JP2004045995A - Electrophotographic photoreceptor, and process cartridge and image forming device each having the electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor excellent in electrophotographic charateristics without causing light scattering and bleed and good in coatability in manufacturing, and to provide a process cartridge and an image forming device having the electrophotographic photoreceptor. <P>SOLUTION: In the electrophotographic photoreceptor having a photoreceptor layer on a supporting body, the photoreceptor layer of the electrophotographic photoreceptor contains a resin expressed by formula (1), where A is a hole-transporting radical, B is an alkylene group of 2C to 6C, R<SP>2</SP>is a substituent or a non-substituent bivalent hydrocarbon group or an alkylene oxyalkylene group of 2C to 10C, R<SP>1</SP>is a substituent or a non-substituent monovalent hydrocarbon group of 1C to 10C excluding an alphatic unsaturated binding, and R<SP>1</SP>s may be the same or different. X is an integer of ≥1, y is an integer of ≥2, and z is an integer of ≥0. <P>COPYRIGHT: (C)2004,JPO

Description

【００１４】
（Ａは正孔輸送性基を示す。Ｂは炭素原子数２〜６のアルキレン基を示す。Ｒ^１は脂肪族不飽和結合を含まない置換もしくは無置換の炭素原子数１〜１０の一価炭化水素基を示し、Ｒ^１は同一であっても違っても良い。Ｒ^２は置換もしくは非置換の炭素原子数２〜１０の二価炭化水素基またはアルキレンオキシアルキレン基を示す。ｘは１以上の整数であり、ｙ及びｚは０以上の整数であるが、（ｙ＋ｚ）は２以上の整数である。）
また、本発明は、上記電子写真感光体を有するプロセスカートリッジ及び画像形成装置である。
【００１５】
【発明の実施の形態】
以下、本発明を詳細に説明する。
【００１６】
上記式（１）中のＡで示される二価有機基としては、電荷輸送性基として知られているものが好ましい。本発明における電荷輸送性とは電荷を輸送する能力のことであり、イオン化ポテンシャルで６．２ｅＶ以下であることが好ましい。つまりＡの水素付加物は、イオン化ポテンシャルが６．２ｅＶ以下であることが好ましく、特には４．５〜６．２ｅＶであることが好ましい。イオン化ポテンシャルが６．２ｅＶを越えると正孔注入が起こりにくく帯電し易くなる。また、４．５ｅＶ未満では化合物が容易に酸化されるために劣化し易くなる。イオン化ポテンシャルは大気下光電子分析法（理研計器製、表面分析装置ＡＣ−１）によって測定される。
【００１７】
このようなＡで表される二価有機基としては具体的には、その水素付加化合物（電荷輸送物質）として示せば、例えば、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、トリフェニルアミン等のトリアリールアミン誘導体、９−（ｐ−ジエチルアミノスチリル）アントラセン、１，１−ビス−（４−ジベンジルアミノフェニル）プロパン、スチリルアントラセン、スチリルピラゾリン、フェニルヒドラゾン類、α−フェニルスチルベン誘導体、チアゾール誘導体、イミダゾール誘導体、トリフェニルアミン等のトリアリールアミン誘導体、９−（ｐ−ジエチルアミノスチリル）アントラセン、１，１−ビス−（４−ジベンジルアミノフェニル）プロパン、スチリルアントラセン、スチリルピラゾリン、フェニルヒドラゾン類、α−フェニルスチルベン誘導体、チアゾール誘導体、トリアゾール誘導体、フェナジン誘導体、アクリジン誘導体、ベンゾフラン誘導体、ベンズイミダゾール誘導体、チオフェン誘導体、Ｎ−フェニルカルバゾール誘導体等が挙げられる。以下に具体例を示す。下式中、Ｐｈはフェニル基であり、Ｍｅはメチル基であり、Ｅｔはエチル基であり、Ｂｕはブチル基であり、Ｐｒはプロピル基を意味する。
【外４】

【００１８】
【外５】

【００１９】
【外６】

【００２０】
【外７】

【００２１】
【外８】

【００２２】
【外９】

【００２３】
【外１０】

【００２４】
【外１１】

【００２５】
【外１２】

【００２６】
【外１３】

【００２７】
【外１４】

【００２８】
【外１５】

【００２９】
【外１６】

【００３０】
これらの中でも、正孔輸送性基Ａには構造が下記式（２）で示されるものが好適に使用できる。
【外１７】

【００３１】
（Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は有機基であり、そのうちの少なくとも１つは芳香族炭化水素環基または複素環基を示し、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は同一であっても異なっていてもよい。Ｒ^６は芳香族炭化水素環基をしめす。）
この際、正孔輸送性基ＡはＲ^２、Ｒ^３、Ｒ^４及びＲ^５のうちの２つの基の水素原子が除かれて形成された基である。
【００３２】
Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５の構造の好ましい具体例を以下に示す。
【外１８】

【００３３】
【外１９】

【００３４】
Ｒ^６の構造の好ましい具体例を以下に示す。
【外２０】

【００３５】
【外２１】

【００３６】
Ｂは炭素数２〜６のアルキレン基であり、具体的にはエチレン基、メチルエチレン基、エチルエチレン基、プロピルエチレン基、ブチルエチレン基、プロピレン基、ブチレン基、１−メチルプロピレン基、ペンチレン基、ヘキシレン基等の直鎖状もしくは分岐鎖状のアルキレン基が例示される。これらの中でもエチレン基、プロピレン基、ブチレン基、ヘキシレン基が好ましい。Ｒ^１は脂肪族不飽和結合を含まない置換もしくは非置換の炭素原子数１〜１０の一価炭化水素基であり、具体的にはメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基；フェニル基、トリル基、キシリル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基；トリフルオロプロピル基、ノナフルオロヘキシル基、ヘプタデカフルオロオクチル基等のフッ化炭化水素基が例示されるが、これらの中でもメチル基またはフェニル基が好ましい。Ｒは置換もしくは非置換の炭素原子数２〜１０の二価炭化水素基またはアルキレンオキシアルキレン基である。二価炭化水素基としては、エチレン基、メチルエチレン基、エチルエチレン基、プロピルエチレン基、ブチルエチレン基、プロピレン基、ブチレン基、１−メチルプロピレン基、ペンチレン基、ヘキシレン基等の直鎖状もしくは分岐鎖状のアルキレン基；ｐ−フェニレン基、ｍ−フェニレン基、ｏ−フェニレン基、２−メチル−１，４−フェニレン基、２−メトキシ−１，４−フェニレン基等のフェニレン基が例示される。アルキレンオキシアルキレン基としては、エチレンオキシエチレン基が例示される。これらの中でもＲは、エチレン基またはｐ−フェニレン基であることが好ましい。ｘは１以上の整数であり、ｙ及びｚは０以上の整数であるが、（ｙ＋ｚ）は２以上である。具体的にはｘは、１〜２０００の範囲であることが好ましくは、２〜１０００の範囲であることがより好ましい。ｙは、２〜２０００の範囲であることが好ましく、２〜１０００の範囲であることがより好ましい。ｚは、通常０〜１０００の範囲である。
【００３７】
一般式（１）で表される樹脂の分子鎖末端は特に限定されないが、例えば、水素原子、水酸基やアルコキシ基等の加水分解性基、置換もしくは非置換の一価炭化水素基、式：Ｒ^７ _３−Ｓｉ−（Ｑ）_ｐ−（式中、Ｒ^７は水素原子、加水分解性基、置換もしくは非置換の一価炭化水素基であり、ｐは０または１であり、Ｑは酸素原子または置換もしくは非置換の二価炭化水素基である。尚、Ｒ^７は同一でも異種でもよい。）で示されるシリル基が挙げられる。また、一般式（１）で表される樹脂の重量平均分子量は、通常、１０００〜１００００００の範囲であり、５０００〜５０００００の範囲であることが好ましい。
【００３８】
このような一般式（１）で表される樹脂の具体例としては、下記式で示される化合物が挙げられる。下式中、Ｐｈはｐ−フェニレン基を表し、Ｍｅはメチル基を表し、Ａは上記のような構造である。
【外２２】

【００３９】
上記一般式（１）で示される樹脂は、ヒドロシリル化反応用触媒の存在下、一般式（３）：Ｂ^１−Ａ−Ｂ^１（式中、Ａは前記と同じであり、Ｂ^１は炭素原子数２〜６のアルケニル基である。）で示される芳香族化合物と、一般式（４）：
【外２３】

