍ） ３部
酸化チタン微粒子（比抵抗：１．５ｘ１０^１０Ω・ｃｍ、平均一次粒径：０．４
μｍ） ２部
トルエン ６００部
◎保護層塗工液３
Ｚ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ６部
【化４７】

酸化チタン微粒子（比抵抗：１．５ｘ１０^１０Ω・ｃｍ、平均一次粒径：０．４
μｍ） ５部
トルエン ６００部
【０１７０】
上記保護層塗工液は、保護層塗工液１、２、３の順に３つのスプレーヘッドを用い、スプレー法により順次塗工した。この順次塗工とは、下層を塗工後、指触乾燥が完了したら、次の塗工液をスプレー法により積層する事を指す。尚、保護層塗工液１、２、３は１μｍ相当ずつ塗工し、合計３μｍの保護層を形成した。
【０１７１】
実施例２１
実施例２０における保護層塗工液１、２、３をそれぞれ以下の組成のものに変更した以外は、実施例２０と同様に感光体を作製した。
◎保護層塗工液１
下記構造式の高分子電荷輸送物質 ７部
【化４８】

酸化錫粉末（比抵抗：１ｘ１０^６Ω・ｃｍ、平均一次粒径：０．２μｍ） ２．５部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液２
下記構造式の高分子電荷輸送物質 ７部
【化４９】

酸化錫粉末（比抵抗：１ｘ１０^６Ω・ｃｍ、平均一次粒径：０．２μｍ） １．５部
シリカ微粒子（比抵抗：４ｘ１０^１３Ω・ｃｍ、平均一次粒径：０．５μｍ） １部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液３
下記構造式の高分子電荷輸送物質 ７部
【化５０】

シリカ微粒子（比抵抗：４ｘ１０^１３Ω・ｃｍ、平均一次粒径：０．５μｍ） ２．５部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
【０１７２】
比較例２４
実施例２０における保護層を保護層塗工液１のみを用い、３μｍの保護層を形成した以外は、実施例２０と全く同様に感光体を作製した。
【０１７３】
比較例２５
実施例２０における保護層を保護層塗工液２のみを用い、３μｍの保護層を形成した以外は、実施例２０と全く同様に感光体を作製した。
【０１７４】
比較例２６
実施例２０における保護層を保護層塗工液３のみを用い、３μｍの保護層を形成した以外は、実施例２０と全く同様に感光体を作製した。
【０１７５】
比較例２７
実施例２０における保護層を積層せず、電荷輸送層を２５μｍ とした以外は、実施例６と同様に感光体を作製した。
【０１７６】
比較例２８
実施例２１における保護層を保護層塗工液１のみを用い、３μｍの保護層を形成した以外は、実施例２１と全く同様に感光体を作製した。
【０１７７】
比較例２９
実施例２１における保護層を保護層塗工液２のみを用い、３μｍの保護層を形成した以外は、実施例２１と全く同様に感光体を作製した。
【０１７８】
比較例３０
実施例２１における保護層を保護層塗工液３のみを用い、３μｍの保護層を形成した以外は、実施例２１と全く同様に感光体を作製した。
【０１７９】
試験例５
以上のように作製した実施例２０、２１および比較例２４〜３０の感光体を第６図に示す電子写真プロセス（ただし、クリーニング前露光は無し）に装着し、画像露光光源を６５５ｎｍのＬＥＤとして、連続して３万枚の印刷を行い、その時の画像を初期と３万枚後に評価した。更に、３万枚おける感光体表面の摩耗量も併せて測定した。以上の結果は、表７に併せて示す。
【０１８０】
【表７】

【０１８１】
実施例２２
実施例２０に使用したフィラーに処理量が２０％になるようにチタネート系カップリング剤による表面処理を行った。このフィラーを用いて、実施例２０における保護層塗工液１、２、３を作製した。これらについて、塗工液中の平均粒径（堀場製作所：ＣＡＰＡ５００で測定）、塗工液の沈降性（試験管内で静置した塗工液粒子の沈降度合いを肉眼で確認）について評価した。結果を表８に示す。尚、表８に示される値は、それぞれの保護層塗工液３の測定結果である。
【０１８２】
実施例２３
実施例２０に使用したフィラーに処理量が２０％になるようにＡｌ_２Ｏ_３による表面処理を行った。このフィラーを用いて、実施例２０における保護層塗工液１、２、３を作製した。これらについて、塗工液中の平均粒径（堀場製作所：ＣＡＰＡ５００で測定）、塗工液の沈降性（試験管内で静置した塗工液粒子の沈降度合いを肉眼で確認）について評価した。結果を表３に示す。尚、表８に示される値は、それぞれの保護層塗工液８の測定結果である。
【０１８３】
【表８】

【０１８４】
実施例２４
実施例２２で作製した分散液を用い、実施例２０と同様に感光体を作製した。
また、透過率測定用サンプルとして、保護層のみをポリエステルフィルム上に形成した。感光体の外観結果、表面粗さＲｚと６５５ｎｍにおける透過率を表９に示す。
【０１８５】
実施例２５
実施例２３で作製した分散液を用い、実施例２０と同様に感光体を作製した。
また、透過率測定用サンプルとして、保護層のみをポリエステルフィルム上に形成した。感光体の外観結果、表面粗さＲｚと６５５ｎｍにおける透過率を表９に示す。
【０１８６】
【表９】

【０１８７】
実施例２６
実施例２４で作製した感光体を先の実施例２０の評価に用いた装置と同じものに搭載し、画像評価を行った。その結果、実施例２０の分散液を用いた感光体より、実施例２２の分散液を用いた感光体の解像度が勝っていた。
【０１８８】
実施例２７
実施例２５で作製した感光体を先の実施例２０の評価に用いた装置と同じものに搭載し、画像評価を行った。その結果、実施例２０の分散液を用いた感光体より、実施例２３の分散液を用いた感光体の解像度が勝っていた。
【０１８９】
実施例２８
アルミニウムシリンダー上に下記組成の下引き層塗工液、電荷発生層塗工液、および電荷輸送層塗工液を、順次塗布・乾燥し、３．５μｍの下引き層、０．２μｍの電荷発生層、２１μｍの電荷輸送層および４μｍの保護層からなる電子写真感光体を形成した。
◎下引き層塗工液
二酸化チタン粉末 ４００部
メラミン樹脂 ６５部
アルキッド樹脂 １２０部
２−ブタノン ４００部
◎電荷発生層塗工液
図８に示すＸＤスペクトルを有するチタニルフタロシアニン ８部
（特開２００１−１９８７１号公報に記載のチタニルフタロシアニン）
ポリビニルブチラール ５部
２−ブタノン ４００部
◎電荷輸送層塗工液
Ｚ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ７部
【化５１】

塩化メチレン ８０部
◎保護層塗工液１
ポリアリレート １０部
下記構造式の電荷輸送物質 ８部
【化５２】

酸化錫−酸化アンチモン粉末
（比抵抗：１０^６Ω・ｃｍ、平均１次粒径０．４μｍ） ６部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液２
ポリアリレート １０部
下記構造式の電荷輸送物質 ８部
【化５３】

酸化錫−酸化アンチモン粉末
（比抵抗：１０^６Ω・ｃｍ、平均１次粒径０．４μｍ） ３部
アルミナ微粒子（比抵抗：２．５ｘ１０^１３Ω・ｃｍ、平均１次粒径０．６μｍ
） ３部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液３
ポリアリレート １０部
下記構造式の電荷輸送物質 ８部
【化５４】

アルミナ微粒子（比抵抗：２．５ｘ１０^１３Ω・ｃｍ、平均１次粒径０．６μｍ
） ６部
テトラヒドロフラン ４００部
シクロヘキサノン
２００部
【０１９０】
上記保護層塗工液は、保護層塗工液１、２、３の順に３つのスプレーヘッドを用い、スプレー法により順次塗工した。この順次塗工とは、下層を塗工後、指触乾燥が完了したら、次の塗工液をスプレー法により積層する事を指す。尚、保護層塗工液１、２は１．５μｍ相当ずつ塗工し、保護層塗工液３は１μｍ相当塗工し、合計４μｍの保護層を形成した。
【０１９１】
比較例３１
実施例２８における保護層を保護層塗工液１のみを用い、４μｍの保護層を形成した以外は、実施例２８と全く同様に感光体を作製した。
【０１９２】
比較例３２
実施例２８における保護層を保護層塗工液２のみを用い、４μｍの保護層を形成した以外は、実施例２８と全く同様に感光体を作製した。
【０１９３】
比較例３３
実施例２８における保護層を保護層塗工液３のみを用い、４μｍの保護層を形成した以外は、実施例２８と全く同様に感光体を作製した。
【０１９４】
比較例３４
実施例２８における保護層を積層せず、電荷輸送層を２５μｍとした以外は、実施例１４と同様に感光体を作製した。
【０１９５】
試験例６
以上のように作製した実施例２８および比較例３１〜３４の感光体を第５図に示す電子写真プロセス用カートリッジに装着し、画像露光光源を７８０ｎｍの半導体レーザー（ポリゴン・ミラーによる画像書き込み）として、連続して２万枚の印刷を行い、その時の画像を初期と２万枚後に評価した。更に、２万枚おける感光体表面の摩耗量も併せて測定した。以上の結果は、表１０に併せて示す。
【０１９６】
【表１０】

【０１９７】
実施例２９
実施例６における保護層塗工液１、２、３をそれぞれ以下の組成のものに変更した以外は、実施例６と同様に感光体を作製した。
◎保護層塗工液１
Ｚ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ６部
【化５５】

酸化錫−酸化アンチモン粉末
（比抵抗：１０^６Ω・ｃｍ、平均１次粒径０．４μｍ） ５部
トルエン ６００部
◎保護層塗工液２
Ｚ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ６部
【化５６】

酸化錫−酸化アンチモン粉末
（比抵抗：１０^６Ω・ｃｍ、平均１次粒径０．４μｍ） ３部
酸化チタン微粒子（比抵抗：１．５ｘ１０^１０Ω・ｃｍ、平均一次粒径：０．４
μｍ） ２部
トルエン ６００部
◎保護層塗工液３
Ｚ型ポリカーボネート １０部
下記構造式の電荷輸送物質 ６部
【化５７】

酸化チタン微粒子（比抵抗：１．５ｘ１０^１０Ω・ｃｍ、平均一次粒径：０．４
μｍ） ５部
トルエン ６００部
【０１９８】
試験例７
以上のように作製した実施例６および２９の感光体を第６図に示す電子写真プロセス（ただし、クリーニング前露光は無し）に装着し、画像露光光源を６５５ｎｍのＬＥＤとして、連続して３万枚の印刷を行い、その時の画像を初期と３万枚後に評価した。更に、３万枚おける感光体表面の摩耗量も併せて測定した。以上の結果は、表１１に併せて示す。
【表１１】

【０１９９】
実施例３０
実施例２０における保護層塗工液１、２、３をそれぞれ以下の組成のものに変更した以外は、実施例２０と同様に感光体を作製した。
◎保護層塗工液１
下記構造式の高分子電荷輸送物質 ７部
【化５８】

酸化錫粉末（比抵抗：１ｘ１０^６Ω・ｃｍ、平均一次粒径：０．２μｍ） ２．５部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液２
下記構造式の高分子電荷輸送物質 ７部
【化５９】

酸化錫粉末（比抵抗：１ｘ１０^６Ω・ｃｍ、平均一次粒径：０．２μｍ） １．５部
シリカ微粒子（比抵抗：４ｘ１０^１３Ω・ｃｍ、平均一次粒径：０．２μｍ） １部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
◎保護層塗工液３
下記構造式の高分子電荷輸送物質 ７部
【化６０】

シリカ微粒子（比抵抗：４ｘ１０^１３Ω・ｃｍ、平均一次粒径：０．２μｍ） ２．５部
テトラヒドロフラン ４００部
シクロヘキサノン ２００部
【０２００】
試験例８
以上のように作製した実施例２０および３０の感光体を第６図に示す電子写真プロセス（ただし、クリーニング前露光は無し）に装着し、画像露光光源を６５５ｎｍのＬＥＤとして、連続して３万枚の印刷を行い、その時の画像を初期と３万枚後に評価した。更に、３万枚おける感光体表面の摩耗量も併せて測定した。以上の結果は、表１２に併せて示す。
【表１２】

【０２０１】
実施例３１
実施例２８において、導電性支持体（ＪＩＳ１０５０）を以下の陽極酸化皮膜処理を行い、次いで下引き層を設けずに、実施例２８と同様に電荷発生層、電荷輸送層、保護層を設け、感光体を作製した。
◎陽極酸化皮膜処理
支持体表面の鏡面研磨仕上げを行い、脱脂洗浄、水洗浄を行った後、液温２０゜C、硫酸１５ ｖｏｌ％の電解浴に浸し、電解電圧１５Ｖにて３０分間陽極酸化皮膜処理を行った。更に、水洗浄を行った後、７％の酢酸ニッケル水溶液（５０゜C）にて封孔処理を行った。その後純水による洗浄を経て、６μｍの陽極酸化皮膜が形成された支持体を得た。
【０２０２】
試験例９
実施例２８、実施例３１で作製した感光体を第７図に示す電子写真プロセス用カートリッジに装着し、画像露光光源を７８０ｎｍの半導体レーザー（ポリゴン・ミラーによる画像書き込み）として、連続して２万枚の印刷を行い、その時の画像を初期と２万枚後に評価した。その結果、 両者の２万枚後の画像を比較すると、いずれも実使用上問題無いものであるが、地肌部の汚れ（黒点）が、実施例３１の画像に比べ、実施例２８の方がわずかに多かった。
【０２０３】
実施例３２
実施例１で作製した感光体を図１０に示す電子写真装置に搭載し、４つすべての画像形成要素は以下に示すプロセス条件にてフルカラー画像２００００枚の画像評価を行った。結果を表１３に示す。
・帯電条件
ＤＣバイアス： −８００Ｖ
ＡＣバイアス： ２．０ｋＶ（ｐｅａｋ ｔｏ ｐｅａｋ）、周波数２ｋＨｚ
・露光条件
６５５ｎｍの半導体レーザー（ポリゴンミラーによる画像書き込み）
【０２０４】
比較例３５
実施例３２で使用した感光体に変えて、比較例１で作製した感光体を使用した以外は、実施例３２と同様に画像評価試験を行った。結果を表１３に示す。
【０２０５】
比較例３６
実施例３２で使用した感光体に変えて、比較例３で作製した感光体を使用した以外は、実施例３２と同様に画像評価試験を行った。結果を表１３に示す。
【表１３】