【００４０】
（式中、Ｒ^１及びＲ^２は前記と同じである。）で示されるジシリル化合物と、必要に応じて、一般式（５）
【外２４】

【００４１】
（式中、Ｗは水素原子もしくは炭素原子数２〜６のアルケニル基であり、Ｒ^１は前記と同じである。）で表されるジシロキサン化合物とを付加重合することによって得ることができる。尚、このとき、上記一般式（４）の有機ケイ素化合物と上記式（５）のジシロキサン化合物の両者を付加重合させてもよい。
【００４２】
上記一般式（１）で示される樹脂を製造する際に用いられる電荷輸送性化合物は一般式（３）：Ｂ^１−Ａ−Ｂ^１で表される。一般式（３）においてＢ^１は炭素原子数２〜６のアルケニル基であり、具体的には、ビニル基、アリル、５−ヘキセニル基が例示される。Ａは前記と同じである。このような芳香族化合物としては、下記式で示される化合物が例示される。
【外２５】

【００４３】
上記一般式（１）で示される樹脂を製造する際に用いられる一般式（４）：
【外２６】

【００４４】
で示される有機ケイ素化合物において、式中、Ｒ^１及びＲ^２は前記と同じである。この有機ケイ素化合物の具体例としては、下記式で示される化合物が挙げられる。下式中、Ｒｈはｐ−フェニレン基を表し、Ｍｅはメチル基を表し、Ｃ_６Ｈ_５はフェニル基を表す。
【外２７】

【００４５】
上記一般式（１）で示される樹脂を製造する際に用いられる一般式（５）：
【外２８】

【００４６】
で表されるジシロキサン化合物において、式中、Ｗは水素原子または炭素数２〜６のアルケニル基であり、Ｒ^１は前記と同じである。このジシロキサン化合物の具体例としては、下記式で示される化合物が挙げられる。下式中、Ｍｅはメチル基を表し、Ｃ_６Ｈ_５はフェニル基を表す。
【外２９】

【００４７】
上記一般式（１）で示される樹脂を製造する際に用いられるヒドロシリル化反応触媒としては、担持型もしくは非担持型の白金系触媒が好ましく、具体的には、白金黒、白金担持のシリカ微粉末、白金担持のカーボン粉末、塩化白金酸、塩化白金酸のアルコール溶液、白金とビニルシロキサンとの錯体、白金とオレフィンとの錯体が例示される。またその添加量は白金金属として１〜２０００ｐｐｍが好ましい。尚、使用後の白金系触媒は、活性炭、シリカゲル、アミノシラン処理シリカゲル、メルカプトシラン処理シリカゲル等を添加混合して吸着させた後、ろ過により除去することができる。
【００４８】
さらに、本発明の電子写真感光体に用いるケイ素系樹脂には、一般式（６）：
【外３０】

【００４９】
（式中、Ｒ^１、Ｒ及びＢ^１は前記と同じである。）で表される有機ケイ素化合物を加えて、前記した各化合物と共に付加重合させてもよい。この有機ケイ素化合物としては、下記式で表される化合物が挙げられる。下式中、Ｍｅはメチル基を表し、Ｃ_６Ｈ_５はフェニル基を表す。
【外３１】

【００５０】
また、本発明の電子写真感光体に用いるケイ素系樹脂には、重合停止剤として、アルコキシ基とケイ素原子結合水素原子を有する有機ケイ素化合物、または、アルコキシ基と炭素原子数２〜６のアルケニル基を有する有機ケイ素化合物を用いることが好ましい。このような重合停止剤としては、下記式で示されるシラン化合物が例示される。下式中、Ｍｅはメチル基を表し、Ｖｉはビニル基を表す。
ＨＳｉ（ＯＭｅ）_３
ＨＳｉ（ＯＣ_２Ｈ_５）_３
ＨＭｅＳｉ（ＯＭｅ）_２
ＨＭｅＳｉ（ＯＣ_２Ｈ_５）_２
ＨＭｅ_２ＳｉＯＭｅ
ＶｉＳｉ（ＯＭｅ）_３
ＶｉＳｉ（ＯＣ_２Ｈ_５）_３
ＶｉＭｅＳｉ（ＯＭｅ）_２
ＶｉＭｅＳｉ（ＯＣ_２Ｈ_５）_２
ＶｉＭｅ_２ＳｉＯＭｅ
ＣＨ_２＝ＣＨＣＨ_２Ｓｉ（ＯＭｅ）_３
ＣＨ_２＝ＣＨＣＨ_２Ｓｉ（ＯＣ_２Ｈ_５）_３
ＣＨ_２＝ＣＨＣＨ_２ＳｉＭｅ（ＯＭｅ）_２
ＣＨ_２＝ＣＨ（ＣＨ_２）_４Ｓｉ（ＯＭｅ）_３
ＣＨ_２＝ＣＨ（ＣＨ_２）_４ＳｉＭｅ（ＯＭｅ）_２
ＣＨ_２＝ＣＨ（ＣＨ_２）_４ＳｉＭｅ（ＯＣ_２Ｈ_５）_２
本発明の電子写真感光体に用いるケイ素系樹脂を合成する段階において、各成分の投入順序は任意であるが、付加重合にあたり、各成分を有機溶剤の溶液としてから混合して反応させてもよい。使用できる有機溶剤としては、例えば、ベンゼン、トルエン、キシレンなどの芳香族系溶剤；シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサンなどの脂肪族系溶剤；トリクロロエチレン、１，１，１−トリクロロエタン、四塩化炭素、クロロホルムなどの塩素系溶剤；ヘキサン、工業用ガソリンなどの脂肪族飽和炭化水素系溶剤、ジエチルエーテル、テトラヒドロフランなどのエーテル類；メチルイソブチルケトンなどのケトン系溶剤；α、α、α−トリフルオロトルエン、ヘキサフルオロキシレンなどのフッ素系溶剤；ヘキサメチルジシロキサン、ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサンなどの揮発性シリコーンが挙げられる。有機溶剤を配合する際には、ケイ素系ポリマーが５〜９０重量％となるような量を配合するのが好ましい。
【００５１】
次に、本発明の電子写真感光体を製造する例を下記に示す。
【００５２】
電子写真感光体の支持体としては支持体自体が導電性を有するもの、例えば、アルミニウム、アルミニウム合金、銅、亜鉛、ステンレス、クロム、チタン、ニッケル、マグネシウム、インジウム、金、白金、銀、鉄等を用いることが出来る。その他にアルミニウム、酸化インジウム、酸化スズ、金、等を蒸着等によりプラスチック等の誘電体基材に被膜形成し、導電層としたものや、導電性微粒子をプラスチックや紙に混合したもの等を用いることが出来る。これらの導電性基材は均一な導電性が求められるとともに平滑な表面が重要である。表面の平滑性はその上層に形成される下引き層、電荷発生層、正孔輸送層の均一性に大きな影響を与えることから、その表面荒さは０．３μｍ以下で用いられることが好ましい。０．３μｍ以上の凹凸は下引き層や電荷発生層のような薄い層に印加される局所電場を大きく変化させてしまうためにその特性が大きく変化してしまい電荷注入や残電のむら等の欠陥を生じ易いことから好ましくない。
【００５３】
特に導電性微粒子をポリマーバインダー中に分散して塗布することにより得られる導電層は形成が容易であり、均質な表面を形成することに適している。このとき用いられる導電性微粒子の１次粒径は１００ｎｍ以下であり、より好ましくは５０ｎｍ以下のものが用いられる。導電性微粒子としては、導電性酸化亜鉛、導電性酸化チタン、Ａｌ、Ａｕ、Ｃｕ、Ａｇ、Ｃｏ、Ｎｉ、Ｆｅ、カーボンブラック、ＩＴＯ、酸化スズ、酸化インジウム、インジウム、等が用いられ、これらを絶縁性微粒子の表面にコーティングして用いてもよい。前記導電性微粒子の含有量は体積抵抗が十分に低くなるように使用され、好ましくは１×１０^１０Ωｃｍ以下の抵抗となるように添加される。より好ましくは１×１０^８Ωｃｍ以下で用いられる。
【００５４】
レーザー等のコヒーレントな光源を用いて露光する場合は干渉による画像劣化を防止するために上記導電性基材の表面に凹凸を形成することも可能である。このときは電荷注入や残留電位のむら等の欠陥が生じにくいように使用する波長の１／２λ程度の凹凸を数μｍ以下の直径のシリカビーズ等の絶縁物を分散することに１０μｍ以下の周期で形成して用いることが可能である。
【００５５】
本発明においては、基材と光導電層の中間に、注入阻止機能と接着機能をもつ下引層を設けることもできる。下引き層の材料としてはカゼイン、ポリビニルアルコール、ニトロセルロース、エチレン−アクリル酸コポリマー、ポリビニルブチラール、フェノール樹脂、ポリアミド、ポリウレタン、ゼラチン、等が挙げられる。下引き層の膜厚は０．１μｍ〜１０μｍであることが好ましく、特には０．３μｍ〜３μｍであることが好ましい。
【００５６】
感光層としては電荷発生物質を含有する電荷発生層と電荷輸送物質を含有する電荷輸送層からなる機能分離タイプのものや電荷発生物質と電荷輸送物質を同一の層に含有する単層タイプが用いられる。
【００５７】
機能分離やタイプの感光層について説明すると、感光層の構成としては、電荷発生層上に電荷輸送層を積層する構成と、電荷輸送層上に電荷発生層を積層する構成がある。
【００５８】
電荷発生材料としては、例えば、セレン−テルル、ピリリウム系染料、チオピリリウム系染料、フタロシアニン系顔料、アントアントロン系顔料、ジベンズピレンキノン系顔料、ピラントロン系顔料、アゾ系顔料、インジゴ系顔料、キナクリドン系顔料、シアニン系顔料等を用いることができる。これらの電荷発生材料のうち、本発明においては、特にアゾ顔料及びフタロシアニン顔料が適している。フタロシアニン顔料としては、無金属フタロシアニン、銅フタロシアニン、ガリウムフタロシアニン、オキシチタニウムフタロシアニン等が挙げられる。このうち特に長波長光に対して高感度を有するオキシチタニウムフタロシアニンが好ましく、例えば特開昭６１−２３９２４８号公報、特開昭６２−６７０９４号公報、特開平３−１２８９７３号公報及び平３−２００７９０号公報に開示がある。これらの中でも、特開平３−１２８９７３号公報に開示のＣｕＫα特性Ｘ線回折におけるブラッグ角（２θ±０．２°）において、９．０°、１４．２°、２３．９°及び２７．１°に特徴的なピークを有する結晶形であるオキシチタニウムフタロシアニンがより好ましい。
【００５９】
結着剤としては、広範な絶縁性樹脂から選択でき、例えばポリビニルブチラール、ポリビニルアルコール、ポリアリレート、ポリアミド、アクリル樹脂、ポリ酢酸ビニル、フェノール樹脂、エポキシ樹脂、ポリエステル、ポリカーボネート、ポリウレタン、セルロース系樹脂等の樹脂が挙げられる。電荷発生層中に含有する樹脂は、８０重量％以下、好ましくは５０重量％以下が適している。電荷発生層の厚さは５μｍ以下、特に０．０５〜２μｍであることが好ましい。
【００６０】
本発明の樹脂は電荷輸送層もしくは正孔輸送能を有する表面保護層として用いることが可能である。
【００６１】
本発明における電荷輸送層の膜厚は１〜４０μｍであることが好ましく、特には３〜３０μｍであることが好ましい。本発明における表面保護層の厚みは、１〜１５μｍであることが好ましい。１μｍ以下では保護効果が十分ではなく、１５μｍを越えると感光層全体の膜厚が増加することにより、画像劣化が生じ易くなってしまうことから好ましくない。
【００６２】
光導電層には前記化合物以外にも機械的特性の改良や耐久性向上のために添加剤を用いることができる。このような添加剤としては、酸化防止剤、紫外線吸収剤、安定化剤、架橋剤、潤滑剤、導電性制御剤等が用いられる。
【００６３】
図１に本発明のプロセスカートリッジを有する画像形成装置の第１の例の概略構成を示す。
【００６４】
図において１はドラム状の本発明の電子写真感光体であり、軸２を中心に矢印方向に所定の周速度で回転駆動される。感光体１は、回転過程において、一次帯電手段３によりその周面に正または負の所定電位の均一帯電を受け、次いで、レーザービーム走査露光等の像露光手段（不図示）からの画像露光４を受ける。こうして感光体１の周面に静電潜像が順次形成されていく。
【００６５】
形成された静電潜像は、現像手段５によりトナー現像され、現像されたトナー現像像は不図示の給紙部から感光体１と転写手段６との間に感光体１の回転と同期取り出されて給紙された転写材７に、転写手段６により順次転写されていく。像転写を受けた転写材７は、感光体面から分離されて像定着手段８へ導入されて像定着を受けることにより複写物（コピー）として装着外にプリントアウトされる。
【００６６】
像転写後の感光体１の表面は、クリーニング手段９によって転写残りトナーの除去を受けて清浄面化され、更に前露光手段（不図示）からの前露光光１０により除電処理された後、繰り返し像形成に使用される。なお、一次帯電手段３が帯電ローラー等を用いた接触帯電手段である場合は、前露光は必ずしも必要ではない。
【００６７】
本発明においては、上述の電子写真感光体１、一次帯電手段３、現像手段５及びクリーニング手段９等の構成要素のうち、複数のものをプロセスカートリッジとして一体に結合して構成し、このプロセスカートリッジを複写機やレーザービームプリンタ等の画像形成装置本体に対して着脱可能に構成してもよい。例えば、一次帯電手段３、現像手段５及びクリーニング手段９の少なくとも１つを感光体１と共に一体に支持してカートリッジ化して、装置本体のレール１２等の案内手段を用いて装置本体に着脱可能なプロセスカートリッジ１７とすることができる。
【００６８】
また、画像露光光４は、電子写真装置が複写機やプリンターである場合には、原稿からの反射光や透過光、あるいは、センサーで原稿を読み取り、信号化し、感光体１と共に一体に支持してカートリッジ化して、装置本体のレール１２等の案内手段を用いて装置本体に着脱可能なプロセスカートリッジ１７とすることができる。
【００６９】
また、画像露光光４は、電子写真装置が複写機やプリンターである場合には、原稿からの反射光や透過光、あるいは、センサーで原稿を読み取り、信号化し、この信号に従って行われるレーザービームの走査、ＬＥＤアレイの駆動及び液晶シャッターアレイの駆動等により照射される光である。
【００７０】
図２に本発明の画像形成装置の第２の例であるカラー複写機の概略構成を示す。
【００７１】
図において２０１はイメージスキャナ部であり、原稿を読み取り、デジタル信号処理を行う部分である。また、２０２はプリンタ部であり、イメージスキャナ２０１に読み取られた原稿画像に対応した画像を用紙にフルカラーでプリント出力する部分である。
【００７２】
イメージスキャナ部２０１において、２００は原稿厚板であり、原稿台ガラス２０３上の原稿２０４は赤外カットフィルター２０８を通ったハロゲンランプ２０５の光で照射され、原稿２０４からの反射光はミラー２０６、２０７に導かれ、レンズ２０９により３本のＣＣＤラインセンサ（ＣＣＤ）２１０上に像を結び、フルカラー情報レッド（Ｒ）、グリーン（Ｇ）、ブルー（Ｂ）成分として信号処理部２１１に送られる。なお、２０５、２０６は速度ｖで、２０７は１／２ｖでラインセンサの電気的走査方向（以下、主走査方向）に対して垂直方向（以下、副走査方向）に機械的に動くことにより、原稿全面を走査する。
【００７３】
信号処理部２１１では読み取られた信号を電気的に処理し、マゼンタ（Ｍ）、シアン（Ｃ）、イエロー（Ｙ）、ブラック（ＢＫ）の各成分に分解し、プリンタ部２００に送られ、計４回の原稿走査により一回のプリントアウトが完成する。イメージスキャナ部２０１より送られてくるＭ，Ｃ，Ｙ，ＢＫの画像信号は、レーザドライバ２１２に送られる。レーザドライバ２１２は画像信号に応じ、半導体レーザ２１３を変調駆動する。レーザ光はポリゴンミラー２１４，ｆ−θレンズ２１５、ミラー２１６を介し、感光体ドラム２１７上を走査する。
【００７４】
２１８は回転現像機であり、マゼンタ現像器２１９、シアン現像器２２０、イエロー現像器２２１、ブラック現像器２２２より構成され、４つの現像器が交互に感光体ドラムに接し、感光体ドラム２１７上に形成されたＭ，Ｃ，Ｙ，ＢＫの静電潜像を対応するトナーで現像する。
【００７５】
２２３は転写ドラムで、用紙カセット２２４または２２５より給紙された用紙をこの転写ドラム２２３に巻付け、感光体ドラム２１７上に現像されたトナー像を用紙に転写する。
【００７６】
このようにしてＭ，Ｃ，Ｙ，ＢＫの４色が順次転写された後に、用紙は定着ユニット２２６を通過して定着後、排紙される。
【００７７】
２２３は転写ドラムで、用紙カセット２２４または２２５より給紙された用紙をこの転写ドラム２２３に巻付け、感光体ドラム２１７上に現像されたトナー像を用紙に転写する。
【００７８】
このようにしてＭ，Ｃ，Ｙ，ＢＫの４色が順次転写された後に、用紙は定着ユニット２２６を通過して定着後、排紙される。
【００７９】
【実施例】
以下、実施例によって本発明を説明する。本発明に用いられる樹脂は、例えば以下のようにして合成した。
【００８０】
（合成例１）
撹拌機、温度計、冷却器を備えたフラスコに、式：
【外３２】