【０２０６】
【発明の効果】
本発明により、高耐久で繰り返し使用に対し安定な高画質画像を作像できる感光体が提供される。また、繰り返し使用においても安定な高画質画像を高速で作像可能な電子写真方法、電子写真装置、ならびに電子写真用プロセスカートリッジが提供される。
【図面の簡単な説明】
【図１】本発明の電子写真感光体の一例の断面図である。
【図２】本発明の電子写真感光体の一例の断面図である。
【図３】本発明の電子写真感光体の一例の断面図である。
【図４】本発明の電子写真感光体の一例の断面図である。
【図５】本発明の電子写真装置の説明用概略図である。
【図６】本発明の電子写真プロセスの説明用概略図である。
【図７】本発明の電子写真プロセスの装置用プロセスカートリッジの説明用概略図である。
【図８】実施例１１で用いられるチタニルフタロシアニンのＸＤスペクトル図である。
【図９】帯電部材側にギャップ形成部材を配置した近接帯電機構の一例を示す図である。
【図１０】本発明のフルカラー電子写真装置の説明用概略図である。
【符号の説明】
１ 導電性支持体
２ 感光層
３ 保護層
４ 電荷発生層
５ 電荷輸送層
６ 感光体
７ 除電ランプ
８ 帯電部材
１０ 画像露光部
１１ 現像ユニット
１２ 転写前チャージャー
１３ レジストローラ
１４ 転写紙
１５ 転写ベルト
１６ 分離爪
１７ クリーニング前チャージャー
１８ ファーブラシ
１９ クリーニングブラシ
２１ 感光体
２２ 駆動ローラー
２３ 帯電ローラー
２４ 像露光源
２５ 転写チャージャー
２６ クリーニング前露光
２７ クリーニングブラシ
２８ 除電光源
３０ 帯電部材
３１ 画像露光部
３２ クリーニングブラシ
３３ 感光体
３４ 転写ローラー
３５ 現像ローラー
３６ 感光体
３７ 帯電ローラー
３８ ギャップ形成部材
３９ 金属シャフト
４０ 画像形成領域
４１ 非画像形成領域
１０１Ｃ，１０１Ｍ，１０１Ｙ，１０１Ｋ 感光体
１０２Ｃ，１０２Ｍ，１０２Ｙ，１０２Ｋ 帯電部材
１０３Ｃ，１０３Ｍ，１０３Ｙ，１０３Ｋ レーザー光
０４Ｃ，１０４Ｍ，１０４Ｙ，１０４Ｋ 現像部材
１０５Ｃ，１０５Ｍ，１０５Ｙ，１０５Ｋ クリーニング部材
１０６Ｃ，１０６Ｍ，１０６Ｙ，１０６Ｋ 画像形成要素
１０７ 転写紙
１０８ 給紙コロ
１０９ レジストローラ
１１０ 転写搬送ベルト
１１１Ｃ，１１１Ｍ，１１１Ｙ，１１１Ｋ 転写ブラシ
１１２ 定着装置[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photoconductor with high sensitivity, high resolution, and high durability. The present invention also relates to an electrophotographic method, an electrophotographic apparatus, and an electrophotographic process cartridge using a photoconductor provided with a protective layer having a specific configuration.
[0002]
[Prior art]
As an electrophotographic method, a Carson process and various deformation processes thereof are known, and are widely used for copying machines, printers, and the like. Among the photoreceptors used in such electrophotographic methods, those using organic photosensitive materials have begun to be used in recent years due to advantages such as low cost, mass productivity, and non-pollution. The organic electrophotographic photoreceptor includes a photoconductive resin typified by polyvinylcarbazole (PVK), a charge transfer complex type typified by PVK-TNF (2,4,7-trinitrofluorenone), Known are a pigment dispersion type typified by a phthalocyanine-binder, a function separation type photoreceptor using a combination of a charge generation material and a charge transport material, and the function separation type photoreceptor is attracting attention.
[0003]
The mechanism of electrostatic latent image formation in this function-separated type photoreceptor is that when the photoreceptor is charged and then irradiated with light, the light passes through the transparent charge transport layer and is absorbed by the charge generation material in the charge generation layer, The charge generating material that has absorbed light generates single charge, and this single charge is injected into the charge transport layer and moves in the charge transport layer in accordance with the electric field generated by the charge to neutralize the charge on the surface of the photoreceptor. Thus, an electrostatic latent image is formed. In the function-separated type photoreceptor, it is known and useful to use a combination of a charge transport material having absorption mainly in the ultraviolet region and a charge generation material having absorption mainly in the visible region.
[0004]
In recent years, there has been a demand for a reduction in the diameter of a photoconductor, and an increase in durability (life extension) of a machine and a photoconductor. As described above, organic photoreceptors have been steadily improved in sensitivity and electrostatic durability by vigorous development of materials. However, the current ability is not necessarily sufficient in terms of mechanical durability, particularly wear resistance. In view of this point, a photoconductor having a function of improving mechanical durability on the surface of an organic photoconductor has been proposed. Many of these studies have been made on the types of binder resins used for the outermost layer of the photoreceptor, but they have not always been satisfactory.
[0005]
Another way of thinking is to use a protective layer on the outermost surface of the photoreceptor. Examination of a protective layer as a surface layer of a photoreceptor starts with an inorganic photoreceptor, and is described in, for example, Japanese Patent Publication No. 2-3171, Japanese Patent Publication No. 2-7058, Japanese Patent Publication No. 3-43618, and the like. Yes. When the protective layer is provided on the surface of the inorganic photoreceptor in this way, a filler having a relatively low resistance is preferably used for the protective layer (Japanese Patent Laid-Open Nos. 63-254462 and 63-63). 254463). For this reason, when the photosensitive member is charged, the protective layer bulk or the protective layer / inorganic photosensitive layer interface is often charged rather than charged on the surface of the photosensitive member. Certainly, when the latent image is formed not inside the photoconductor surface but inside the protective layer (including the interface with the inorganic photoconductive layer), the merit that the influence of the photoconductor surface shape (such as scratches) is reduced is found. It was. However, when an attempt is made to give the surface layer a function as a protective layer, it is necessary to add a large amount of a conductive metal oxide as a filler to be added to the surface layer. In this case, even if the transparency of the surface layer is ensured by the selection of the material, the bulk or surface resistance of the surface layer is lowered, so that a defect of image blur may appear during repeated use. In order to eliminate such drawbacks, Japanese Patent Publication No. 2-7057 and Japanese Patent Publication No. 2675035 disclose a method of changing the conductive metal oxide concentration in the surface layer in the depth direction from the coating film surface. Has been. As a result, the image blur / flow is eliminated.
[0006]
Further, as a method for eliminating image blur by in-process processing, means for mounting a drum heater for heating a photosensitive member is used. Although the occurrence of image blur can be suppressed by heating the photoconductor, the diameter of the photoconductor must be large in order to mount a drum heater. It cannot be applied to a photoconductor, and it has been difficult to improve the durability of a small-diameter photoconductor. In addition, the installation of a drum heater necessitates an increase in the size of the device, resulting in a significant increase in power consumption and the fact that it takes a lot of time to start up the device. It was.
[0007]
On the other hand, a surface layer (protective layer) using a filler with low resistance is laminated on a photoreceptor (commonly called OPC) using an organic charge generating material and charge transporting material by applying the above-mentioned technique. However, when the repeated use test was performed, image flow occurred due to poor matching with OPC. In addition, even when a method of providing a concentration distribution in the surface layer of the conductive metal oxide, which was effective for an inorganic photoreceptor, the results were almost the same. The cause of this is unknown, but in recent electrophotographic processes using organic photoreceptors, digital signals are used by dot-writing on the photoreceptor. Is significantly different from the time when the mainstream of photoconductors. It can be said that the resolution level required from the machine side has changed greatly, and this phenomenon (defect) has become prominent.
[0008]
Under such circumstances, it is essential to use a filler having high resistance instead of conductivity for the surface layer of the organic photoreceptor. However, when a highly resistive filler is used, there may be a problem that the residual potential increases. The increase in the residual potential that is often observed leads to a high bright portion potential in the electrophotographic apparatus, which leads to a decrease in image density and gradation. In order to compensate for this, it is necessary to increase the dark part potential. However, if the dark part potential is increased, the electric field strength increases, which not only causes image defects such as background stains, but also reduces the life of the photoreceptor. Connected.
[0009]
In view of such a point, the idea of using a mixture of two types of fillers has also been tried, but the problem of image blurring during repeated use has been solved if many low-resistance fillers exist on the surface of the photoreceptor. However, the fundamental solution has not been reached. For this reason, in order to solve the above-mentioned problem, when two types of fillers having different specific resistances are used in combination, a configuration is required in which fillers having a low specific resistance are excluded from the photoreceptor surface side as much as possible. .
[0010]
In addition, as a method for suppressing the increase in residual potential in the prior art, a method using a protective layer as a photoconductive layer (Japanese Patent Publication No. 44-834, Japanese Patent Publication No. 43-16198, Japanese Patent Publication No. 49-10258) is available. It is disclosed. However, since the amount of light reaching the photosensitive layer is reduced by the absorption of light by the protective layer, there arises a problem that the sensitivity of the photosensitive member is lowered, and the effect is slight.
[0011]
On the other hand, when the average particle size of the metal or metal oxide contained as the filler is 0.3 μm or less (Japanese Patent Laid-Open No. 57-30846), the protective layer becomes substantially transparent and the residual potential is accumulated. A method of suppressing this is disclosed. Although this method has an effect of suppressing an increase in the residual potential, the effect is insufficient, and the actual situation is that the problem has not been solved. This is because the increase in the residual potential caused when the filler is contained is more likely to be caused by charge traps and filler dispersibility due to the presence of the filler than the charge generation efficiency. Even if the average particle size of the filler is 0.3 μm or more, it is possible to obtain transparency by increasing the dispersibility, and even if the average particle size is 0.3 μm or less, the filler is considerably aggregated. If this is the case, the transparency of the film will be reduced.
[0012]
As another means for suppressing the increase in the residual potential, a method of adding a Lewis acid or the like in the protective layer (Japanese Patent Laid-Open No. 53-133444), a method of adding an organic protonic acid to the protective layer (Japanese Patent Laid-Open No. 55-55). 157748), a method of containing an electron accepting substance (Japanese Patent Laid-Open No. 2-4275), and a method of containing a wax having an acid value of 5 (mg KOH / g) or less (Japanese Patent Laid-Open No. 2000-66434). Has been. These methods improve the charge injectability at the protective layer / charge transport layer interface, and because the low resistance portion is formed in the protective layer, the charge easily reaches the surface. It is believed that Although this method has an effect of reducing the residual potential, it tends to cause image blur, and has a side effect in which the influence on the image is noticeable. Moreover, since it becomes easy to cause the dispersibility fall of a filler when adding an organic acid, the effect is not enough and it is the actual condition that it has not resulted in the solution of a subject.
[0013]
In addition, in order to achieve high image quality in an electrophotographic photosensitive member containing a filler for high durability, not only the above-mentioned image blurring and residual potential increase are suppressed, but also the charge is protected. It is also important that the charge reaches the surface of the photoreceptor linearly without being hindered by the filler inside. This is greatly influenced by the dispersibility of the filler in the protective layer film. In the state where the filler is aggregated, when the charge injected into the protective layer from the charge transport layer moves to the surface, the progress is easily hindered by the filler, and as a result, the dots formed by the toner are scattered. The resolution is greatly reduced. In addition, when the protective layer is provided, if the writing light is scattered by the filler and the light transmittance is lowered, the resolution is similarly adversely affected. However, the influence on the light transmittance is also affected by the filler. It is closely related to dispersibility. Further, the dispersibility of the filler greatly affects the wear resistance, the filler causes strong aggregation, and the wear resistance is greatly lowered in a state where the dispersibility is poor. Therefore, in the electrophotographic photosensitive member in which a protective layer containing a filler for high durability is formed, in order to realize high image quality at the same time, not only the generation of image blur and the increase in residual potential are suppressed, It is important to increase the dispersibility of the filler in the protective layer film.
[0014]
However, effective means that can solve them simultaneously have not been found, and when filler is included in the outermost surface layer of the photoreceptor for high durability, the effect of image blur and residual potential rise appears strongly, The reality is that there are still issues with high image quality. In addition, since it is necessary to install a drum heater to reduce these effects, the high durability of the small-diameter photoreceptor, which is required to be the most durable, has not been realized. In fact, it has become a major obstacle to reducing power consumption.
[0015]
In addition, it is an organic photoconductor that has surpassed inorganic photoconductors in terms of photosensitivity, spectral sensitivity range, pollution-free property, electrostatic durability, etc., but mechanical durability is required to make full use of its advantages. Improving performance is an urgent issue, and its development has been eagerly awaited for the design of highly durable machines and processes.
[0016]
In addition, when a surface layer such as a protective layer is provided on the organic photosensitive layer, it is necessary to add a filler for the purpose of imparting abrasion resistance. However, the specific resistance as used in inorganic photosensitive members is required. When a small material (conductive material) is used, an abnormal image such as image blur or image flow is generated during initial or repeated use. Therefore, it is necessary to use a filler having a large specific resistance. However, when a filler having a large specific resistance is used, an abnormal image such as image blur can be avoided, but a new problem that a residual potential (post-exposure potential) becomes high has occurred.
[0017]
Inorganic photoreceptors that have been used in the past have been used with positive charge regardless of the presence or absence of a protective layer. On the other hand, both the hole transport type and the electron transport type have been developed as the charge transport material used in the organic photoreceptor, but the one that has actually reached the practical level is the hole transport type. For this reason, in the function-separated laminated photoconductor designed to make the best use of the characteristics of OPC, negative charge occupies most of it. Some single-layer photosensitive layers and reverse-layer photosensitive layers have been developed, but are not the mainstream.
[0018]
As described above, one of the reasons why the protective layer technology developed for inorganic photoreceptors cannot be applied horizontally to organic photoreceptors is probably due to this charged polarity. That is, the charging potential is used at substantially the same level for both the inorganic photoreceptor and the organic photoreceptor. At this time, when considering the discharge efficiency of the charger, as a general rule, the positive charge has a higher charge efficiency. In addition, when comparing the amount of reactive gas generated during positive charging and negative charging, it is known that the amount of generation of negative charging is overwhelmingly larger. It is understood that the phenomenon of image blur is caused at least by a decrease in the surface resistance of the photoconductor, and this decrease in surface resistance is caused by adhesion of a low resistance substance generated by a reactive gas to the surface of the photoconductor. It is also known to be the main cause.
[0019]
In order to improve such a point, a contact-type charging method has also been proposed. Although positive data has been disclosed that the ozone concentration in the vicinity of the charging member is certainly low, the inventors have disclosed it. According to the measurement results, it has been clarified that the amount of the low-resistance substance adhering to the surface of the photoconductor is almost the same as that when a non-contact type charging member is used. This is because, by using a contact-type charging member, the voltage applied to the charging member can be lowered, but the distance to the photosensitive member for discharge is narrowed, and the air current does not flow well or is a low resistance material because it is in contact. This could be caused by pressing directly onto the surface of the photoreceptor.
[0020]
In view of the above points, when providing a protective layer for imparting abrasion resistance to a negatively charged photoreceptor, it is essential to use a filler having a large specific resistance, and inorganic photosensitive materials disclosed in the past are essential. It was found that the protective layer used on the body essentially needs to be changed.
[0021]
As a full-color image forming apparatus using an electrophotographic system, two systems are generally known. One is a so-called single method or single drum method, in which one electrophotographic photosensitive member is mounted in the apparatus and four color developing members are mounted. In this method, four colors (cyan, magenta, yellow, and black) on the photosensitive member or on the transfer target member (directly transferred to the output paper or once transferred to the intermediate transfer member and then transferred to the paper) are used. A toner image is formed. In this case, the charging member, the exposure member, the transfer member, the cleaning member, and the fixing member arranged around the photosensitive member can be shared, and are designed to be smaller and less expensive than the tandem method described later. Is possible.