【００８１】
で表される１，４−ビス（ジメチルシリル）フェニレン０．８ｇ（４ミリモル）とトルエン２ｇを投入し、これらを４０〜５０℃で撹拌しながら、白金とジビニルテトラメチルシロキサンとの錯体溶液を系中の白金金属自体の含有量が３０ｐｐｍとなるような量添加した。ついでこれに、式：
【外３３】

【００８２】
で表されるジビニルベンジン２．１ｇ（４ミリモル）とトルエン８ｇの混合液を滴下して、６時間撹拌して付加重合を行った。その後、減圧下で揮発分を除去して、室温で固形の反応生成物２．７ｇを得た。この反応生成物の収率は９４％であった。このようにして得られた反応生成物を、トルエンを溶媒としたゲル浸透クロマトグラフィー（以下、ＧＰＣ）、フーリエ変換赤外線分光分析（以下、ＦＴ−ＩＲ）、^１３Ｃ−核磁気共鳴スペクトル分析（以下、^１３Ｃ−ＮＭＲ）及び^２９Ｓｉ−核磁気共鳴スペクトル分析（以下、^２９Ｓｉ−ＮＭＲ）により分析したところ、次式で表される芳香族含ケイ素ポリマーであることが判明した。
【外３４】

【００８３】
（合成例２）
撹拌機、温度計、冷却器を備えたフラスコに、式：
【外３５】

【００８４】
で表される１，４−ビス（ジメチルシリル）フェニレン１．７ｇ（８．７ミリモル）とトルエン３ｇを投入し、これらを５０℃で撹拌しながら、白金とジビニルテトラメチルシロキサンとの錯体溶液を系中の白金金属自体の含有量が３０ｐｐｍとなるような量添加した。ついでこれに、式：
【外３６】

【００８５】
で表されるジビニルベンジジン４．２７ｇ（７．９ミリモル）とトルエン１０ｇの混合液を滴下して、２時間加熱した。続いてビニルトリメトキシシラン０．４３ｇ（２．９ミリモル）を投入して、更に１時間加熱した。その後、減圧下で揮発分を除去して、室温で固形の反応生成物６ｇを得た。この反応生成物の収率は９４％であった。このようにして得られた反応生成物を、ＧＰＣ、ＦＴ−ＩＲ、^１３Ｃ−ＮＭＲ及び^２９Ｓｉ−ＮＭＲにより分析したところ、次式で表される芳香族含ケイ素ポリマーであることが判明した。
【外３７】

【００８６】
（実施例１）
引き抜き加工により得られた外径３０ｍｍのアルミニウムシリンダー上に、フェノール樹脂（商品名　プライオーフェン、大日本インキ化学工業（株）製）１６７部をメチルセロソルブ１００部に溶解したものへ導電性硫酸バリウム超微粒子（１次粒径５０ｎｍ）２００部及び平均粒径２μｍのシリコーン樹脂粒子３部を分散したものを浸せきコーティング法により塗工し、乾燥後の膜厚が１５μｍの導電層を形成した。
【００８７】
上記導電層上にアルコール可溶性共重合ナイロン（商品名　アミランＣＭ−８０００、東レ（株）製）５部をメタノール９５部に溶解した溶液を浸せきコーティング法により塗工した。８０℃で１０分間乾燥して、膜厚が０．５μｍの下引き層を形成した。
【００８８】
次に、電荷発生層用分散液としてＣｕＫα特性Ｘ線回折におけるブラッグ角（２θ±０．２°）の９．０°、１４．２°、２３．９°及び２７．９°に強いピークを有するオキシチタニルフタロシアニン顔料５部をシクロヘキサノン９５部にポリビニルベンザール（ベンザール化度７５％以上）２部を溶解した液に加え、サンドミルで２時間分散した。
【００８９】
この分散液を先に形成した下引き層の上に乾燥後の膜厚が０．２μｍとなるように浸せきコーティング法で塗工した。
【００９０】
ついで、合成例１で合成した樹脂２０部をトルエン３０部に加え溶解したものを前記の電荷発生層の上に浸せきコーティング法により塗工した。１２０℃で３時間乾燥して電荷輸送層の膜厚２０μｍの透明で均一な電荷輸送層を作成した。この電子写真感光体を−６００Ｖに帯電し、波長６８０ｎｍの光を用いて電子写真特性を測定したところ、Ｅ１／２（−３００Ｖまで帯電電位が減少するために必要な露光量）が０．１７Ｊ／ｃｍ２、残留電位が−２８Ｖと非常に良好であった。
【００９１】
本電子写真感光体をキャノン製レーザービームプリンタＬＢＰ−８ＩＶの改造機（（１／ｅ２）を副走査方向で６３．５μｍ、主走査方向で２０μｍの照射スポット径となるように改造）を用い初期帯電−６００Ｖに設定して画像評価をおこなったところ、４０００枚の耐久試験後においても画像の劣化がなく、６００ｄｐｉ相当の入力信号においてのハイライト部の１画素再現性も十分であった。
（比較例１）
実施例１と同様にして、電荷発生層まで形成した。
【００９２】
次いで、下記のトリアリールアミン化合物６部と、
【外３８】