[0022]
On the other hand, another system is called a tandem system or a tandem drum system. This is one in which a plurality of electrophotographic photosensitive members are mounted at least in the apparatus. In general, each drum, one member for charging, exposure, development, and cleaning, is arranged on one drum to form one electrophotographic element, and a plurality (generally four) of them are mounted. Has been. In this method, a single color toner image is formed by one electrophotographic element, and the toner image is sequentially transferred to a transfer target to form a full color image. The merit of this method is that high-speed image formation is possible. This is because the toner images of the respective colors can be produced by parallel processing as described above. For this reason, compared with the single method, the image forming processing time is about one-fourth, and it is possible to cope with four times higher speed printing. The second merit is that the durability of each member provided in the electrophotographic element including the photoreceptor can be substantially increased. This is because, in the single method, each process of charging, exposure, and development is performed four times with one photoconductor to form one full color image, whereas in the tandem method, the above operation is performed once with one photoconductor. This is because they only do it.
[0023]
However, it also has the demerit that the entire device becomes large and the cost becomes high. As for the size of the entire apparatus, measures have been taken by reducing the diameter of the photosensitive member, reducing the size of each member installed around the photosensitive member, and reducing the size of one electrophotographic element. As a result, the effect of reducing the material cost as well as the size of the device has been produced, and the cost of the entire device has been reduced somewhat. However, with the downsizing and miniaturization of the apparatus, a new problem has arisen that the durability of each member including the photoreceptor mounted on the electrophotographic element has to be increased.
[0024]
Furthermore, in tandem image formation, since a plurality of image forming elements must be simultaneously formed, the plurality of image forming elements have substantially the same characteristics even at the beginning and after aging (repeated use). There is also the problem of having to. The most influential in this regard is the electrostatic properties of the photoreceptor in the image forming element. A large variation in the characteristics of the photoconductor used for a plurality of image forming elements changes the color balance of the output image, which is fatal for a full-color image forming apparatus in which color reproducibility differs from the input original drawing. Problems would occur.
[0025]
[Problems to be solved by the present invention]
An object of the present invention is to provide a photoconductor that can form a high-quality image that is highly durable and stable for repeated use. Specifically, the present invention provides a photoconductor that has high durability, suppresses image deterioration due to residual potential increase or image blurring, and can stably obtain a high-quality image even when used repeatedly for a long period of time. It is in. Another object of the present invention is to provide a photoreceptor having good color reproducibility even after repeated use in a tandem image forming apparatus.
[0026]
In addition, by using these photoconductors, it is not necessary to replace the photoconductors, and it is possible to reduce the size of the apparatus accompanying high-speed printing or reducing the diameter of the photoconductor. An electrophotographic method, an electrophotographic apparatus, and an electrophotographic process cartridge are provided.
[0027]
[Means to solve the problem]
There are three trade-offs: improving wear resistance, reducing residual potential, improving wear resistance and reducing image blur, improving wear resistance and improving resolution. Tend to be in a relationship. Therefore, as a result of repeated studies in the direction of improving the layer structure of the protective layer, the present inventors have used two types of fillers having different specific resistances in the protective layer, and have a configuration in which the abundance ratio of the two types of fillers is provided. It was found that the above three problems could be cleared simultaneously by adopting (a structure in which the ratio of the filler having a high specific resistance to the total filler amount was continuously increased from the support side to the surface side), and it was used repeatedly with high durability. An electrophotographic method, an electrophotographic apparatus, and an electrophotographic process cartridge capable of designing a photoconductor capable of forming a stable high-quality image, and capable of forming a stable high-quality image at high speed even during repeated use. I found out that it can be designed.
[0028]
Furthermore, it is composed of at least two layers of protective layers, and two or more kinds of fillers having different particle diameters are used. On the outermost surface side, a filler having a large filler particle diameter is used, and on the photosensitive layer side, the filler particle diameter is Tandem-type full-color image forming apparatus with excellent color reproducibility even after repeated use, by reducing the variation in electrostatic characteristics and variation in the amount of wear of the photoreceptor between a plurality of image-forming elements. Can be designed.
[0029]
According to the present invention, in an electrophotographic photosensitive member in which a photosensitive layer containing at least an organic charge generating material and an organic charge transporting material and a protective layer are provided on a conductive support, the protective layer has two types having different specific resistances. An electron comprising the above filler and having a gradient in which the ratio of the filler having the largest specific resistance with respect to all fillers in the protective layer is continuously increased from the photosensitive layer side to the surface side. It is a photographic photoreceptor. In addition, the ratio of the filler having a large specific resistance continuously increases that the protective layer is composed of a single layer, and the mixing ratio of two or more fillers continuously changes in the single protective layer. Is expressed.
[0030]
Further, in the electrophotographic photosensitive member in which a photosensitive layer containing at least an organic charge generating substance and an organic charge transporting substance and a protective layer are provided on a conductive support, the protective layer is composed of two or more layers, Each protective layer contains two or more kinds of fillers having different specific resistances, and the ratio of the filler having the largest specific resistance with respect to all fillers in the protective layer increases from the photosensitive layer side to the surface side layer in order. An electrophotographic photosensitive member characterized by the above. Sequentially, the ratio of the filler having a large specific resistance increases, which means that the protective layer is composed of a plurality of layers, and the mixing ratio of two or more fillers changes stepwise in the plurality of protective layers. It is.
[0031]
Further, in an electrophotographic method in which at least charging, image exposure, development, and transfer are repeatedly performed on an electrophotographic photosensitive member, the electrophotographic method uses the electrophotographic photosensitive member. An electrophotographic apparatus comprising at least a charging unit, an image exposing unit, a developing unit, a transferring unit, and an electrophotographic photosensitive member, wherein the electrophotographic photosensitive unit uses the electrophotographic photosensitive member. . Furthermore, a process cartridge for an electrophotographic apparatus comprising at least an electrophotographic photosensitive member, wherein the process cartridge for an electrophotographic apparatus is characterized by using the electrophotographic photosensitive member.
[0032]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the electrophotographic photosensitive member used in the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view showing a structural example of the electrophotographic photosensitive member of the present invention. A single-layer photosensitive layer 2 mainly composed of a charge generating material and a charge transporting material is provided on a conductive support 1. Further, a protective layer 3 is provided on the surface of the photosensitive layer. In this case, the protective layer 3 contains two or more kinds of fillers having different specific resistances, and the ratio of fillers having high specific resistance to all fillers is continuously increased from the support side to the surface side (of the mixing ratio). With a slope).
[0033]
FIG. 2 is a cross-sectional view showing another structural example of the electrophotographic photosensitive member of the present invention, in which a charge generation layer 4 mainly composed of a charge generation material and a charge transport material are mainly formed on a conductive support 1. The charge transport layer 5 as a component is laminated, and the protective layer 3 is further provided on the charge transport layer. In this case, the protective layer 3 contains two or more kinds of fillers having different specific resistances, and the ratio of fillers having high specific resistance to all fillers is continuously increased from the support side to the surface side (of the mixing ratio). It has a structure with a slope.
[0034]
FIG. 3 is a cross-sectional view showing a structural example of the electrophotographic photosensitive member of the present invention. A single-layer photosensitive layer 2 mainly composed of a charge generating material and a charge transporting material is provided on a conductive support 1. Further, a plurality of protective layers having different mixing ratios of two kinds of fillers having different specific resistances are provided on the photosensitive layer surface. In this case, the protective layer contains two or more kinds of fillers having different specific resistances, and the ratio of the filler having high specific resistance to all fillers is gradually increased from the support side layer to the surface side layer. It consists of
[0035]
FIG. 4 is a cross-sectional view showing another structural example of the electrophotographic photosensitive member of the present invention, in which a charge generation layer 4 mainly composed of a charge generation material and a charge transport material are mainly formed on a conductive support 1. The charge transport layer 5 as a component is laminated, and a plurality of protective layers 3 having different mixing ratios of two kinds of fillers having different specific resistances are provided on the surface of the photosensitive layer. In this case, the protective layer 3 contains two or more kinds of fillers having different specific resistances, and the ratio of the filler having a high specific resistance to the total filler is gradually increased from the support side layer to the surface side layer. It consists of a structure.
[0036]
1 to 4 described above, the two kinds of fillers having different filler specific resistances may be made of the same material (material) or different materials. When it is not desired to greatly change the characteristics as the bulk of the protective layer, stable characteristics can be obtained by using the same material. On the other hand, when it is desired to set a large transmittance as a protective layer bulk, if a component having a small particle diameter is included on the surface side, image blurring is likely to occur or wear resistance is reduced. It is not preferable to contain a filler having a small particle size on the surface side. Therefore, by increasing the particle diameter of the filler having a large specific resistance and decreasing the particle diameter of the filler having a small specific resistance, it is possible to form the gradient of the specific resistance and simultaneously add the gradient of the particle diameter. The effect of this is made more remarkable.
[0037]
The conductive support 1 has a volume resistance of 10¹⁰Films having conductivity of Ω · cm or less, for example, metal such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, metal oxide such as tin oxide, indium oxide, etc. are deposited or sputtered. Shaped or cylindrical plastic, paper-coated, or aluminum, aluminum alloy, nickel, stainless steel, etc., and after making them into tubes by methods such as extrusion and drawing, cutting, superfinishing, polishing, etc. A surface-treated tube or the like can be used. Further, an endless nickel belt and an endless stainless steel belt disclosed in Japanese Patent Laid-Open No. 52-36016 can also be used as the conductive support 1.
[0038]
Of these, a cylindrical support made of aluminum, which can be easily subjected to the anodic oxide film treatment, can be most preferably used. As used herein, aluminum includes both pure aluminum and aluminum alloys. Specifically, JIS 1000, 3000, and 6000 series aluminum or aluminum alloy is most suitable. The anodized film is obtained by anodizing various metals and various alloys in an electrolyte solution. Among them, a film called alumite obtained by anodizing aluminum or an aluminum alloy in an electrolyte solution is used in the present invention. Is most suitable for. In particular, it is excellent in preventing point defects (black spots, background stains) that occur when used in reversal development (negative / positive development).
[0039]
The anodizing treatment is performed in an acidic bath such as chromic acid, sulfuric acid, oxalic acid, phosphoric acid, boric acid, sulfamic acid. Of these, treatment with a sulfuric acid bath is most suitable. For example, sulfuric acid concentration: 10-20%, bath temperature: 5-25 ° C., current density: 1-4 A / dm²The treatment is carried out in the range of electrolytic voltage: 5 to 30 V, treatment time: about 5 to 60 minutes, but is not limited thereto. Since the anodic oxide film thus produced is porous and has high insulation, the surface is very unstable. For this reason, there is a change with time after fabrication, and the physical property value of the anodized film is likely to change. In order to avoid this, it is desirable to further seal the anodized film. Examples of the sealing treatment include a method of immersing the anodized film in an aqueous solution containing nickel fluoride and nickel acetate, a method of immersing the anodized film in boiling water, and a method of treating with pressurized steam. Among these, the method of immersing in the aqueous solution containing nickel acetate is the most preferable. Subsequent to the sealing treatment, the anodic oxide film is washed. The main purpose of this is to remove excess metal salts and the like attached by the sealing treatment. If this remains excessively on the surface of the support (anodized film), it not only adversely affects the quality of the coating film formed on this surface, but also generally low resistance components remain, resulting in the occurrence of soiling. It can also be a cause. The cleaning may be performed once with pure water, but is usually performed at another stage. At this time, it is preferable that the final cleaning liquid is as clean (deionized) as possible. Moreover, it is desirable to perform physical rubbing cleaning with a contact member in one of the other cleaning processes. The film thickness of the anodized film formed as described above is desirably about 5-15 μm. If it is too thin, the effect of the barrier property as an anodic oxide film is not sufficient, and if it is thicker than this, the time constant as an electrode becomes too large, resulting in the generation of residual potential and the response of the photoreceptor. There is a case.
[0040]
In addition to the above, a conductive support dispersed in an appropriate binder resin can be used as the conductive support 1 of the present invention. Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc and silver, or metal oxide powder such as conductive tin oxide and ITO. It is done. The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, Examples thereof include thermoplastic, thermosetting resins, and photocurable resins such as melamine resin, urethane resin, phenol resin, and alkyd resin. Such a conductive layer can be provided by dispersing and coating these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.
[0041]
Furthermore, a conductive layer is provided on a suitable cylindrical substrate by a heat-shrinkable tube containing the conductive powder in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, and Teflon. Can be used favorably as the conductive support 1 of the present invention.
[0042]
Next, the photosensitive layer will be described. The photosensitive layer may be a single layer or a laminated layer, but for convenience of explanation, the case where it is composed of the charge generation layer 4 and the charge transport layer 5 will be described first.
[0043]
The charge generation layer 4 is a layer mainly composed of a charge generation material. As the charge generation material, known charge generation materials can be used, and representative examples thereof include monoazo pigments, disazo pigments, trisazo pigments, perylene pigments, perinone pigments, quinacridone pigments, and quinone condensed polycyclic compounds. Squalic acid dyes, other phthalocyanine pigments, naphthalocyanine pigments, azulenium salt dyes and the like are used. These charge generation materials may be used alone or in combination of two or more.
[0044]
Of these, azo pigments and / or phthalocyanine pigments are effectively used. In particular, at least 27.2 as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to characteristic X-rays (wavelength 1.542 mm) of azo pigments represented by the following structural formula (I) and titanyl phthalocyanine, particularly CuKα. Titanyl phthalocyanine having a maximum diffraction peak at ° can be used effectively.
[Chemical 1]

Where Cp₁, Cp₂Represents a coupler residue and may be the same or different. R₂₀₁, R₂₀₂Each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a cyano group, which may be the same or different. Cp₁, Cp₂Is represented by the following formula (II):
[Chemical 2]

Where R₂₀₃Represents a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or an aryl group such as a phenyl group. R₂₀₄, R₂₀₅, R₂₀₆, R₂₀₇, R₂₀₈Are each a hydrogen atom, a nitro group, a cyano group, a halogen atom such as fluorine, chlorine, bromine or iodine, an alkyl group such as a trifluoromethyl group, a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, or a dialkyl An amino group and a hydroxyl group are represented, and Z represents an atomic group necessary for constituting a substituted or unsubstituted aromatic carbocyclic ring or a substituted or unsubstituted aromatic heterocyclic ring.
[0045]
In particular, the Cp₁And Cp₂Asymmetric azo pigments with different structures are Cp₁And Cp₂In many cases, the photosensitivity is better than that of the target type azo pigments having the same structure, which can cope with the reduction in the diameter of the photoreceptor and the speed of the use process, and is used effectively. Among the titanyl phthalocyanines having a maximum diffraction peak at 27.2 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ, titanyl phthalocyanine having a peak at 7.3 ° as a minimum angle (Japanese Patent Laid-Open No. 2001-19871). Is described in Japanese Patent Publication No. 3), and is highly sensitive and has a small decrease in chargeability in repeated use, and can be used particularly effectively.
[0046]
The charge generation layer 4 is dispersed in a suitable solvent together with a binder resin as necessary using a ball mill, attritor, sand mill, ultrasonic wave, etc., and this is applied onto a conductive support and dried. It is formed.
[0047]
As the binder resin used for the charge generation layer 4 as necessary, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, polysulfone, poly-N -Vinylcarbazole, polyacrylamide, polyvinyl benzal, polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polyamide, polyvinyl pyridine, cellulosic resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Can be mentioned. The amount of the binder resin is suitably 0 to 500 parts by weight, preferably 10 to 300 parts by weight with respect to 100 parts by weight of the charge generating material.
[0048]
Examples of the solvent used here include isopropanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, ligroin and the like. In particular, ketone solvents, ester solvents, and ether solvents are preferably used. As a coating method of the coating solution, methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating, and the like can be used.
[0049]
The thickness of the charge generation layer 4 is suitably about 0.01 to 5 μm, preferably 0.1 to 2 μm.
[0050]
The charge transport layer 5 can be formed by dissolving or dispersing a charge transport material and a binder resin in an appropriate solvent, and applying and drying the solution on the charge generation layer. Moreover, a plasticizer, a leveling agent, antioxidant, etc. can also be added as needed.
[0051]
Charge transport materials include hole transport materials and electron transport materials. Examples of the charge transport material include chloroanil, bromanyl, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-tri Examples thereof include electron-accepting substances such as nitrodibenzothiophene-5,5-dioxide and benzoquinone derivatives.
[0052]
Examples of hole transport materials include poly-N-vinylcarbazole and derivatives thereof, poly-γ-carbazolylethyl glutamate and derivatives thereof, pyrene-formaldehyde condensates and derivatives thereof, polyvinylpyrene, polyvinylphenanthrene, polysilane, oxazole derivatives, Oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, 9-styrylanthracene derivatives, pyrazolines Derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, etc., bisstilbene derivatives, enamine derivatives, etc. Other known materials may be mentioned. These charge transport materials may be used alone or in combination of two or more.
[0053]
Examples of the binder resin include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, Polyvinylidene chloride, polyarate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol Examples thereof include thermoplastic or thermosetting resins such as resins and alkyd resins.
[0054]
The amount of the charge transport material is appropriately 20 to 300 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin. The thickness of the charge transport layer is preferably 25 μm or less from the viewpoint of resolution and responsiveness. Regarding the lower limit, although it differs depending on the system to be used (particularly the charging potential), it is preferably 5 μm or more.
[0055]
As the solvent used here, tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone and the like are used.
[0056]
In the photoreceptor of the present invention, a plasticizer or a leveling agent may be added to the charge transport layer 5. As the plasticizer, those used as general plasticizers such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is suitably about 0 to 30% by weight based on the binder resin. As the leveling agent, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, polymers or oligomers having a perfluoroalkyl group in the side chain are used, and the amount used is 0 to 0 with respect to the binder resin. 1% by weight is suitable.
[0057]
Next, the case of the photosensitive layer 2 having a single layer structure will be described. A photoreceptor in which the above-described charge generating material is dispersed in a binder resin can be used. The single-layer photosensitive layer can be formed by dissolving or dispersing a charge generating substance, a charge transporting substance, and a binder resin in a suitable solvent, and applying and drying them. Further, the photosensitive layer may be a function separation type to which the above-described charge transport material is added, and can be used satisfactorily. Moreover, a plasticizer, a leveling agent, antioxidant, etc. can also be added as needed.
[0058]
As the binder resin, the binder resin previously mentioned in the charge transport layer 5 may be used as it is, or the binder resin mentioned in the charge generation layer 4 may be mixed and used. Of course, the polymer charge transport materials mentioned above can also be used favorably. The amount of the charge generating material with respect to 100 parts by weight of the binder resin is preferably 5 to 40 parts by weight, and the amount of the charge transporting material is preferably 0 to 190 parts by weight, and more preferably 50 to 150 parts by weight. A single-layer photosensitive layer is formed by dip coating or spraying with a coating solution dispersed with a disperser using a solvent such as tetrahydrofuran, dioxane, dichloroethane, or cyclohexane together with a charge transport material, if necessary, with a charge generating material and a binder resin. It can be formed by coating with a coat or bead coat. The film thickness of the single photosensitive layer is suitably about 5 to 25 μm.
[0059]
In the photoreceptor of the present invention, an undercoat layer can be provided between the conductive support 1 and the photosensitive layer. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is coated with a solvent on these resins, the resin may be a resin having high solvent resistance with respect to a general organic solvent. desirable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, a metal oxide fine powder pigment exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential.
[0060]
These undercoat layers can be formed using an appropriate solvent and coating method as in the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention. In addition, the undercoat layer of the present invention includes Al.₂O₃Anodic oxidation, organic materials such as polyparaxylylene (parylene), and SiO₂, SnO₂TiO₂, ITO, CeO₂A material provided with an inorganic material such as a vacuum thin film can also be used favorably. In addition, known ones can be used. The thickness of the undercoat layer is suitably from 0 to 5 μm.
[0061]
In the photoreceptor of the present invention, the protective layer 3 is provided on the photosensitive layer for the purpose of protecting the photosensitive layer. The protective layer 3 contains two types of fillers having different specific resistances, and is configured such that the ratio of fillers having high specific resistance to all fillers sequentially increases from the support-side layer to the surface-side layer. Or it is comprised so that the ratio of the filler with a high specific resistance with respect to all the fillers may become large continuously. As a result, it is possible to achieve both improvement of the wear resistance of the surface of the photoreceptor, reduction of residual potential, transparency, and reduction of image blur.
[0062]
The filler concentration in the protective layer varies depending on the type of filler used and also on the electrophotographic process conditions using the photoreceptor, but the ratio of filler to the total solid content on the outermost layer side of the protective layer is preferably 50% by weight or less, preferably About 30% by weight or less is good. On the most photosensitive layer side of the protective layer, 30% by weight or less, preferably about 10% by weight or less is good.
[0063]
Among the fillers used, the volume average particle diameter of the filler having the larger specific resistance is preferably in the range of 0.1 μm to 2 μm, and preferably in the range of 0.3 μm to 1 μm. In this case, if the average particle size is too small, the wear resistance is not sufficiently exhibited, and if it is too large, the surface property of the coating film is deteriorated or the coating film itself cannot be formed. The average particle size of the filler in the present invention is a volume average particle size unless otherwise specified, and is determined by an ultracentrifugal automatic particle size distribution analyzer: CAPA-700 (manufactured by Horiba). At this time, the particle diameter (Median diameter) corresponding to 50% of the cumulative distribution was calculated. In addition, it is important that the standard deviation of each particle measured simultaneously is 1 μm or less. If the standard deviation is larger than this, the particle size distribution may be too wide, and the effects of the present invention may not be obtained remarkably.
[0064]
The mixing ratio of fillers having different specific resistances is not particularly limited, but in the outermost layer of the surface layer, the ratio of fillers having high specific resistance is 50% or more, preferably 70% or more of all fillers. It is desirable.
[0065]
Materials used for the protective layer 3 are ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, polybutylene. , Polybutylene terephthalate, polycarbonate, polyarylate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylbenten, polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resin, butadiene-styrene copolymer, polyurethane, poly Examples thereof include resins such as vinyl chloride, polyvinylidene chloride, and epoxy resin. Of these, polycarbonate or polyarylate can be most preferably used.
[0066]
Among the filler materials added to the protective layer of the photoreceptor, examples of the organic filler material include fluorine resin powder such as polytetrafluoroethylene, silicone resin powder, a-carbon powder, and the like. Materials include metal powders such as copper, tin, aluminum and indium, silica, tin oxide, zinc oxide, titanium oxide, indium oxide, antimony oxide, bismuth oxide, tin oxide doped with antimony, tin-doped indium oxide, etc. And inorganic materials such as metal oxides and potassium titanate. In particular, it is advantageous to use an inorganic material among them from the viewpoint of the hardness of the filler. In particular, silica, titanium oxide, and alumina can be used effectively.
[0067]
Further, the pH of the filler, which is one of the constituent requirements of the present invention, greatly affects the resolution and the dispersibility of the filler. One possible reason is that hydrochloric acid or the like remains in the filler, particularly the metal oxide, during production. When the remaining amount is large, the occurrence of image blur is unavoidable, and depending on the remaining amount, the dispersibility of the filler may be affected. Another reason is due to the difference in chargeability on the surface of the filler, particularly the metal oxide. Usually, particles dispersed in a liquid are charged positively or negatively, and ions having opposite charges gather to try to keep it electrically neutral, and an electric double layer is formed there. The dispersed state of the particles is stabilized. The potential (zeta potential) gradually decreases with increasing distance from the particle, and the potential of a region that is sufficiently away from the particle and electrically neutral is zero. Therefore, the stability increases as the repulsive force of the particles increases due to the increase in the absolute value of the zeta potential, and the particles tend to aggregate and become unstable as they approach zero. On the other hand, the zeta potential varies greatly depending on the pH value of the system, and at a certain pH value, the potential becomes zero and has an isoelectric point. Therefore, the dispersion system is stabilized by increasing the absolute value of the zeta potential as far as possible from the isoelectric point of the system.
[0068]
In the configuration of the present invention, the filler having a pH at the isoelectric point of at least 5 is preferably from the viewpoint of image blur suppression, and the more basic the filler, the higher the effect. It was confirmed that there was. The filler having a high basic pH at the isoelectric point has a higher zeta potential when the system is acidic, so that dispersibility and stability thereof are improved.
[0069]
Here, the pH of the filler in the present invention is the pH value at the isoelectric point from the zeta potential. At this time, the zeta potential was measured with a laser zeta potentiometer manufactured by Otsuka Electronics Co., Ltd.
[0070]
Furthermore, as a filler that hardly causes image blur, a filler having high electrical insulation (specific resistance is 10%).¹⁰(Ω · cm or more) is preferable, and those having a filler pH of 5 or more and those having a dielectric constant of 5 or more can be used particularly effectively. In addition, a filler having a pH of 5 or more or a filler having a dielectric constant of 5 or more can be used alone, or two or more fillers having a pH of 5 or less and a filler having a pH of 5 or more can be mixed. It is also possible to use a mixture of two or more fillers having a dielectric constant of 5 or less and a filler having a dielectric constant of 5 or more. Among these fillers, α-type alumina, which has high insulation properties, high thermal stability, and high wear resistance, is a hexagonal close-packed structure, from the viewpoint of suppressing image blur and improving wear resistance. It is particularly useful.
[0071]
The specific resistance of the filler used in the present invention is defined as follows. Since the specific resistance value of a powder such as a filler varies depending on the filling rate, it is necessary to measure under certain conditions. In the present invention, an apparatus having the same configuration as the measuring apparatus shown in Japanese Patent Laid-Open No. 5-94049 (particularly, FIG. 1) and Japanese Patent Laid-Open No. 5-113688 (particularly, FIG. 1) is used. Then, the specific resistance value of the filler was measured and used. In the measuring device, the electrode area is 4.0 cm.²It is. Prior to the measurement, a load of 4 kg is applied to the electrode on one side for 1 minute, and the sample amount is adjusted so that the distance between the electrodes is 4 mm. At the time of measurement, the measurement is performed with the upper electrode weight (1 kg) loaded, and the applied voltage is measured at 100V. 10⁶The region above Ω · cm was measured with HIGH RESISTING METER (Yokogawa Hewlett Packard), and the region below it was measured with a digital multimeter (Fluk). The specific resistance value obtained in this way is defined as the specific resistance value according to the present invention.
[0072]
The dielectric constant of the filler was measured as follows. Using a cell similar to the measurement of the specific resistance as described above, after applying a load, the capacitance was measured, and the dielectric constant was determined from this. For the measurement of the capacitance, a dielectric loss measuring device (Ando Electric) was used.
[0073]
Further, these fillers can be surface-treated with at least one kind of surface treatment agent, and it is preferable from the viewpoint of dispersibility of the fillers. Decreasing the dispersibility of the filler not only increases the residual potential, but also decreases the transparency of the coating, causes defects in the coating, and decreases the wear resistance. It can develop into a big problem. As the surface treatment agent, all conventionally used surface treatment agents can be used, but a surface treatment agent capable of maintaining the insulating properties of the filler is preferable. For example, titanate coupling agents, aluminum coupling agents, zircoaluminate coupling agents, higher fatty acids, etc., or mixed treatment of these with silane coupling agents, Al₂O₃TiO₂, ZrO₂, Silicone, aluminum stearate, etc., or a mixture thereof is more preferable from the viewpoint of filler dispersibility and image blur. The treatment with the silane coupling agent is strongly influenced by image blur, but the influence may be suppressed by performing a mixing treatment of the surface treatment agent and the silane coupling agent. The surface treatment amount varies depending on the average primary particle size of the filler used, but is preferably 3 to 30 wt%, more preferably 5 to 20 wt%. If the surface treatment amount is less than this, the filler dispersion effect cannot be obtained, and if it is too much, the residual potential is significantly increased. These filler materials may be used alone or in combination of two or more. The surface treatment amount of the filler is defined by the weight ratio of the surface treatment agent to be used with respect to the filler amount as described above.
[0074]
In addition, about 0.1-10 micrometers is suitable for the thickness of a protective layer. These filler materials can be dispersed by using an appropriate disperser. Further, from the viewpoint of the transmittance of the protective layer, it is preferable that the filler used is dispersed to the primary particle level and has less aggregates.
[0075]
As a method for forming the protective layer, a normal coating method is employed. Among them, the spray method is an effective means, and the following method can be mentioned as the optimum method. One is a method in which a plurality of protective layer coating liquids having different filler ratios are sequentially laminated by a spray method before the lower layer is dried. In this case, it is desirable to prepare as many spray heads as the number of coating liquids and perform coating continuously. Another one is a method in which a plurality of protective layer coating liquids having different filler ratios are sequentially laminated by spraying after the lower layer finger drying. In this case, it is desirable to prepare as many spray heads as the number of coating liquids and perform coating continuously. Another method is to prepare as many spray heads as the number of fillers to be used, create a dispersion of each filler alone, change the discharge amount from the photosensitive layer side to the protective side, and the presence of each filler. There is a method of providing a ratio distribution.
[0076]
Further, the protective layer 3 may contain a charge transport material for reducing the residual potential and improving the response. As the charge transport material, the materials described in the description of the charge transport layer can be used. When a low molecular charge transport material is used as the charge transport material, a concentration gradient in the protective layer may be provided. In order to improve wear resistance, it is an effective means to reduce the concentration of the surface side. The concentration here refers to the ratio of the weight of the low-molecular charge transporting substance to the total weight of all the materials constituting the protective layer, and the concentration gradient is a gradient that lowers the concentration on the surface side in the above weight ratio. It shows that.
[0077]
In addition, a polymer charge transport material having a function as a charge transport material and a binder resin is also preferably used for the protective layer. The protective layer composed of these polymer charge transport materials is excellent in wear resistance. As the polymer charge transport material, known materials can be used, and in particular, a polycarbonate containing a triarylamine structure in the main chain and / or side chain is preferably used. Among these, the polymer charge transport materials represented by the formulas (III) to (XII) are favorably used, and these are exemplified below and specific examples are shown.
[0078]
(III) Formula
[Chemical Formula 3]

Where R₁, R₂, R₃Each independently represents a substituted or unsubstituted alkyl group or a halogen atom, R₄Is a hydrogen atom or a substituted or unsubstituted alkyl group, R₅, R₆Is a substituted or unsubstituted aryl group, o, p and q are each independently an integer of 0 to 4, k and j are compositions, 0.1 ≦ k ≦ 1, 0 ≦ j ≦ 0.9, n Represents the number of repeating units and is an integer of 5 to 5000. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula.
[Formula 4]

Where R₁₀₁, R₁₀₂Each independently represents a substituted or unsubstituted alkyl group, aryl group or halogen atom. l and m are integers of 0 to 4, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-, -SO₂-, -CO-, -CO-O-Z-O-CO- (wherein Z represents an aliphatic divalent group) or
[Chemical formula 5]

(Wherein, a is an integer of 1 to 20, b is an integer of 1 to 2000, R₁₀₃, R₁₀₄Represents a substituted or unsubstituted alkyl group or aryl group. ). Where R₁₀₁And R₁₀₂, R₁₀₃And R₁₀₄May be the same or different.
[0079]
(IV) Formula
[Chemical 6]

Where R₇, R₈Is a substituted or unsubstituted aryl group, Ar₁, Ar₂, Ar₃Represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (III).
[0080]
(V) Formula
[Chemical 7]

Where R₉, R₁₀Is a substituted or unsubstituted aryl group, Ar₄, Ar₅, Ar₆Represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (III).
[0081]
(VI) Formula
[Chemical 8]

Where R₁₁, R₁₂Is a substituted or unsubstituted aryl group, Ar₇, Ar₈, Ar₉Are the same or different arylene groups, and p represents an integer of 1 to 5. X, k, j and n are the same as in the case of the formula (III).
[0082]
(VII) Formula
[Chemical 9]

Where R₁₃, R₁₄Is a substituted or unsubstituted aryl group, Ar₁₀, Ar₁₁, Ar₁₂Are the same or different arylene groups, X₁, X₂Represents a substituted or unsubstituted ethylene group or a substituted or unsubstituted vinylene group. X, k, j and n are the same as in the case of the formula (III).
[0083]
(VIII) Formula
[Chemical Formula 10]