【００９３】
ポリカーボネート樹脂（商品名Ｚ２００、三菱瓦斯化学（株）製）６部をクロロベンゼン７０部に溶解した電荷輸送層用の液を実施例２の電荷発生層の上に浸漬コーティング法により塗工することによって、乾燥後の膜厚が２０μｍの電荷輸送層を形成した。この電子写真感光体を−６００Ｖに帯電し、波長６８０ｎｍの光を用いて電子写真特性を測定したところ、Ｅ１／２（−３００Ｖまで帯電電位が減少するために必要な露光量）が０．３８Ｊ／ｃｍ２、残留電位が−１２０Ｖと大きかった。
【００９４】
本電子写真感光体をキャノン製レーザービームプリンタＬＢＰ−８ＩＶの改造機（（１／ｅ２）を副走査方向で６３．５μｍ、主走査方向で４０μｍの照射スポット径となるように改造）を用い初期帯電−６００Ｖに設定して画像評価をおこなったところ、４０００枚の耐久試験後は干渉縞及び黒ポチが認められ、６００ｄｐｉ相当の入力信号においてのハイライト部の１画素再現性も不十分でむらがあった。
【００９５】
（実施例２）
実施例１と同様のアルミニウムシリンダー上に、フェノール樹脂（商品名　プライオーフェン、大日本インキ化学工業（株）製）１６７部をメチルセロソルブ１００部に溶解したものへ導電性硫酸バリウム超微粒子（１次粒径５０ｎｍ）２００部を分散したものを浸せきコーティング法により、乾燥後の膜厚が１０μｍとなるように塗工した。この導電性支持体に実施例２と同様にして膜厚１μｍの下引き層及び膜厚０．２μｍの電荷発生層を形成した。
【００９６】
ついで、合成例２で合成した樹脂２０部をトルエン３０部に加え溶解したものを前記の電荷発生層の上に浸せきコーティング法により塗工した。１２０℃で３時間乾燥して電荷輸送層の膜厚２０μｍの透明で均一な電荷輸送層を作成した。この電子写真感光体を−６００Ｖに帯電し、波長６８０ｎｍの光を用いて電子写真特性を測定したところ、Ｅ１／２（−３００Ｖまで帯電電位が減少するために必要な露光量）が０．１６Ｊ／ｃｍ２、残留電位が−２４Ｖと非常に良好であった。
【００９７】
本電子写真感光体を実施例２と同様のキャノン製レーザービームプリンタを用い初期帯電−５００Ｖに設定して画像評価をおこなったところ、４０００枚の耐久試験後においても画像の劣化がなく、６００ｄｐｉ相当の入力信号においてのハイライト部の１画素再現性も十分であった。
【００９８】
（実施例３）
外径８０ｍｍのアルミニウムシリンダー上に、１０％の酸化アンチモンを含有する酸化錫で被覆した導電性酸化チタン粉末５０部、フェノール樹脂２５部、メチルセロソルブ３０部、メタノール３０部及びシリコーンオイル（ポリメチルシロキサンポリオキシアルキレン共重合体、重量平均分子量３０００）０．００２部を１φｍｍガラスビーズを用いたサンドミル装置で２時間分散して調整した導電層用塗料を浸漬塗布し、１４０℃で３０分間乾燥して膜厚２０μｍの導電層を形成した。
【００９９】
次にアルコール可溶性共重合ナイロン（商品名　アミランＣＭ−８０００、東レ（株）製）５部をメタノール９５部に溶解した溶液を浸せきコーティング法により塗工した。８０℃で１０分間乾燥して、膜厚が１μｍの下引き層を形成した。
【０１００】
次に、電荷発生層として下記のビスアゾ顔料５部をシクロヘキサノン９５部にポリビニルベンザール（ベンザール化度７５％以上）２部を溶解した液に加え、サンドミルで２０時間分散した。この分散液を先に形成した下引き層の上に乾燥後の膜厚が０．２μｍとなるように浸せきコーティング法で塗工した。
【外３９】

【０１０１】
ついで、合成例１で合成した樹脂２０部をトルエン３０部に加え溶解したものを前記の電荷発生層の上に浸せきコーティング法により塗工した。１２０℃で３時間乾燥して電荷輸送層の膜厚２０μｍの透明で均一な電荷輸送層を作成した。
【０１０２】
この電子写真感光体を−６００Ｖに帯電し、波長６８０ｎｍの光を用いて電子写真特性を測定したところ、Ｅ１／２（−２５０Ｖまで帯電電位が減少するために必要な露光量）が０．５５Ｊ／ｃｍ２、残留電位が−１８Ｖと非常に良好であった。
【０１０３】
本電子写真感光体をキャノン製デジタルフルカラー複写機ＣＬＣ−５００を副走査方向で６３．５μｍ、主走査方向で２０μｍの照射スポット径となるように改造した評価機にて初期帯電−６００Ｖに設定して画像評価をおこなったところ、初期及び１０万枚耐久試験後も黒ポチ等の電荷注入及び干渉縞もなく、均一性の優れた画像出力が得られ、階調再現性も４００ｄｐｉで２５６階調と極めて良好であった。
【０１０４】
（比較例２）
実施例３と同様にして、電荷発生層まで形成した。
【０１０５】
次いで、下記のトリアリールアミン化合物６部と、
【外４０】

【０１０６】
ポリカーボネート樹脂（商品名Ｚ２００、三菱瓦斯化学（株）製）６部をクロロベンゼン７０部に溶解した電荷輸送層用の液を実施例２の電荷発生層の上に浸漬コーティング法により塗工することによって、乾燥後の膜厚が２０μｍの電荷輸送層を形成した。この電子写真感光体を−６００Ｖに帯電し、波長６８０ｎｍの光を用いて電子写真特性を測定したところ、Ｅ１／２（−３００Ｖまで帯電電位が減少するために必要な露光量）が１．５Ｊ／ｃｍ２、残留電位が−５８Ｖと大きかった。
【０１０７】
本電子写真感光体を実施例３と同様に画像評価したところ、２万枚の耐久試験後に黒ポチ等が大量に発生したために良好な画像は得られなかった。
【０１０８】
（実施例４）
実施例３と同様にして、電荷発生層まで形成した。
【０１０９】
ついで、合成例２で合成した樹脂２０部をトルエン３０部に加え溶解したものを前記の電荷発生層の上に浸せきコーティング法により塗工した。１２０℃で３時間乾燥して電荷輸送層の膜厚２０μｍの透明で均一な電荷輸送層を作成した。この電子写真感光体を−６００Ｖに帯電し、波長６８０ｎｍの光を用いて電子写真特性を測定したところ、Ｅ１／２（−３００Ｖまで帯電電位が減少するために必要な露光量）が０．５２Ｊ／ｃｍ２、残留電位が−１２Ｖと非常に良好であった。
【０１１０】
本電子写真感光体をキャノン製デジタルフルカラー複写機ＣＬＣ−５００を副走査方向で６３．５μｍ、主走査方向で２０μｍの照射スポット径となるように改造した評価機にて初期帯電−５００Ｖに設定して画像評価をおこなったところ、初期及び１０万枚耐久試験後も黒ポチ等の電荷注入及び干渉縞もなく、均一性の優れた画像出力が得られ、階調再現性も４００ｄｐｉで２５６階調と極めて良好であった。
【０１１１】
【発明の効果】
以上のように本発明によれば、光散乱やブリードがなく、高感度かつ低残留電位であって、製造時の塗工性が良好である電子写真感光体、及び該電子写真感光体を有するプロセスカートリッジ及び画像形成装置を提供することができた。
【図面の簡単な説明】
【図１】本発明の画像形成装置の第１の例の概略構成を示す図である。
【図２】本発明の画像形成装置の第２の例の概略構成を示す図である。
【符号の説明】
１　本発明の電子写真感光体
２　軸
３　一次帯電手段
４　画像露光光
５　現像手段
６　転写手段
７　転写材
８　像定着手段
９　クリーニング手段
１０　前露光光
１１　プロセスカートリッジ
１２　案内手段[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member having a specific photosensitive layer, a process cartridge having the electrophotographic photosensitive member, and an image forming apparatus.
[0002]
[Prior art]
Conventionally, inorganic photoconductive substances such as selenium, cadmium sulfide, and zinc oxide have been widely used for a photosensitive layer of an electrophotographic photosensitive member. In recent years, due to advantages such as high safety, suitable for mass production, and low cost, research on using an organic photoconductive substance for a photosensitive layer of an electrophotographic photosensitive member has been actively conducted, and many photosensitive members have been proposed. Has been put to practical use. Among them, the mainstream of research has been the laminated photoreceptor, in which the function is separated into a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material, because of its excellent sensitivity, durability, and the like. I have. However, even with the above-mentioned laminated photoreceptor, by repeating the image forming processes such as charging, exposure, development, transfer, and static elimination with a copying machine or a laser beam printer, the charged potential decreases and the residual potential increases, and the image fogged. Defects such as blurring and blurring occur, and the electrical durability is not sufficient.
[0003]
In addition, the surface of the electrophotographic photoreceptor is mechanically affected directly by a charging unit, a developing unit, a transfer unit, a cleaning unit, and the like, and is required to have mechanical durability against them.
[0004]
Specifically, it is required to have durability against abrasion and scratches on the surface of the photoreceptor due to rubbing, and deterioration of the surface of the photoreceptor due to ozone which is likely to be generated during corona charging under high humidity. In addition, there is a problem that toner adheres to the surface of the photoconductor due to the repetition of development and cleaning.
[0005]
Attempts have been made to provide various surface protective layers containing a resin as a main component on the photosensitive layer in order to satisfy the various characteristics required for the photosensitive member surface as described above. For example, JP-A-57-30843 proposes a protective layer in which resistance is controlled by adding metal oxide particles as conductive particles.
[0006]
It has also been studied to improve the physical properties of the photoreceptor surface by adding various substances to the surface layer. For example, additives focused on low surface energy of silicone include silicone oil (JP-A-61-132954), polydimethylsiloxane, silicone resin powder (JP-A-4-324454), cross-linked silicone resin, and poly (carbonate silicone). ) Block copolymers, modified silicone polyurethanes, modified silicone polyesters have been reported.
[0007]
A typical polymer having a low surface energy is a fluorine-based polymer, and examples of the fluorine-based polymer include polytetrafluoroethylene powder and carbon fluoride powder.
[0008]
However, although a surface protective layer containing a metal oxide or the like having high hardness can be obtained, there is a problem in cleaning properties and the like because the surface energy tends to increase. Silicone resins are excellent in that they have low surface energy, but they do not show sufficient compatibility with other resins, so they tend to agglomerate in the additive system, causing light scattering or bleeding and segregating on the surface. There were problems such as not exhibiting stable characteristics. Further, since a fluorine-based polymer which is a polymer having a low surface energy is generally insoluble in a solvent and has poor dispersibility, it is difficult to obtain a smooth photoreceptor surface. Silicone resins are excellent in that they have low surface energy, but they do not show sufficient compatibility with other resins, so they tend to agglomerate in the additive system, causing light scattering or bleeding and segregating on the surface. There were problems such as not exhibiting stable characteristics. In addition, fluoropolymers, which are low surface energy polymers, are generally insoluble in solvents and poor in dispersibility, making it difficult to obtain a smooth photoreceptor surface, and having a small refractive index. There is a problem that scattering is apt to occur, which causes deterioration of transparency. Further, fluorine-based polymers generally have a problem that they are easily damaged due to softness.
[0009]
Further, the use of the surface protective layer and the additives has a problem that the electrophotographic characteristics such as sensitivity and residual charge are deteriorated.
[0010]
On the other hand, as a light source for electrophotography, a semiconductor laser is used in terms of cost and size of the device, but the semiconductor laser currently mainly used has an oscillation wavelength in a red to near infrared region. Electrophotographic photoreceptors having sufficient sensitivity to long-wavelength light have been developed. Phthalocyanine compounds are extremely effective as charge generation materials having sensitivity up to such a long wavelength region. In particular, oxytitanyl phthalocyanine has excellent sensitivity as compared with conventional phthalocyanine compounds. JP-A-61-239248, JP-A-62-67094, JP-A-63-218768, JP-A-64-17066, etc., which are highly sensitive to various crystalline oxytitanium phthalocyanines. Have been reported.
[0011]
Electrophotographic photoreceptors using oxytitanium phthalocyanine have excellent sensitivity characteristics as described above, but have the disadvantage that the residual potential is relatively high. Such characteristics have the disadvantage that potential contrast is difficult to obtain in a system in which the process speed of electrophotography is high, or in a system with a short process cycle, or a system with a small laser spot when using laser exposure. In addition, for example, in the case where a laminated photoreceptor is to be formed using oxytitanium phthalocyanine as a charge generation layer, the formulation design latitude of an intermediate layer, a surface protective layer, and the like is undesirably narrow.
[0012]
[Problems to be solved by the invention]
An object of the present invention is to solve the above-mentioned problems, that is, there is no light scattering or bleed, high sensitivity and low residual potential, and an electrophotographic photoreceptor having good coatability during production, and An object of the present invention is to provide a process cartridge and an image forming apparatus having the electrophotographic photosensitive member.
[0013]
[Means for Solving the Problems]
That is, the present invention provides an image forming apparatus in which an electrophotographic photosensitive member having a photosensitive layer on a support contains a resin having a structural unit represented by the following formula (1). It is in.
[Outside 3]