Where R₁₅, R₁₆, R₁₇, R₁₈Is a substituted or unsubstituted aryl group, Ar₁₃, Ar₁₄, Ar₁₅, Ar₁₆Are the same or different arylene groups, Y₁, Y₂, Y₃Represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group, which may be the same or different. X, k, j and n are the same as in the case of the formula (III).
[0084]
(IX) Formula
Embedded image

Where R₁₉, R₂₀Represents a hydrogen atom, a substituted or unsubstituted aryl group, and R₁₉And R₂₀May form a ring. Ar₁₇, Ar₁₈, Ar₁₉Represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (III).
[0085]
(X) Formula
Embedded image

Where R₂₁Is a substituted or unsubstituted aryl group, Ar₂₀, Ar₂₁, Ar₂₂, Ar₂₃Represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (III).
[0086]
(XI) Formula
Embedded image

Where R₂₂, R₂₃, R₂₄, R₂₅Is a substituted or unsubstituted aryl group, Ar₂₄, Ar₂₅, Ar₂₆, Ar₂₇, Ar₂₈Represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (III).
[0087]
(XII) formula
Embedded image

Where R₂₆, R₂₇Is a substituted or unsubstituted aryl group, Ar₂₉, Ar₃₀, Ar₃₁Represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (III).
[0088]
In addition to the polymer charge transport material described above, the polymer charge transport material used in the protective layer is a monomer or oligomer having an electron-donating group at the time of film formation of the protective layer. Alternatively, a polymer having a two-dimensional or three-dimensional crosslinked structure is finally included by carrying out a crosslinking reaction..
[0089]
A protective layer composed of a polymer having these electron donating groups or a polymer having a crosslinked structure is excellent in wear resistance. Usually, in the electrophotographic process, since the charging potential (unexposed portion potential) is constant, if the surface layer of the photoreceptor is worn by repeated use, the electric field strength applied to the photoreceptor increases accordingly. As the electric field strength increases, the occurrence frequency of scumming increases. Therefore, the high wear resistance of the photosensitive member is advantageous for scumming. The protective layer composed of a polymer having these electron-donating groups is a polymer compound, so it has excellent film-forming properties and has a higher density of charge transport sites than a protective layer composed of a low molecular dispersion type polymer. It is possible to form the structure and has excellent charge transport ability. For this reason, a photoreceptor having a protective layer using a polymer charge transport material can be expected to have a high response speed.
[0090]
Examples of the other polymer having an electron donating group include a copolymer of a known monomer, a block polymer, a graft polymer, a star polymer, and for example, JP-A-3-109406, JP-A 20000- It is also possible to use a cross-linked polymer having an electron donating group as disclosed in JP-A-206723 and JP-A No. 2001-34001.
[0091]
In the photoreceptor of the present invention, a binder resin is generally used as a main component in the intermediate layer in which an intermediate layer can be provided between the photosensitive layer and the protective layer. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As a method for forming the intermediate layer, a normal coating method is employed as described above. In addition, about 0.05-2 micrometers is suitable for the thickness of an intermediate | middle layer.
[0092]
In the present invention, in order to improve environmental resistance, for the purpose of preventing a decrease in sensitivity and an increase in residual potential, an antioxidant, a plasticizer, a lubricant, an ultraviolet absorber, and a low molecular charge transport material are used for each layer. And leveling agents can be added. Representative materials of these compounds are described below.
[0093]
Examples of the antioxidant that can be added to each layer include phenolic compounds, paraphenylenediamines, hydroquinones, organic sulfur compounds, and organic phosphorus compounds.
[0094]
Plasticizers that can be added to each layer include phosphate ester plasticizers, phthalate ester plasticizers, aromatic carboxylic ester plasticizers, aliphatic dibasic ester plasticizers, fatty acid ester derivatives, and oxyacid ester plasticizers. Agent, epoxy plasticizer, dihydric alcohol ester plasticizer, chlorine-containing plasticizer, polyester plasticizer, sulfonic acid derivative, citric acid derivative, terphenyl, partially hydrogenated terphenyl, camphor, 2-nitrodiphenyl, dinonyl Naphthalene, methyl abietate and the like can be mentioned.
[0095]
Examples of the lubricant that can be added to each layer include hydrocarbon compounds, fatty acid compounds, fatty acid amide compounds, ester compounds, alcohol compounds, metal soaps, natural waxes, silicone compounds, and fluorine compounds.
[0096]
Examples of the ultraviolet absorber that can be added to each layer include benzophenone, salicylate, benzotriazole, cyanoacrylate, quencher (metal complex), and HALS (hindered amine) compounds.
[0097]
Next, the electrophotographic method and the electrophotographic apparatus of the present invention will be described in detail with reference to the drawings. FIG. 5 is a schematic view for explaining the electrophotographic process and the electrophotographic apparatus of the present invention, and the following modifications also belong to the category of the present invention.
[0098]
In FIG. 5, the photoreceptor 6 is formed by providing a plurality of protective layers having different mixing ratios of two kinds of fillers having a specific resistance different from that of the photosensitive layer on a conductive support. Alternatively, the photoreceptor 1 is formed by providing a protective layer having a gradient in the mixing ratio of a filler having a specific resistance different from that of the photosensitive layer on a conductive support. The photosensitive member 6 has a drum shape, but may be a sheet shape or an endless belt shape. As the charging member 8, the pre-transfer charger 12, and the pre-cleaning charger 17, known means such as a corotron, a scorotron, a solid state charger (solid state charger), and a charging roller are used. As the charging member, a member that is in contact with or close to the photoreceptor is preferably used.
[0099]
The contact-type charging member here is a type in which the surface of the charging member is in contact with the surface of the photosensitive member, and includes a charging roller, a charging blade, and a charging brush. Among them, a charging roller and a charging brush are used favorably.
[0100]
Further, the charging member arranged in the proximity is a type in which the charging member is arranged in a non-contact state so as to have a gap (gap) of 200 μm or less between the surface of the photosensitive member and the surface of the charging member. It is distinguished from known chargers typified by corotron and scorotron from the distance of the gap. The adjacently arranged charging member used in the present invention may have any shape as long as it has a mechanism capable of appropriately controlling the gap with the surface of the photoreceptor. For example, the rotation shaft of the photosensitive member and the rotation shaft of the charging member may be mechanically fixed so as to have an appropriate gap. Among them, using a charging member in the shape of a charging roller, a gap forming member is disposed at both ends of the non-image forming portion of the charging member, and only this portion is brought into contact with the surface of the photoreceptor, and the image forming region is disposed in a non-contact manner. Alternatively, the gap forming member at both ends of the non-photosensitive portion of the photoconductor is disposed, and only this portion is brought into contact with the surface of the charging member, and the image forming region is disposed in a non-contact manner, so that the gap can be stably stabilized. It is a method that can be maintained. In particular, the methods described in Japanese Patent Application Nos. 13-21448 and 13-226432 can be used satisfactorily. An example of the proximity charging mechanism in which the gap forming member is disposed on the charging member side is shown in FIG.
[0101]
Further, when charging the photosensitive member with the charging member, charging unevenness can be effectively reduced by charging the photosensitive member with an electric field in which an alternating current component is superimposed on a direct current component on the charging member.
[0102]
As the transfer means, the above charger can be generally used, but a combination of a transfer charger and a separation charger is effective. Light sources such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), an electroluminescence (EL), etc. All things can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
[0103]
Such a light source or the like irradiates the photosensitive member with light by providing a transfer step, a static elimination step, a cleaning step, or a pre-exposure step in combination with light irradiation in addition to the steps shown in FIG.
[0104]
The toner developed on the photosensitive member 6 by the developing unit 11 is transferred to the transfer paper 14, but not all is transferred, and some toner remains on the photosensitive member 6. Such toner is removed from the photoreceptor by the fur brush 18 and the blade. Cleaning may be performed only with a cleaning brush, and a known brush such as a fur brush or a mag fur brush is used as the cleaning brush.
[0105]
When the electrophotographic photosensitive member is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner. A known method is applied to the developing unit, and a known method is also used for the charge eliminating unit.
[0106]
FIG. 6 shows another example of the electrophotographic process according to the present invention. The photoreceptor 21 has, on the conductive support, at least a photosensitive layer and at least a plurality of protective layers having different mixing ratios of two types of fillers having different specific resistances, or a mixing ratio gradient of fillers having different specific resistances. A protective layer is provided. Driven by driving rollers 22a and 22b, charging by a charging roller (charger) 23, image exposure by a light source 24, development (not shown), transfer using a transfer charger (charger) 25, exposure before cleaning by a light source 26, Cleaning with the brush 27 and static elimination with the light source 28 are repeated. In FIG. 6, the photoconductor 21 (of course, the support is translucent in this case) is irradiated with pre-cleaning exposure light from the support side.
[0107]
The above illustrated electrophotographic process is illustrative of an embodiment of the present invention, and of course other embodiments are possible. For example, in FIG. 6, the pre-cleaning exposure is performed from the support side, but this may be performed from the photosensitive layer side, or image exposure and neutralization light irradiation may be performed from the support side. On the other hand, in the light irradiation process, image exposure, pre-cleaning exposure, and static elimination exposure are illustrated. In addition, pre-exposure exposure, pre-exposure of image exposure, and other known light irradiation processes are provided to light the photosensitive member. Irradiation can also be performed.
[0108]
The image forming means as described above may be fixedly incorporated in a copying apparatus, a facsimile, or a printer, but may be incorporated in these apparatuses in the form of a process cartridge. A process cartridge is a single device (part) that contains a photosensitive member and includes a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, and a charge eliminating unit. There are many shapes and the like of the process cartridge, but a general example is the one shown in FIG. The photosensitive member 33 incorporated here is a protective layer of a plurality of layers having different mixing ratios of at least a photosensitive layer and at least two types of fillers having different specific resistances or fillers having different specific resistances on a conductive support. A protective layer having a mixing ratio gradient is provided.
[0109]
FIG. 10 is a schematic view for explaining the tandem-type full-color electrophotographic apparatus of the present invention, and the following modifications also belong to the category of the present invention. In FIG. 10, reference numerals 101C, 101M, 101Y, and 101K denote drum-shaped photoconductors. The photoconductors 101C, 101M, 101Y, and 101K rotate in the direction of the arrows in the figure, and at least in the order of rotation around the charging members. 102C, 102M, 102Y, and 102K, developing members 104C, 104M, 104Y, and 104K, and cleaning members 105C, 105M, 105Y, and 105K are arranged. The charging members 102C, 102M, 102Y, and 102K are charging members that constitute a charging device for uniformly charging the surface of the photoreceptor. The photosensitive member surface between the charging members 102C, 102M, 102Y, and 102K and the developing members 104C, 104M, 104Y, and 104K is irradiated with laser beams 103C, 103M, 103Y, and 103K from an exposure member (not shown), and the photosensitive member 101C, Electrostatic latent images are formed on 101M, 101Y, and 101K. Then, four image forming elements 106C, 106M, 106Y, and 106K centering on such photoconductors 101C, 101M, 101Y, and 101K are juxtaposed along a transfer conveyance belt 110 that is a transfer material conveyance unit. The transfer conveyance belt 110 contacts the photosensitive members 101C, 101M, 101Y, and 101K between the developing members 104C, 104M, 104Y, and 104K and the cleaning members 105C, 105M, 105Y, and 105K of the image forming units 106C, 106M, 106Y, and 106K. Transfer brushes 111C, 111M, 111Y, and 111K for applying a transfer bias are disposed on a surface (back surface) that is in contact with and contacts the back side of the transfer conveyor belt 110 on the photoconductor side. Each of the image forming elements 106C, 106M, 106Y, and 106K applies a DC component only to the black toner image forming charging member 102K according to the present invention when the toner color inside the developing device is different, and for toner images other than black. An alternating electric field in which an AC component is superimposed on a DC component is applied to the charging members 102C, 102M, and 102Y, and the rest of the configuration is the same.
[0110]
In the color electrophotographic apparatus having the configuration shown in FIG. 10, the image forming operation is performed as follows. First, in each of the image forming elements 106C, 106M, 106Y, and 106K, the photosensitive members 101C, 101M, 101Y, and 101K are charged by the charging members 102C, 102M, 102Y, and 102K that rotate in the direction of the arrow (the direction along with the photosensitive member). Next, an electrostatic latent image corresponding to each color image to be created is formed by the laser beams 103C, 103M, 103Y, and 103K in the exposure unit. Next, the latent image is developed by the developing members 104C, 104M, 104Y, and 104K to form a toner image. The developing members 104C, 104M, 104Y, and 104K are developing members that perform development with toners of C (cyan), M (magenta), Y (yellow), and K (black), respectively, and the four photosensitive members 101C, 101M, and 101Y. , 101K, each color toner image is superimposed on the transfer paper. The transfer paper 107 is fed out from the tray by a paper feed roller 108, temporarily stopped by a pair of registration rollers 109, and sent to the transfer conveyance belt 110 in synchronism with the image formation on the photosensitive member. The transfer paper 107 held on the transfer conveyance belt 110 is conveyed, and each color toner image is transferred at a contact position (transfer portion) with each of the photoconductors 101C, 101M, 101Y, and 101K. The toner image on the photoconductor is transferred onto the transfer paper 107 by an electric field formed by a potential difference between the transfer bias applied to the transfer brushes 111C, 111M, 111Y, and 111K and the photoconductors 101C, 101M, 101Y, and 101K. The Then, the transfer paper 107 on which the four color toner images are passed through the four transfer portions is conveyed to the fixing device 112 where the toner is fixed and discharged to a paper discharge portion (not shown). In addition, residual toner remaining on the photosensitive members 101C, 101M, 101Y, and 101K without being transferred by the transfer unit is collected by the cleaning devices 105C, 105M, 105Y, and 105K. In the example of FIG. 1, the image forming elements are arranged in the order of C (cyan), M (magenta), Y (yellow), and K (black) from the upstream side to the downstream side in the transfer paper conveyance direction. However, it is not limited to this order, and the color order is arbitrarily set. In addition, when creating a black-only document, providing a mechanism that stops the image forming elements (106C, 106M, 106Y) other than black can be used particularly effectively in the present invention. Further, in FIG. 10, the charging member is in contact with the photosensitive member, but by providing an appropriate gap (about 10 to 200 μm) between them, the wear amount of both can be reduced and the charging member can be applied to the charging member. Less toner filming and good use.
[0111]
The image forming means as described above may be fixedly incorporated in a copying apparatus, facsimile, or printer, but each electrophotographic element may be incorporated in the apparatus in the form of a process cartridge. A process cartridge is a single device (part) that contains a photoconductor and further includes a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, a neutralizing unit, and the like.
[0112]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not restrict | limited by an Example. All parts are parts by weight.
[0113]
Example 1
An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition are sequentially applied and dried on an aluminum cylinder to generate a 3.5 μm undercoat layer and a 0.2 μm charge generation. An electrophotographic photosensitive member comprising a layer, a 20 μm charge transport layer, and a 5 μm protective layer was formed. The undercoat layer, charge generation layer, and charge transport layer were applied by a dip coating method, and the protective layer was applied by a spray method.
◎ Undercoat layer coating solution
400 parts of titanium dioxide powder
65 parts of melamine resin
120 parts alkyd resin
2-butanone 400 parts
◎ Charge generation layer coating solution
12 parts of bisazo pigment with the following structure
Embedded image

Polyvinyl butyral 5 parts
2-butanone 200 parts
400 parts of cyclohexanone
◎ Charge transport layer coating solution
10 parts of A type polycarbonate
8 parts of charge transport material of the following structural formula
Embedded image

Tetrahydrofuran 200 parts
◎ Protective layer coating solution 1
10 parts of C type polycarbonate
7 parts of charge transport material with the following structural formula
Embedded image

Tin oxide powder
(Specific resistance: 10⁶Ω · cm, average primary particle size: 0.2 μm) 5 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 2
10 parts of C type polycarbonate
7 parts of charge transport material with the following structural formula
Embedded image

Tin oxide powder (specific resistance: 10⁶Ω · cm, average primary particle size: 0.2 μm) 3 parts
Alumina fine particles (specific resistance: 2.5 × 10¹²Ω · cm, average primary particle size: 0.4μ
m) 2 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 3
10 parts of C type polycarbonate
7 parts of charge transport material with the following structural formula
Embedded image

Alumina fine particles
(Specific resistance: 2.5 × 10¹²Ω · cm, average primary particle size: 0.4 μm) 5 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
[0114]
The protective layer coating solution was applied continuously by a spray method using three spray heads in the order of the protective layer coating solutions 1, 2, and 3. In this case, the term “continuous” means that the next coating liquid is laminated by a spray method after the lower layer is coated and before the touch is dried. The protective layer coating solutions 1 and 2 were applied in an amount corresponding to 2 μm, and the protective layer coating solution 3 was applied in an amount corresponding to 1 μm to form a total protective layer of 5 μm.
[0115]
Example 2
A photoconductor was prepared in the same manner as in Example 1 except that the protective layer coating solutions 1, 2, and 3 in Example 1 were changed to those having the following compositions, respectively.
◎ Protective layer coating solution 1
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Tin oxide powder (specific resistance: 10⁶Ω · cm, average primary particle size: 0.2 μm) 2 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 2
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Tin oxide powder (specific resistance: 10⁶Ω · cm, average primary particle size: 0.2 μm) 1 part
Alumina fine particles (specific resistance: 2.5 × 10¹²Ω · cm, average primary particle size: 0.4μ
m) 1 copy
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 3
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Alumina fine particles (specific resistance: 2.5 × 10¹²Ω · cm, average primary particle size: 0.4μ
m) 2 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
[0116]
Comparative Example 1
A photoconductor was prepared in exactly the same manner as in Example 1 except that only the protective layer coating solution 1 was used as the protective layer in Example 1 and a 5 μm protective layer was formed.
[0117]
Comparative Example 2
A photoconductor was prepared in exactly the same manner as in Example 1 except that only the protective layer coating solution 2 was used as the protective layer in Example 1 and a 5 μm protective layer was formed.
[0118]
Comparative Example 3
A photoconductor was prepared in exactly the same manner as in Example 1 except that only the protective layer coating solution 3 was used as the protective layer in Example 1 and a 5 μm protective layer was formed.
[0119]
Comparative Example 4
A photoconductor was prepared in exactly the same manner as in Example 2, except that only the protective layer coating solution 1 was used as the protective layer in Example 2 and a 5 μm protective layer was formed.
[0120]
Comparative Example 5
A photoconductor was prepared in exactly the same manner as in Example 2, except that only the protective layer coating solution 2 was used as the protective layer in Example 2 and a 5 μm protective layer was formed.
[0121]
Comparative Example 6
A photoconductor was prepared in exactly the same manner as in Example 2, except that only the protective layer coating solution 3 was used as the protective layer in Example 2 and a 5 μm protective layer was formed.
[0122]
Test example 1
The photoconductors of Examples 1 and 2 and Comparative Examples 1 to 6 produced as described above were mounted on the electrophotographic process shown in FIG. 5 (however, there was no exposure before cleaning, and the charging member was a scorotron charger). The exposure light source was a semiconductor laser of 655 nm (image writing by a polygon mirror), and 20,000 sheets were printed continuously, and the images at that time were evaluated initially and after 20,000 sheets. In addition, the amount of wear on the surface of the photoreceptor on 20,000 sheets was also measured. The above results are also shown in Table 1.
[Table 1]

[0123]
Example 3
The charging member of the electrophotographic process shown in FIG. 3 used in Example 1 was changed from the scorotron charger to the charging roller, and the charging roller was disposed so as to contact the photoreceptor. The photoconductor produced in Example 1 was mounted on this apparatus, and the same evaluation as in Example 1 was performed under the following charging conditions.
Charging condition: DC bias: -800V
[0124]
The initial image and the 20,000th image were both good, but a very slight abnormal image (background stain) based on the charging roller stain (toner filming) was observed in the image after 20,000 copies. However, the ozone odor during continuous printing was much less than that in Example 1.
[0125]
Example 4
An insulating tape having a thickness of 50 μm and a width of 5 mm was attached to both ends of the charging roller used in Example 3, and arranged so as to have a spatial gap (50 μm) between the charging roller surface and the photoreceptor surface. The other conditions were evaluated in the same manner as in Example 3. As a result, no charging roller contamination was observed in Example 3, and both the initial and 20,000th images were good. However, when a halftone image was output after 20,000 sheets, image unevenness based on charging unevenness was recognized although it was very slight.
[0126]
Example 5
In the evaluation of Example 4, the same evaluation as in Example 4 was performed except that the charging conditions were changed as follows.
Charging condition: DC bias: -800V
AC bias: 1.6 kV (peak to peak), frequency 1.6 kHz
[0127]
The initial image and the image after 20,000 sheets were good. The charging roller stains observed in Example 3 and the halftone image unevenness observed in Example 4 were not recognized at all.
[0128]
Example 6
An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition are sequentially applied and dried on a nickel belt, and a 3 μm undercoat layer, a 0.3 μm charge generation layer, An electrophotographic photoreceptor comprising a 22 μm charge transport layer and a 3 μm protective layer was formed. The undercoat layer, charge generation layer, and charge transport layer were applied by a dip coating method, and the protective layer was applied by a spray method.
◎ Undercoat layer coating solution
100 parts of titanium dioxide powder
100 parts of alcohol-soluble nylon
500 parts of methanol
300 parts of butanol
◎ Charge generation layer coating solution
10 parts of bisazo pigment with the following structure
Embedded image

Polyvinyl butyral 2 parts
2-butanone 200 parts
400 parts of cyclohexanone
◎ Charge transport layer coating solution
10 parts of Z-type polycarbonate
7 parts of charge transport material with the following structural formula
Embedded image

Tetrahydrofuran 200 parts
◎ Protective layer coating solution 1
10 parts of Z-type polycarbonate
6 parts of charge transport material of the following structural formula
Embedded image

Tin oxide-antimony oxide powder
(Specific resistance: 10⁶Ω · cm, average primary particle size 0.4μm) 5 parts
600 parts of toluene
◎ Protective layer coating solution 2
10 parts of Z-type polycarbonate
6 parts of charge transport material of the following structural formula
Embedded image

Tin oxide-antimony oxide powder
(Specific resistance: 10⁶Ω · cm, average primary particle size 0.4μm) 3 parts
Titanium oxide fine particles (specific resistance: 1.5 × 10¹⁰Ω · cm, average primary particle size: 0.6
μm) 2 parts
600 parts of toluene
◎ Protective layer coating solution 3
10 parts of Z-type polycarbonate
6 parts of charge transport material of the following structural formula
Embedded image

Titanium oxide fine particles (specific resistance: 1.5 × 10¹⁰Ω · cm, average primary particle size: 0.6
μm) 5 parts
600 parts of toluene
[0129]
The protective layer coating solution was continuously applied by the spray method in the order of the protective layer coating solutions 1, 2, and 3. In this case, the term “continuous” means that the next coating liquid is laminated by a spray method after the lower layer is coated and before the touch is dried. The protective layer coating solutions 1, 2, and 3 were applied in an amount corresponding to 1 μm to form a total protective layer of 3 μm.
[0130]
Example 7
A photoconductor was prepared in the same manner as in Example 6 except that the protective layer coating solutions 1, 2, and 3 in Example 6 were changed to those having the following compositions, respectively.
◎ Protective layer coating solution 1
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Tin oxide-antimony oxide powder (specific resistance: 10⁶Ω · cm, average primary particle size: 0.6
μm) 2.5 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 2
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Tin oxide-antimony oxide powder
(Specific resistance: 10⁶Ω · cm, average primary particle size 0.6 μm) 1.5 parts
Silica fine particles (specific resistance: 4 × 10¹³Ω · cm, average primary particle size: 0.5 μm) 1 part
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 3
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Silica fine particles (specific resistance: 4 × 10¹³Ω · cm, average primary particle size: 0.5 μm) 2.5 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
[0131]
Comparative Example 7
A photoconductor was prepared in the same manner as in Example 6 except that only the protective layer coating solution 1 was used as the protective layer in Example 6 and a 3 μm protective layer was formed.
[0132]
Comparative Example 8
A photoconductor was prepared in the same manner as in Example 6 except that only the protective layer coating solution 2 was used as the protective layer in Example 6 and a 3 μm protective layer was formed.
[0133]
Comparative Example 9
A photoconductor was prepared in the same manner as in Example 6 except that only the protective layer coating solution 3 was used as the protective layer in Example 6 and a 3 μm protective layer was formed.
[0134]
Comparative Example 10
A photoconductor was prepared in the same manner as in Example 6 except that the protective layer in Example 6 was not laminated and the charge transport layer was 25 μm.
[0135]
Comparative Example 11
A photoconductor was prepared in exactly the same manner as in Example 7, except that only the protective layer coating solution 1 was used as the protective layer in Example 7 and a 3 μm protective layer was formed.
[0136]
Comparative Example 12
A photoconductor was prepared in the same manner as in Example 7 except that only the protective layer coating solution 2 was used as the protective layer in Example 7 and a 3 μm protective layer was formed.
[0137]
Comparative Example 13
A photoconductor was prepared in the same manner as in Example 7 except that only the protective layer coating solution 3 was used as the protective layer in Example 7 and a protective layer of 3 μm was formed.
[0138]
Test example 2
The photoconductors of Examples 6 and 7 and Comparative Examples 7 to 13 produced as described above were mounted in the electrophotographic process shown in FIG. 6 (however, no exposure before cleaning), and the image exposure light source was an LED of 655 nm. Then, 30,000 sheets were printed continuously, and the images at that time were evaluated at the initial stage and after 30,000 sheets. Furthermore, the amount of wear on the surface of the photoreceptor on 30,000 sheets was also measured. The above results are also shown in Table 2.
[Table 2]

[0139]
Example 8
The filler used in Example 6 was surface-treated with a titanate coupling agent so that the treatment amount was 20%. Using this filler, protective layer coating solutions 1, 2, and 3 in Example 6 were produced. About these, the average particle diameter (Horiba Seisakusho: measured with CAPA700) in a coating liquid and the settling property of a coating liquid (The sedimentation degree of the coating liquid particle | grains left still in a test tube was confirmed with the naked eye). The results are shown in Table 3. In addition, the value shown in Table 3 is a measurement result of each protective layer coating liquid 3.
[0140]
Example 9
The filler used in Example 6 was treated with Al so that the treatment amount was 20%.₂O₃The surface treatment was performed. Using this filler, protective layer coating solutions 1, 2, and 3 in Example 6 were produced. About these, the average particle diameter (Horiba Seisakusho: measured with CAPA700) in a coating liquid and the settling property of a coating liquid (The sedimentation degree of the coating liquid particle | grains left still in a test tube was confirmed with the naked eye). The results are shown in Table 3. In addition, the value shown in Table 3 is a measurement result of each protective layer coating liquid 3.
[0141]
[Table 3]

[0142]
Example 10
Using the dispersion prepared in Example 8, a photoconductor was prepared in the same manner as in Example 6. Moreover, only the protective layer was formed on the polyester film as a transmittance measurement sample. Table 4 shows the appearance results of the photoreceptor, the surface roughness Rz, and the transmittance at 655 nm.
[0143]
Example 11
Using the dispersion prepared in Example 9, a photoconductor was prepared in the same manner as in Example 6. Moreover, only the protective layer was formed on the polyester film as a transmittance measurement sample. Table 4 shows the appearance results of the photoreceptor, the surface roughness Rz, and the transmittance at 655 nm.
[0144]
[Table 4]

[0145]
Example 12
The photoconductor produced in Example 10 was mounted on the same apparatus used for the evaluation in Example 6 and image evaluation was performed. As a result, the resolution of the photoconductor using the dispersion liquid of Example 8 was superior to that of the photoconductor using the dispersion liquid of Example 6.
[0146]
Example 13
The photoconductor produced in Example 11 was mounted on the same apparatus used for the evaluation in Example 6 above, and image evaluation was performed. As a result, the resolution of the photoconductor using the dispersion liquid of Example 9 was superior to that of the photoconductor using the dispersion liquid of Example 6.
[0147]
Example 14
An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition are sequentially applied and dried on an aluminum cylinder to generate a 3.5 μm undercoat layer and a 0.2 μm charge generation. An electrophotographic photoreceptor comprising a layer, a 21 μm charge transport layer and a 4 μm protective layer was formed.
◎ Undercoat layer coating solution
400 parts of titanium dioxide powder
65 parts of melamine resin
120 parts alkyd resin
2-butanone 400 parts
◎ Charge generation layer coating solution
8 parts titanyl phthalocyanine having the spectrum of FIG.
(Titanyl phthalocyanine described in JP 2001-19871 A)
Polyvinyl butyral 5 parts
2-butanone 400 parts
◎ Charge transport layer coating solution
10 parts of Z-type polycarbonate
7 parts of charge transport material with the following structural formula
Embedded image

80 parts of methylene chloride
◎ Protective layer coating solution 1
10 parts of polyarylate
8 parts of charge transport material of the following structural formula
Embedded image

Tin oxide powder (specific resistance: 10⁵Ω · cm, average primary particle size 0.4μm) 6 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 2
10 parts of polyarylate
8 parts of charge transport material of the following structural formula
Embedded image

Powder (specific resistance: 10⁵Ω · cm, average primary particle size 0.4μm) 3 parts
Alumina fine particles (specific resistance: 2.5 × 10¹²Ω · cm, average primary particle size 0.4 μm
3 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 3
10 parts of polyarylate
8 parts of charge transport material of the following structural formula
Embedded image

Alumina fine particles (2.5x10¹²Ω · cm, average primary particle size 0.4μm) 6 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
[0148]
The protective layer coating solution was continuously applied by the spray method in the order of the protective layer coating solutions 1, 2, and 3. In this case, the term “continuous” means that the next coating liquid is laminated by a spray method after the lower layer is coated and before the touch is dried. The protective layer coating solutions 1 and 2 were applied in an amount corresponding to 1.5 μm, and the protective layer coating solution 3 was applied in an amount corresponding to 1 μm to form a total protective layer of 4 μm.
[0149]
Comparative Example 14
A photoconductor was prepared in the same manner as in Example 14 except that only the protective layer coating solution 1 was used as the protective layer in Example 14 and a 4 μm protective layer was formed.
[0150]
Comparative Example 15
A photoconductor was prepared in the same manner as in Example 14 except that only the protective layer coating solution 2 was used as the protective layer in Example 14 and a 4 μm protective layer was formed.
[0151]
Comparative Example 16
A photoconductor was prepared in the same manner as in Example 14 except that only the protective layer coating solution 3 was used as the protective layer in Example 14 and a 4 μm protective layer was formed.
[0152]
Comparative Example 17
A photoconductor was prepared in the same manner as in Example 14 except that the protective layer in Example 14 was not laminated and the charge transport layer was 25 μm.
[0153]
Test example 3
The photoconductors of Example 14 and Comparative Examples 14-17 produced as described above are mounted on the electrophotographic process cartridge shown in FIG. 7, and the image exposure light source is a 780 nm semiconductor laser (image writing by a polygon mirror). Then, 20,000 sheets were continuously printed, and the images at that time were evaluated at the initial stage and after 20,000 sheets. In addition, the amount of wear on the surface of the photoreceptor on 20,000 sheets was also measured. The above results are also shown in Table 5.
[Table 5]