[0014]
(A represents a hole transporting group; B represents an alkylene group having 2 to 6 carbon atoms. R ¹ represents a substituted or unsubstituted monovalent monovalent having 1 to 10 carbon atoms containing no aliphatic unsaturated bond. R ¹ may be the same or different, and R ² represents a substituted or unsubstituted divalent hydrocarbon group having 2 to 10 carbon atoms or an alkyleneoxyalkylene group, and x represents 1 (Y and z are integers of 0 or more, but (y + z) is an integer of 2 or more.)
Further, the present invention is a process cartridge and an image forming apparatus having the above electrophotographic photosensitive member.
[0015]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
[0016]
As the divalent organic group represented by A in the above formula (1), those known as charge transporting groups are preferable. The charge transporting property in the present invention refers to the ability to transport charges, and preferably has an ionization potential of 6.2 eV or less. That is, the hydrogenated product of A preferably has an ionization potential of 6.2 eV or less, particularly preferably 4.5 to 6.2 eV. If the ionization potential exceeds 6.2 eV, hole injection is unlikely to occur and charging becomes easy. If it is less than 4.5 eV, the compound is easily oxidized and thus easily deteriorates. The ionization potential is measured by an atmospheric photoelectron analysis method (manufactured by Riken Keiki Co., Ltd., surface analyzer AC-1).
[0017]
Specific examples of such a divalent organic group represented by A include hydrogenation compounds (charge transport substances) such as oxazole derivatives, oxadiazole derivatives, imidazole derivatives, and triphenylamine. Triarylamine derivatives, 9- (p-diethylaminostyryl) anthracene, 1,1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives , Imidazole derivatives, triarylamine derivatives such as triphenylamine, 9- (p-diethylaminostyryl) anthracene, 1,1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, phenylhydrazone S, alpha-phenyl stilbene derivative, a thiazole derivative, a triazole derivative, phenazine derivative, acridine derivative, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives, etc. N- phenyl carbazole derivatives. Specific examples are shown below. In the following formula, Ph represents a phenyl group, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Pr represents a propyl group.
[Outside 4]

[0018]
[Outside 5]

[0019]
[Outside 6]

[0020]
[Outside 7]

[0021]
[Outside 8]

[0022]
[Outside 9]

[0023]
[Outside 10]

[0024]
[Outside 11]

[0025]
[Outside 12]

[0026]
[Outside 13]

[0027]
[Outside 14]

[0028]
[Outside 15]

[0029]
[Outside 16]

[0030]
Among them, those having a structure represented by the following formula (2) can be suitably used for the hole transporting group A.
[Outside 17]

[0031]
(R ² , R ³ , R ⁴ and R ⁵ are organic groups, at least one of which represents an aromatic hydrocarbon ring group or a heterocyclic group, and R ² , R ³ , R ⁴ and R ⁵ are the same R ⁶ represents an aromatic hydrocarbon ring group.)
At this time, the hole transporting group A is a group formed by removing hydrogen atoms of two groups out of R ² , R ³ , R ⁴ and R ⁵ .
[0032]
Preferred specific examples of the structure of R ² , R ³ , R ⁴ and R ⁵ are shown below.
[Outside 18]

[0033]
[Outside 19]

[0034]
Preferred specific examples of the structure of R ⁶ are shown below.
[Outside 20]

[0035]
[Outside 21]

[0036]
B is an alkylene group having 2 to 6 carbon atoms, specifically, an ethylene group, a methylethylene group, an ethylethylene group, a propylethylene group, a butylethylene group, a propylene group, a butylene group, a 1-methylpropylene group, a pentylene group And a straight-chain or branched-chain alkylene group such as a hexylene group. Among these, an ethylene group, a propylene group, a butylene group, and a hexylene group are preferred. R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms not containing an aliphatic unsaturated bond, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Alkyl group such as hexyl group; aryl group such as phenyl group, tolyl group and xylyl group; aralkyl group such as benzyl group and phenethyl group; and fluorocarbonization such as trifluoropropyl group, nonafluorohexyl group and heptadecafluorooctyl group A hydrogen group is exemplified, and among them, a methyl group or a phenyl group is preferable. R is a substituted or unsubstituted divalent hydrocarbon group having 2 to 10 carbon atoms or an alkyleneoxyalkylene group. Examples of the divalent hydrocarbon group include linear or linear groups such as ethylene group, methylethylene group, ethylethylene group, propylethylene group, butylethylene group, propylene group, butylene group, 1-methylpropylene group, pentylene group, and hexylene group. A branched alkylene group; phenylene groups such as p-phenylene group, m-phenylene group, o-phenylene group, 2-methyl-1,4-phenylene group and 2-methoxy-1,4-phenylene group; You. Examples of the alkyleneoxyalkylene group include an ethyleneoxyethylene group. Among them, R is preferably an ethylene group or a p-phenylene group. x is an integer of 1 or more, y and z are integers of 0 or more, and (y + z) is 2 or more. Specifically, x is preferably in the range of 1 to 2,000, and more preferably in the range of 2 to 1,000. y is preferably in the range of 2 to 2,000, and more preferably in the range of 2 to 1,000. z is usually in the range of 0 to 1000.
[0037]
The molecular chain terminal of the resin represented by the general formula (1) is not particularly limited, and examples thereof include a hydrogen atom, a hydrolyzable group such as a hydroxyl group and an alkoxy group, a substituted or unsubstituted monovalent hydrocarbon group, and a compound represented by the formula: R _{^{7 3 -Si- (Q) p -}} ( wherein, ^{R 7} is a hydrogen atom, a hydrolyzable group, a substituted or unsubstituted monovalent hydrocarbon group, p is 0 or 1, Q represents an oxygen atom Or a substituted or unsubstituted divalent hydrocarbon group, wherein R ⁷ may be the same or different.) The weight average molecular weight of the resin represented by the general formula (1) is generally in the range of 1,000 to 1,000,000, and preferably in the range of 5,000 to 500,000.
[0038]
Specific examples of the resin represented by the general formula (1) include a compound represented by the following formula. In the following formula, Ph represents a p-phenylene group, Me represents a methyl group, and A has the above structure.
[Outside 22]