[0154]
Example 15
An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition are sequentially applied and dried on an aluminum cylinder to generate a 3.5 μm undercoat layer and a 0.2 μm charge generation. An electrophotographic photosensitive member comprising a layer, a 20 μm charge transport layer, and a 5 μm protective layer was formed. The undercoat layer, charge generation layer, and charge transport layer were applied by a dip coating method, and the protective layer was applied by a spray method.
◎ Undercoat layer coating solution
400 parts of titanium dioxide powder
65 parts of melamine resin
120 parts alkyd resin
2-butanone 400 parts
◎ Charge generation layer coating solution
12 parts of bisazo pigment with the following structure
Embedded image

Polyvinyl butyral 5 parts
2-butanone 200 parts
400 parts of cyclohexanone
◎ Charge transport layer coating solution
10 parts of A type polycarbonate
8 parts of charge transport material of the following structural formula
Embedded image

Tetrahydrofuran 200 parts
◎ Protective layer coating solution 1
10 parts of C type polycarbonate
7 parts of charge transport material with the following structural formula
Embedded image

Tin oxide powder
(Resistivity: 1x10⁵Ω · cm, average primary particle size: 0.2 μm) 5 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 2
10 parts of C type polycarbonate
7 parts of charge transport material with the following structural formula
Embedded image

Tin oxide powder (specific resistance: 1 × 10⁵Ω · cm, average primary particle size: 0.2 μm) 3 parts
Alumina fine particles (specific resistance: 2.5 × 10¹²Ω · cm, average primary particle size: 0.4μ
m) 2 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 3
10 parts of C type polycarbonate
7 parts of charge transport material with the following structural formula
Embedded image

Alumina fine particles
(Specific resistance: 2.5 × 10¹²Ω · cm, average primary particle size: 0.4 μm) 5 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
[0155]
The above-mentioned protective layer coating solution was sequentially applied by a spray method using three spray heads in the order of the protective layer coating solutions 1, 2, and 3. This sequential coating refers to laminating the next coating solution by the spray method after the touch-drying is completed after coating the lower layer. The protective layer coating solutions 1 and 2 were applied in an amount corresponding to 2 μm, and the protective layer coating solution 3 was applied in an amount corresponding to 1 μm to form a total protective layer of 5 μm.
[0156]
Example 16
A photoconductor was prepared in the same manner as in Example 1 except that the protective layer coating solutions 1, 2, and 3 in Example 15 were changed to those having the following compositions, respectively.
◎ Protective layer coating solution 1
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Tin oxide powder (specific resistance: 1 × 10⁶Ω · cm, average primary particle size: 0.4 μm) 2 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 2
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Tin oxide powder (specific resistance: 1 × 10⁶Ω · cm, average primary particle size: 0.4 μm) 1 part
Alumina fine particles (specific resistance: 2.5 × 10¹²Ω · cm, average primary particle size: 0.4μ
m) 1 copy
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 3
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Alumina fine particles (specific resistance: 2.5 × 10¹²Ω · cm, average primary particle size: 0.4μ
m) 2 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
[0157]
Comparative Example 18
A photoconductor was prepared in exactly the same manner as in Example 15 except that only the protective layer coating solution 1 was used as the protective layer in Example 15 and a 5 μm protective layer was formed.
[0158]
Comparative Example 19
A photoconductor was prepared in the same manner as in Example 15 except that only the protective layer coating solution 2 was used as the protective layer in Example 15 and a 5 μm protective layer was formed.
[0159]
Comparative Example 20
A photoconductor was prepared in exactly the same manner as in Example 15 except that only the protective layer coating solution 3 was used as the protective layer in Example 15 and a 5 μm protective layer was formed.
[0160]
Comparative Example 21
A photoconductor was prepared in the same manner as in Example 16 except that only the protective layer coating solution 1 was used as the protective layer in Example 16 and a 5 μm protective layer was formed.
[0161]
Comparative Example 22
A photoconductor was prepared in the same manner as in Example 16 except that only the protective layer coating solution 2 was used as the protective layer in Example 16 and a 5 μm protective layer was formed.
[0162]
Comparative Example 23
A photoconductor was prepared in the same manner as in Example 16 except that only the protective layer coating solution 3 was used as the protective layer in Example 16 and a 5 μm protective layer was formed.
[0163]
Comparative Example 24
The photoconductors of Examples 15 and 16 and Comparative Examples 18 to 23 produced as described above were mounted on the electrophotographic process shown in FIG. 5 (however, there was no exposure before cleaning, and the charging member was a scorotron charger). The exposure light source was a semiconductor laser of 655 nm (image writing by a polygon mirror), and 20,000 sheets were printed continuously, and the images at that time were evaluated initially and after 20,000 sheets. In addition, the amount of wear on the surface of the photoreceptor on 20,000 sheets was also measured. The above results are also shown in Table 6.
[Table 6]

[0164]
Example 17
The charging member of the electrophotographic process shown in FIG. 5 used in Example 15 was changed from the scorotron charger to the charging roller, and the charging roller was disposed so as to contact the photoreceptor. The photoconductor produced in Example 15 was mounted on this apparatus, and the same evaluation as in Example 15 was performed under the following charging conditions.
Charging condition: DC bias: -850V
[0165]
The initial image and the 20,000th image were both good, but a very slight abnormal image (background stain) based on the charging roller stain (toner filming) was observed in the image after 20,000 copies. However, the ozone odor during continuous printing was much less than that in Example 15.
[0166]
Example 18
An insulating tape having a thickness of 50 μm and a width of 5 mm was attached to both ends of the charging roller used in Example 17, and arranged so as to have a spatial gap (50 μm) between the charging roller surface and the photoreceptor surface. The other conditions were evaluated in the same manner as in Example 17. As a result, no charging roller contamination was observed in Example 17, and both the initial image and the 20,000th image were good. However, when a halftone image was output after 20,000 sheets, image unevenness based on charging unevenness was recognized although it was very slight.
[0167]
Example 19
In the evaluation of Example 18, the same evaluation as in Example 18 was performed except that the charging conditions were changed as follows.
Charging condition: DC bias: -850V
AC bias: 1.8 kV (peak to peak), frequency 1.5 kHz
[0168]
The initial image and the image after 20,000 sheets were good. The charging roller stains observed in Example 17 and the halftone image unevenness observed in Example 18 were not recognized at all.
[0169]
Example 20
An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition are sequentially applied and dried on a nickel belt, and a 3 μm undercoat layer, a 0.3 μm charge generation layer, An electrophotographic photoreceptor comprising a 22 μm charge transport layer and a 3 μm protective layer was formed. The undercoat layer, charge generation layer, and charge transport layer were applied by a dip coating method, and the protective layer was applied by a spray method.
◎ Undercoat layer coating solution
100 parts of titanium dioxide powder
100 parts of alcohol-soluble nylon
500 parts of methanol
300 parts of butanol
◎ Charge generation layer coating solution
10 parts of bisazo pigment with the following structure
Embedded image

Polyvinyl butyral 2 parts
2-butanone 200 parts
400 parts of cyclohexanone
◎ Charge transport layer coating solution
10 parts of Z-type polycarbonate
7 parts of charge transport material with the following structural formula
Embedded image

Tetrahydrofuran 200 parts
◎ Protective layer coating solution 1
10 parts of Z-type polycarbonate
6 parts of charge transport material of the following structural formula
Embedded image

Tin oxide powder (specific resistance: 1 × 10⁶Ω · cm, average primary particle size: 0.4 μm) 5 parts
600 parts of toluene
◎ Protective layer coating solution 2
10 parts of Z-type polycarbonate
6 parts of charge transport material of the following structural formula
Embedded image

Tin oxide powder (specific resistance: 1 × 10⁶Ω · cm, average primary particle size: 0.4 μm) 3 parts
Titanium oxide fine particles (specific resistance: 1.5 × 10¹⁰Ω · cm, average primary particle size: 0.4
μm) 2 parts
600 parts of toluene
◎ Protective layer coating solution 3
10 parts of Z-type polycarbonate
6 parts of charge transport material of the following structural formula
Embedded image

Titanium oxide fine particles (specific resistance: 1.5 × 10¹⁰Ω · cm, average primary particle size: 0.4
μm) 5 parts
600 parts of toluene
[0170]
The above-mentioned protective layer coating solution was sequentially applied by a spray method using three spray heads in the order of the protective layer coating solutions 1, 2, and 3. This sequential coating refers to laminating the next coating solution by the spray method after the touch-drying is completed after coating the lower layer. The protective layer coating solutions 1, 2, and 3 were applied in an amount corresponding to 1 μm to form a total protective layer of 3 μm.
[0171]
Example 21
A photoconductor was prepared in the same manner as in Example 20 except that the protective layer coating solutions 1, 2, and 3 in Example 20 were changed to those having the following compositions, respectively.
◎ Protective layer coating solution 1
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Tin oxide powder (specific resistance: 1 × 10⁶Ω · cm, average primary particle size: 0.2 μm) 2.5 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 2
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Tin oxide powder (specific resistance: 1 × 10⁶Ω · cm, average primary particle size: 0.2 μm) 1.5 parts
Silica fine particles (specific resistance: 4 × 10¹³Ω · cm, average primary particle size: 0.5 μm) 1 part
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 3
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Silica fine particles (specific resistance: 4 × 10¹³Ω · cm, average primary particle size: 0.5 μm) 2.5 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
[0172]
Comparative Example 24
A photoconductor was prepared in the same manner as in Example 20, except that only the protective layer coating solution 1 was used as the protective layer in Example 20 and a 3 μm protective layer was formed.
[0173]
Comparative Example 25
A photoconductor was prepared in exactly the same manner as in Example 20, except that only the protective layer coating solution 2 was used as the protective layer in Example 20 and a 3 μm protective layer was formed.
[0174]
Comparative Example 26
A photoconductor was prepared in the same manner as in Example 20, except that only the protective layer coating solution 3 was used as the protective layer in Example 20 and a 3 μm protective layer was formed.
[0175]
Comparative Example 27
A photoconductor was prepared in the same manner as in Example 6 except that the protective layer in Example 20 was not laminated and the charge transport layer was 25 μm.
[0176]
Comparative Example 28
A photoconductor was prepared in the same manner as in Example 21 except that only the protective layer coating solution 1 was used as the protective layer in Example 21 and a protective layer of 3 μm was formed.
[0177]
Comparative Example 29
A photoconductor was prepared in the same manner as in Example 21 except that only the protective layer coating solution 2 was used as the protective layer in Example 21 and a 3 μm protective layer was formed.
[0178]
Comparative Example 30
A photoconductor was prepared in the same manner as in Example 21 except that only the protective layer coating solution 3 was used as the protective layer in Example 21 and a protective layer of 3 μm was formed.
[0179]
Test Example 5
The photoconductors of Examples 20 and 21 and Comparative Examples 24 to 30 prepared as described above were mounted in the electrophotographic process shown in FIG. 6 (however, no exposure before cleaning), and the image exposure light source was an LED of 655 nm. Then, 30,000 sheets were printed continuously, and the images at that time were evaluated at the initial stage and after 30,000 sheets. Furthermore, the amount of wear on the surface of the photoreceptor on 30,000 sheets was also measured. The above results are also shown in Table 7.
[0180]
[Table 7]

[0181]
Example 22
The filler used in Example 20 was surface-treated with a titanate coupling agent so that the treatment amount was 20%. Using this filler, protective layer coating solutions 1, 2, and 3 in Example 20 were produced. About these, the average particle diameter (Horiba Seisakusho: measured by CAPA500) in a coating liquid and the sedimentation property of a coating liquid (The sedimentation degree of the coating liquid particle | grains left still in a test tube was confirmed with the naked eye). The results are shown in Table 8. In addition, the value shown in Table 8 is a measurement result of each protective layer coating liquid 3.
[0182]
Example 23
The filler used in Example 20 was treated with Al so that the treatment amount was 20%.₂O₃The surface treatment was performed. Using this filler, protective layer coating solutions 1, 2, and 3 in Example 20 were produced. About these, the average particle diameter (Horiba Seisakusho: measured by CAPA500) in a coating liquid and the sedimentation property of a coating liquid (The sedimentation degree of the coating liquid particle | grains left still in a test tube was confirmed with the naked eye). The results are shown in Table 3. In addition, the value shown in Table 8 is a measurement result of each protective layer coating liquid 8.
[0183]
[Table 8]

[0184]
Example 24
A photoconductor was prepared in the same manner as in Example 20 using the dispersion prepared in Example 22.
Moreover, only the protective layer was formed on the polyester film as a transmittance measurement sample. Table 9 shows the appearance results of the photoreceptor, the surface roughness Rz, and the transmittance at 655 nm.
[0185]
Example 25
A photoconductor was prepared in the same manner as in Example 20 using the dispersion liquid prepared in Example 23.
Moreover, only the protective layer was formed on the polyester film as a transmittance measurement sample. Table 9 shows the appearance results of the photoreceptor, the surface roughness Rz, and the transmittance at 655 nm.
[0186]
[Table 9]

[0187]
Example 26
The photoconductor produced in Example 24 was mounted on the same apparatus as used in the evaluation of Example 20, and image evaluation was performed. As a result, the resolution of the photoreceptor using the dispersion liquid of Example 22 was superior to that of the photoreceptor using the dispersion liquid of Example 20.
[0188]
Example 27
The photoconductor produced in Example 25 was mounted on the same apparatus as used in the evaluation of Example 20, and image evaluation was performed. As a result, the resolution of the photoconductor using the dispersion liquid of Example 23 was superior to that of the photoconductor using the dispersion liquid of Example 20.
[0189]
Example 28
An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition are sequentially applied and dried on an aluminum cylinder to generate a 3.5 μm undercoat layer and a 0.2 μm charge generation. An electrophotographic photoreceptor comprising a layer, a 21 μm charge transport layer and a 4 μm protective layer was formed.
◎ Undercoat layer coating solution
400 parts of titanium dioxide powder
65 parts of melamine resin
120 parts alkyd resin
2-butanone 400 parts
◎ Charge generation layer coating solution
8 parts titanyl phthalocyanine having the XD spectrum shown in FIG.
(Titanyl phthalocyanine described in JP 2001-19871 A)
Polyvinyl butyral 5 parts
2-butanone 400 parts
◎ Charge transport layer coating solution
10 parts of Z-type polycarbonate
7 parts of charge transport material with the following structural formula
Embedded image

80 parts of methylene chloride
◎ Protective layer coating solution 1
10 parts of polyarylate
8 parts of charge transport material of the following structural formula
Embedded image

Tin oxide-antimony oxide powder
(Specific resistance: 10⁶Ω · cm, average primary particle size 0.4μm) 6 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 2
10 parts of polyarylate
8 parts of charge transport material of the following structural formula
Embedded image

Tin oxide-antimony oxide powder
(Specific resistance: 10⁶Ω · cm, average primary particle size 0.4μm) 3 parts
Alumina fine particles (specific resistance: 2.5 × 10¹³Ω · cm, average primary particle size 0.6μm
3 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 3
10 parts of polyarylate
8 parts of charge transport material of the following structural formula
Embedded image