[0039]
The resin represented by the above general formula (1) is obtained by preparing a resin represented by the following general formula (3): B ¹ -AB ¹ (where A is the same as described above, and B ¹ is a carbon atom in the presence of a hydrosilylation reaction catalyst). An alkenyl group having 2 to 6 atoms) and a general formula (4):
[Outside 23]

[0040]
(Wherein R ¹ and R ² are the same as described above), and if necessary, a general formula (5)
[Outside 24]

[0041]
(Wherein W is a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms, and R ¹ is the same as described above). The compound can be obtained by addition polymerization. At this time, both the organosilicon compound of the above general formula (4) and the disiloxane compound of the above formula (5) may be subjected to addition polymerization.
[0042]
The charge transporting compound used when producing the resin represented by the general formula (1) is represented by the general formula (3): B ¹ -AB ¹ . In the general formula (3), B ¹ is an alkenyl group having 2 to 6 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, and a 5-hexenyl group. A is the same as above. As such an aromatic compound, a compound represented by the following formula is exemplified.
[Outside 25]

[0043]
General formula (4) used when producing the resin represented by the general formula (1):
[Outside 26]

[0044]
In the formula, R ¹ and R ² are the same as described above. Specific examples of the organosilicon compound include a compound represented by the following formula. In the following formula, Rh represents a p-phenylene group, Me represents a methyl group, and C ₆ H ₅ represents a phenyl group.
[Outside 27]

[0045]
General formula (5) used when producing the resin represented by the general formula (1):
[Outside 28]

[0046]
In the formula, W is a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms, and R ¹ is the same as described above. Specific examples of the disiloxane compound include a compound represented by the following formula. In the following formula, Me represents a methyl group, and C ₆ H ₅ represents a phenyl group.
[Outside 29]

[0047]
As the hydrosilylation reaction catalyst used when producing the resin represented by the above general formula (1), a supported or non-supported platinum-based catalyst is preferable. Specifically, platinum black and platinum-supported silica fine catalyst are used. Examples thereof include powder, carbon powder carrying platinum, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a complex of platinum and vinylsiloxane, and a complex of platinum and olefin. The addition amount is preferably 1 to 2000 ppm as platinum metal. The used platinum-based catalyst can be removed by adding and mixing activated carbon, silica gel, silica gel treated with aminosilane, silica gel treated with mercaptosilane and the like, followed by filtration.
[0048]
Further, the silicon-based resin used in the electrophotographic photoreceptor of the present invention has a general formula (6)
[Outside 30]

[0049]
(Wherein R ¹ , R and B ¹ are the same as described above), and may be subjected to addition polymerization together with each of the compounds described above. Examples of the organosilicon compound include compounds represented by the following formula. In the following formula, Me represents a methyl group, and C ₆ H ₅ represents a phenyl group.
[Outside 31]