Alumina fine particles (specific resistance: 2.5 × 10¹³Ω · cm, average primary particle size 0.6μm
6 parts
Tetrahydrofuran 400 parts
Cyclohexanone
200 copies
[0190]
The above-mentioned protective layer coating solution was sequentially applied by a spray method using three spray heads in the order of the protective layer coating solutions 1, 2, and 3. This sequential coating refers to laminating the next coating solution by the spray method after the touch-drying is completed after coating the lower layer. The protective layer coating solutions 1 and 2 were applied in an amount corresponding to 1.5 μm, and the protective layer coating solution 3 was applied in an amount corresponding to 1 μm to form a total protective layer of 4 μm.
[0191]
Comparative Example 31
A photoconductor was prepared in the same manner as in Example 28 except that only the protective layer coating solution 1 was used as the protective layer in Example 28 and a 4 μm protective layer was formed.
[0192]
Comparative Example 32
A photoconductor was prepared in the same manner as in Example 28 except that only the protective layer coating solution 2 was used as the protective layer in Example 28 and a 4 μm protective layer was formed.
[0193]
Comparative Example 33
A photoconductor was prepared in the same manner as in Example 28 except that only the protective layer coating solution 3 was used as the protective layer in Example 28 and a 4 μm protective layer was formed.
[0194]
Comparative Example 34
A photoconductor was prepared in the same manner as in Example 14 except that the protective layer in Example 28 was not laminated and the charge transport layer was 25 μm.
[0195]
Test Example 6
The photoconductors of Example 28 and Comparative Examples 31 to 34 produced as described above are mounted on the electrophotographic process cartridge shown in FIG. 5, and the image exposure light source is a 780 nm semiconductor laser (image writing by a polygon mirror). Then, 20,000 sheets were continuously printed, and the images at that time were evaluated at the initial stage and after 20,000 sheets. In addition, the amount of wear on the surface of the photoreceptor on 20,000 sheets was also measured. The above results are also shown in Table 10.
[0196]
[Table 10]

[0197]
Example 29
A photoconductor was prepared in the same manner as in Example 6 except that the protective layer coating solutions 1, 2, and 3 in Example 6 were changed to those having the following compositions, respectively.
◎ Protective layer coating solution 1
10 parts of Z-type polycarbonate
6 parts of charge transport material of the following structural formula
Embedded image

Tin oxide-antimony oxide powder
(Specific resistance: 10⁶Ω · cm, average primary particle size 0.4μm) 5 parts
600 parts of toluene
◎ Protective layer coating solution 2
10 parts of Z-type polycarbonate
6 parts of charge transport material of the following structural formula
Embedded image

Tin oxide-antimony oxide powder
(Specific resistance: 10⁶Ω · cm, average primary particle size 0.4μm) 3 parts
Titanium oxide fine particles (specific resistance: 1.5 × 10¹⁰Ω · cm, average primary particle size: 0.4
μm) 2 parts
600 parts of toluene
◎ Protective layer coating solution 3
10 parts of Z-type polycarbonate
6 parts of charge transport material of the following structural formula
Embedded image

Titanium oxide fine particles (specific resistance: 1.5 × 10¹⁰Ω · cm, average primary particle size: 0.4
μm) 5 parts
600 parts of toluene
[0198]
Test Example 7
The photoconductors of Examples 6 and 29 produced as described above were mounted in the electrophotographic process shown in FIG. 6 (however, exposure before cleaning was not performed), and the image exposure light source was an LED of 655 nm and was continuously 30,000. Sheets were printed, and the images at that time were evaluated at the initial stage and after 30,000 sheets. Furthermore, the amount of wear on the surface of the photoreceptor on 30,000 sheets was also measured. The above results are also shown in Table 11.
[Table 11]

[0199]
Example 30
A photoconductor was prepared in the same manner as in Example 20 except that the protective layer coating solutions 1, 2, and 3 in Example 20 were changed to those having the following compositions, respectively.
◎ Protective layer coating solution 1
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Tin oxide powder (specific resistance: 1 × 10⁶Ω · cm, average primary particle size: 0.2 μm) 2.5 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 2
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Tin oxide powder (specific resistance: 1 × 10⁶Ω · cm, average primary particle size: 0.2 μm) 1.5 parts
Silica fine particles (specific resistance: 4 × 10¹³Ω · cm, average primary particle size: 0.2 μm) 1 part
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
◎ Protective layer coating solution 3
Polymer charge transport material of the following structural formula: 7 parts
Embedded image

Silica fine particles (specific resistance: 4 × 10¹³Ω · cm, average primary particle size: 0.2 μm) 2.5 parts
Tetrahydrofuran 400 parts
200 parts of cyclohexanone
[0200]
Test Example 8
The photoconductors of Examples 20 and 30 produced as described above were mounted in the electrophotographic process shown in FIG. 6 (however, exposure before cleaning was not performed), and the image exposure light source was an LED of 655 nm and was continuously 30,000. Sheets were printed, and the images at that time were evaluated at the initial stage and after 30,000 sheets. Furthermore, the amount of wear on the surface of the photoreceptor on 30,000 sheets was also measured. The above results are also shown in Table 12.
[Table 12]

[0201]
Example 31
In Example 28, the conductive support (JIS1050) was subjected to the following anodic oxide film treatment, and then a charge generation layer, a charge transport layer, and a protective layer were provided in the same manner as in Example 28 without providing an undercoat layer. A photoconductor was prepared.
◎ Anodic oxide film treatment
The surface of the support was mirror-polished, degreased and washed with water, then immersed in an electrolytic bath at a liquid temperature of 20 ° C. and sulfuric acid of 15 vol. . Further, after washing with water, sealing treatment was performed with a 7% nickel acetate aqueous solution (50 ° C.). Thereafter, washing with pure water was performed to obtain a support on which a 6 μm anodic oxide film was formed.
[0202]
Test Example 9
The photoconductors produced in Example 28 and Example 31 were mounted on the electrophotographic process cartridge shown in FIG. 7, and the image exposure light source was a 780 nm semiconductor laser (image writing by a polygon mirror). Sheets were printed, and the images at that time were evaluated at the initial stage and after 20,000 sheets. As a result, when both images after 20,000 sheets are compared, there is no problem in practical use. Slightly more.
[0203]
Example 32
The photoreceptor prepared in Example 1 was mounted on the electrophotographic apparatus shown in FIG. 10, and all four image forming elements were subjected to image evaluation of 20000 full-color images under the process conditions shown below. The results are shown in Table 13.
・ Charging conditions
DC bias: -800V
AC bias: 2.0 kV (peak to peak), frequency 2 kHz
・ Exposure conditions
655nm semiconductor laser (image writing by polygon mirror)
[0204]
Comparative Example 35
An image evaluation test was conducted in the same manner as in Example 32 except that the photoconductor produced in Comparative Example 1 was used instead of the photoconductor used in Example 32. The results are shown in Table 13.
[0205]
Comparative Example 36
An image evaluation test was conducted in the same manner as in Example 32 except that the photoconductor produced in Comparative Example 3 was used instead of the photoconductor used in Example 32. The results are shown in Table 13.
[Table 13]

[0206]
【The invention's effect】
According to the present invention, a photoconductor capable of forming a high-quality image that is highly durable and stable for repeated use is provided. There are also provided an electrophotographic method, an electrophotographic apparatus, and an electrophotographic process cartridge capable of forming a stable high-quality image at high speed even after repeated use.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of an example of an electrophotographic photosensitive member of the present invention.
FIG. 2 is a cross-sectional view of an example of the electrophotographic photosensitive member of the present invention.
FIG. 3 is a cross-sectional view of an example of the electrophotographic photosensitive member of the present invention.
FIG. 4 is a cross-sectional view of an example of the electrophotographic photosensitive member of the present invention.
FIG. 5 is a schematic diagram for explaining an electrophotographic apparatus of the present invention.
FIG. 6 is a schematic diagram for explaining an electrophotographic process of the present invention.
FIG. 7 is a schematic diagram for explaining a process cartridge for an apparatus of an electrophotographic process according to the present invention.
8 is an XD spectrum diagram of titanyl phthalocyanine used in Example 11. FIG.
FIG. 9 is a diagram illustrating an example of a proximity charging mechanism in which a gap forming member is disposed on the charging member side.
FIG. 10 is a schematic diagram for explaining the full-color electrophotographic apparatus of the present invention.
[Explanation of symbols]
1 Conductive support
2 Photosensitive layer
3 Protective layer
4 Charge generation layer
5 Charge transport layer
6 Photoconductor
7 Static elimination lamp
8 Charging member
10 Image exposure section
11 Development unit
12 Pre-transfer charger
13 Registration roller
14 Transfer paper
15 Transfer belt
16 Separating nails
17 Charger before cleaning
18 Fur brush
19 Cleaning brush
21 photoconductor
22 Driving roller
23 Charging roller
24 Image exposure source
25 Transcription charger
26 Exposure before cleaning
27 Cleaning brush
28 Static elimination light source
30 Charging member
31 Image exposure unit
32 Cleaning brush
33 photoconductor
34 Transfer roller
35 Development roller
36 photoconductor
37 Charging roller
38 Gap forming member
39 Metal shaft
40 Image formation area
41 Non-image forming area
101C, 101M, 101Y, 101K photoconductor
102C, 102M, 102Y, 102K Charging member
103C, 103M, 103Y, 103K Laser light
04C, 104M, 104Y, 104K Development member
105C, 105M, 105Y, 105K Cleaning member
106C, 106M, 106Y, 106K Image forming elements
107 Transfer paper
108 Feed roller
109 Registration Roller
110 Transfer conveyor belt
111C, 111M, 111Y, 111K transfer brush
112 Fixing device

Claims (32)

In an electrophotographic photosensitive member in which a photosensitive layer containing at least an organic charge generating substance and an organic charge transporting substance and a protective layer are provided on a conductive support, the protective layer contains two or more kinds of fillers having different specific resistances. An electrophotographic photosensitive member characterized in that the proportion of the filler having the largest specific resistance with respect to all fillers in the protective layer has a slope that continuously increases from the photosensitive layer side to the surface side. In an electrophotographic photosensitive member in which a photosensitive layer containing at least an organic charge generating substance and an organic charge transporting substance and a protective layer are provided on a conductive support, the protective layer is composed of two or more layers, The protective layer contains two or more kinds of fillers having different specific resistances, and the ratio of the filler having the largest specific resistance to all fillers in the protective layer is gradually increased from the photosensitive layer side to the surface side layer. An electrophotographic photosensitive member characterized by the above. 3. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer has a laminated structure of a charge generation layer containing at least an organic charge generation material and a charge transport layer containing an organic charge transport material. The electrophotographic photoreceptor according to claim 1, wherein the organic charge generating substance is an azo pigment or a phthalocyanine pigment. The electrophotographic photosensitive member according to claim 1, wherein the filler having a large specific resistance contained in the protective layer is an inorganic pigment having a specific resistance of 10 ¹⁰ Ω · cm or more. The electrophotographic photosensitive member according to claim 5, wherein the inorganic pigment is a metal oxide having a specific resistance of 10 ¹⁰ Ω · cm or more. The electrophotographic photosensitive member according to claim 6, wherein the metal oxide is selected from the group consisting of silica, alumina, and titanium oxide. 6. The electrophotographic photosensitive member according to claim 5, wherein the inorganic pigment has a pH of 5 or more. 6. The electrophotographic photosensitive member according to claim 5, wherein the dielectric constant of the inorganic pigment is 5 or more. 6. The electrophotographic photosensitive member according to claim 5, wherein the inorganic pigment is subjected to surface treatment with at least one kind of surface treatment agent. The inorganic pigment surface treatment agent is one selected from the group consisting of titanate coupling agents, aluminum coupling agents, higher fatty acid series, Al ₂ O ₃ , TiO ₂ , and ZrO ₂ , or those The electrophotographic photosensitive member according to claim 10, wherein the electrophotographic photosensitive member is a mixture of the above and a mixture thereof with a silane coupling agent. The electrophotographic photosensitive member according to claim 10 or 11, wherein the surface treatment amount of the inorganic pigment contained in the protective layer is 3 to 30 wt%. The average primary particle diameter of the filler having a large specific resistance among the fillers contained in the protective layer of the photoreceptor is 0.3 μm to 1.0 μm. The electrophotographic photosensitive member described. The electrophotography according to claim 1, wherein in the outermost layer of the protective layer of the photoreceptor, the ratio of fillers having a large specific resistance among all fillers contained is 70% or more. Photoconductor. The filler used for the said protective layer WHEREIN: The specific resistance of a filler with a small volume average particle diameter is smaller than the specific resistance of a filler with a large volume average particle diameter, The any one of Claims 1-14 characterized by the above-mentioned. The electrophotographic photoreceptor described in 1. The electrophotographic photosensitive member according to claim 1, wherein the protective layer contains a charge transport material. 17. The electrophotographic photoreceptor according to claim 16, wherein the charge transport material contained in the protective layer is a polymer charge transport material. 18. The electrophotographic photoreceptor according to claim 17, wherein the polymer charge transport material contained in the protective layer is a polycarbonate containing at least a triarylamine structure in the main chain or side chain. The electrophotographic photosensitive member according to any one of claims 1 to 18, wherein the binder resin contained in the protective layer contains at least one of a polycarbonate resin and a polyarylate resin. The electrophotographic photosensitive member according to any one of claims 1 to 19, wherein the surface of the conductive support of the electrophotographic photosensitive member is anodized. Two or more types of filler dispersions with different specific resistances are sprayed simultaneously using two or more spray heads, and the ratio of the discharge amount is continuously changed to protect the two types of fillers in proportion. 2. The method for producing an electrophotographic photosensitive member according to claim 1, wherein a layer is formed. Two or more types of fillers having different specific resistances are sprayed simultaneously using two or more spray heads, and the ratio of the discharge amount is changed stepwise, and a plurality of different types of fillers are present in different proportions. The method for producing an electrophotographic photosensitive member according to claim 2, wherein a protective layer is formed. Using two or more types of coating liquids with different abundance ratios of two types of fillers with different specific resistances, coating is performed in order from the liquid with the smaller abundance ratio of fillers with larger specific resistances. 2. The method for producing an electrophotographic photosensitive member according to claim 1, wherein a protective layer is formed by laminating the following coating solution before the coated film is dry to the touch. Using two or more types of coating liquids with different abundance ratios of two types of fillers with different specific resistances, coating is performed in order from the liquid with the smaller abundance ratio of fillers with larger specific resistances. 3. The method for producing an electrophotographic photosensitive member according to claim 2, wherein when the coated film is dry to the touch, the next coating solution is laminated to form a protective layer. A so-called digital electronic device in which at least charging, image exposure, development, and transfer are repeatedly performed on an electrophotographic photosensitive member, and an electrostatic latent image is written on the photosensitive member by an LD or LED during image exposure. 21. An electrophotographic method according to claim 1, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 1 to 20. 21. An electrophotographic apparatus comprising at least a charging unit, an image exposing unit, a developing unit, a transferring unit, and an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is an electron according to any one of claims 1 to 20. An electrophotographic apparatus which is a photographic photosensitive member. In an electrophotographic apparatus comprising at least a charging unit, an image exposing unit, a developing unit, a transferring unit, and an electrophotographic photosensitive member, an electrostatic latent image is formed on the photosensitive member by using an LD or an LED as the image exposing unit. 21. A so-called digital electrophotographic apparatus in which writing is performed, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 1 to 20. 28. The electrophotographic apparatus according to claim 26 or 27, wherein the charging means comprises a charging member arranged in contact with or close to the photosensitive member. 29. The electrophotographic apparatus according to claim 28 , wherein a gap between the charging member and the photosensitive member is 200 [mu] m or less when the charging member and the photosensitive member are disposed close to each other . 30. The electrophotographic apparatus according to claim 26, wherein an alternating current component is superimposed on a direct current component on the charging member to charge the photosensitive member. A full-color electrophotographic apparatus in which a plurality of image forming elements comprising at least an electrophotographic photosensitive member, a charging unit, an image exposing unit, a developing unit, and a transferring unit are arranged, wherein the electrophotographic photosensitive unit is defined in claims 1 to 20. A full-color electrophotographic apparatus, which is the electrophotographic photosensitive member according to any one of the above. A process cartridge for an electrophotographic apparatus comprising at least an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 1 to 20. Process cartridge for electrophotographic equipment.

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