[0050]
The silicon-based resin used in the electrophotographic photoreceptor of the present invention includes, as a polymerization terminator, an organosilicon compound having an alkoxy group and a silicon-bonded hydrogen atom, or an alkoxy group and an alkenyl group having 2 to 6 carbon atoms. It is preferable to use an organosilicon compound having the following formula: Examples of such a polymerization terminator include a silane compound represented by the following formula. In the following formula, Me represents a methyl group, and Vi represents a vinyl group.
HSi (OMe) ₃
HSi (OC ₂ H ₅ ) ₃
HMeSi (OMe) ₂
HMeSi (OC ₂ H ₅ ) ₂
HMe ₂ SiOMe
ViSi (OMe) ₃
ViSi (OC ₂ H ₅ ) ₃
ViMeSi (OMe) ₂
ViMeSi (OC ₂ H ₅ ) ₂
ViMe ₂ SiOMe
CH ₂ ＣＨCHCH ₂ Si (OMe) ₃
CH ₂ ＣＨCHCH ₂ Si (OC ₂ H ₅ ) ₃
CH ₂ ＣＨCHCH ₂ SiMe (OMe) ₂
CH ₂ ＣＨCH (CH ₂ ) ₄ Si (OMe) ₃
CH ₂ ＣＨCH (CH ₂ ) ₄ SiMe (OMe) ₂
CH ₂ ＣＨCH (CH ₂ ) ₄ SiMe (OC ₂ H ₅ ) ₂
In the step of synthesizing the silicon-based resin used in the electrophotographic photoreceptor of the present invention, the order of adding each component is optional, but upon addition polymerization, each component may be mixed and reacted from a solution of an organic solvent. . Examples of usable organic solvents include, for example, aromatic solvents such as benzene, toluene and xylene; aliphatic solvents such as cyclohexane, methylcyclohexane and dimethylcyclohexane; trichloroethylene, 1,1,1-trichloroethane, carbon tetrachloride, chloroform Chlorine-based solvents such as hexane; aliphatic saturated hydrocarbon-based solvents such as hexane and industrial gasoline; ethers such as diethyl ether and tetrahydrofuran; ketone-based solvents such as methyl isobutyl ketone; α, α, α-trifluorotoluene; Fluorinated solvents such as fluoroxylene; and volatile silicones such as hexamethyldisiloxane, hexamethylcyclotrisiloxane, and octamethylcyclotetrasiloxane. When blending the organic solvent, it is preferred to blend the silicon-based polymer in an amount of 5 to 90% by weight.
[0051]
Next, an example of producing the electrophotographic photoreceptor of the present invention will be described below.
[0052]
As the support of the electrophotographic photoreceptor, a support having conductivity itself, for example, aluminum, aluminum alloy, copper, zinc, stainless steel, chromium, titanium, nickel, magnesium, indium, gold, platinum, silver, iron, etc. Can be used. In addition, aluminum, indium oxide, tin oxide, gold, etc. are used to form a conductive layer by forming a film on a dielectric substrate such as plastic by vapor deposition or the like, or a mixture of conductive fine particles in plastic or paper is used. I can do it. For these conductive substrates, uniform conductivity is required and a smooth surface is important. Since the surface smoothness greatly affects the uniformity of the undercoat layer, charge generation layer and hole transport layer formed thereon, the surface roughness is preferably used at 0.3 μm or less. The unevenness of 0.3 μm or more greatly changes the local electric field applied to a thin layer such as an undercoat layer or a charge generation layer, and the characteristics thereof are greatly changed, resulting in defects such as charge injection and uneven remaining charge. This is not preferred because it tends to cause
[0053]
In particular, a conductive layer obtained by dispersing and applying conductive fine particles in a polymer binder is easy to form and is suitable for forming a uniform surface. The primary particle size of the conductive fine particles used at this time is 100 nm or less, and more preferably 50 nm or less. As the conductive fine particles, conductive zinc oxide, conductive titanium oxide, Al, Au, Cu, Ag, Co, Ni, Fe, carbon black, ITO, tin oxide, indium oxide, indium, and the like are used. The surface of the insulating fine particles may be coated before use. The content of the conductive fine particles is used so that the volume resistance is sufficiently low, and is preferably added so as to have a resistance of 1 × 10 ¹⁰ Ωcm or less. More preferably, it is used at 1 × 10 ⁸ Ωcm or less.
[0054]
When exposure is performed using a coherent light source such as a laser, it is possible to form irregularities on the surface of the conductive substrate in order to prevent image deterioration due to interference. In this case, irregularities of about 1 / 2λ of the wavelength used to disperse insulators such as silica beads having a diameter of several μm or less in a period of 10 μm or less so that defects such as charge injection and residual potential unevenness do not easily occur. It can be formed and used.
[0055]
In the present invention, an undercoat layer having an injection blocking function and an adhesion function may be provided between the base material and the photoconductive layer. Examples of the material of the undercoat layer include casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, phenol resin, polyamide, polyurethane, and gelatin. The thickness of the undercoat layer is preferably from 0.1 μm to 10 μm, particularly preferably from 0.3 μm to 3 μm.
[0056]
As the photosensitive layer, a function separation type including a charge generation layer containing a charge generation substance and a charge transport layer containing a charge transport substance, and a single layer type containing the charge generation substance and the charge transport substance in the same layer are used. Can be
[0057]
The structure of the photosensitive layer will be described. The structure of the photosensitive layer includes a structure in which a charge transport layer is stacked on the charge generation layer and a structure in which the charge generation layer is stacked on the charge transport layer.
[0058]
Examples of the charge generation material include selenium-tellurium, pyrylium dyes, thiopyrylium dyes, phthalocyanine pigments, anthantrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, azo pigments, indigo pigments, and quinacridone pigments. Pigments, cyanine-based pigments, and the like can be used. Among these charge generating materials, in the present invention, azo pigments and phthalocyanine pigments are particularly suitable. Examples of the phthalocyanine pigment include metal-free phthalocyanine, copper phthalocyanine, gallium phthalocyanine, and oxytitanium phthalocyanine. Of these, oxytitanium phthalocyanine having high sensitivity to long-wavelength light is particularly preferable. For example, JP-A-61-239248, JP-A-62-67094, JP-A-3-128973 and JP-A-3-200790. There is a disclosure in Japanese Patent Publication No. Among these, 9.0 °, 14.2 °, 23.9 °, and 27.1 at the Bragg angles (2θ ± 0.2 °) in the CuKα characteristic X-ray diffraction disclosed in JP-A-3-128973. Oxytitanium phthalocyanine, which is a crystalline form having a characteristic peak at °, is more preferred.
[0059]
The binder can be selected from a wide range of insulating resins, for example, polyvinyl butyral, polyvinyl alcohol, polyarylate, polyamide, acrylic resin, polyvinyl acetate, phenol resin, epoxy resin, polyester, polycarbonate, polyurethane, cellulose resin, and the like. Resins. The resin contained in the charge generation layer is suitably at most 80% by weight, preferably at most 50% by weight. The thickness of the charge generation layer is preferably 5 μm or less, particularly preferably 0.05 to 2 μm.
[0060]
The resin of the present invention can be used as a charge transporting layer or a surface protective layer having a hole transporting ability.
[0061]
The thickness of the charge transport layer in the invention is preferably from 1 to 40 μm, and particularly preferably from 3 to 30 μm. The thickness of the surface protective layer in the present invention is preferably from 1 to 15 μm. If the thickness is 1 μm or less, the protective effect is not sufficient, and if it exceeds 15 μm, the film thickness of the entire photosensitive layer increases, which is not preferable since image deterioration is likely to occur.
[0062]
Additives other than the above compounds can be used in the photoconductive layer in order to improve mechanical properties and durability. As such additives, antioxidants, ultraviolet absorbers, stabilizers, cross-linking agents, lubricants, conductivity control agents, and the like are used.
[0063]
FIG. 1 shows a schematic configuration of a first example of an image forming apparatus having the process cartridge of the present invention.
[0064]
In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around a shaft 2 at a predetermined peripheral speed in a direction indicated by an arrow. In the rotation process, the photosensitive member 1 is uniformly charged with a predetermined positive or negative potential on the peripheral surface thereof by the primary charging means 3, and then the image exposure 4 from an image exposure means (not shown) such as laser beam scanning exposure. Receive. Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 1.
[0065]
The formed electrostatic latent image is developed with toner by a developing unit 5, and the developed toner developed image is taken out from a paper feeding unit (not shown) between the photoconductor 1 and the transfer unit 6 in synchronization with the rotation of the photoconductor 1. The transfer means 6 sequentially transfers the transfer material 7 to the supplied and supplied transfer material 7. The transfer material 7 which has undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing to be printed out as a copy as a copy.
[0066]
The surface of the photoreceptor 1 after the image transfer is cleaned and cleaned by removing the untransferred toner by a cleaning unit 9, and further subjected to a static elimination process by a pre-exposure light 10 from a pre-exposure unit (not shown). Used for imaging. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not necessarily required.
[0067]
In the present invention, among the above-described components such as the electrophotographic photosensitive member 1, the primary charging unit 3, the developing unit 5, and the cleaning unit 9, a plurality of components are integrally connected as a process cartridge. May be configured to be detachable from a main body of an image forming apparatus such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photoreceptor 1 to form a cartridge, which can be attached to and detached from the apparatus main body using a guide unit such as a rail 12 of the apparatus main body. The process cartridge 17 can be used.
[0068]
When the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 reads reflected light or transmitted light from the original, or reads the original with a sensor, converts it into a signal, and supports it together with the photoconductor 1. Then, the process cartridge 17 can be detachably attached to the apparatus main body by using a guide means such as the rail 12 of the apparatus main body.
[0069]
When the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 is a light reflected from or transmitted from the original, or the original is read by a sensor and converted into a signal. Light emitted by scanning, driving of an LED array, driving of a liquid crystal shutter array, and the like.
[0070]
FIG. 2 shows a schematic configuration of a color copying machine which is a second example of the image forming apparatus of the present invention.
[0071]
In the figure, reference numeral 201 denotes an image scanner unit which reads a document and performs digital signal processing. Reference numeral 202 denotes a printer unit which prints out an image corresponding to the document image read by the image scanner 201 on a sheet in full color.
[0072]
In the image scanner unit 201, reference numeral 200 denotes an original plate, an original 204 on an original platen glass 203 is irradiated with light from a halogen lamp 205 passing through an infrared cut filter 208, and reflected light from the original 204 is reflected by a mirror 206. The light is guided to a lens 207, forms an image on three CCD line sensors (CCD) 210 by a lens 209, and is sent to a signal processing unit 211 as full-color information red (R), green (G), and blue (B) components. Note that 205 and 206 are speeds v, and 207 is ｖ v, by mechanically moving the line sensor in a direction perpendicular to an electrical scanning direction (hereinafter, main scanning direction) (hereinafter, sub-scanning direction). Scans the entire original.
[0073]
The signal processing unit 211 electrically processes the read signal, decomposes the signals into magenta (M), cyan (C), yellow (Y), and black (BK) components. One printout is completed by scanning the document four times. The M, C, Y, and BK image signals sent from the image scanner unit 201 are sent to the laser driver 212. The laser driver 212 modulates and drives the semiconductor laser 213 according to the image signal. The laser beam scans on the photosensitive drum 217 via the polygon mirror 214, the f-θ lens 215, and the mirror 216.
[0074]
Reference numeral 218 denotes a rotary developing device, which includes a magenta developing device 219, a cyan developing device 220, a yellow developing device 221 and a black developing device 222. The four developing devices alternately contact the photosensitive drum, and The formed M, C, Y, and BK electrostatic latent images are developed with corresponding toner.
[0075]
Reference numeral 223 denotes a transfer drum which winds a sheet fed from the sheet cassette 224 or 225 around the transfer drum 223 and transfers a toner image developed on the photosensitive drum 217 to the sheet.
[0076]
After the four colors of M, C, Y, and BK are sequentially transferred in this manner, the sheet passes through the fixing unit 226, is fixed, and is discharged.
[0077]
Reference numeral 223 denotes a transfer drum which winds a sheet fed from the sheet cassette 224 or 225 around the transfer drum 223 and transfers a toner image developed on the photosensitive drum 217 to the sheet.
[0078]
After the four colors of M, C, Y, and BK are sequentially transferred in this manner, the sheet passes through the fixing unit 226, is fixed, and is discharged.
[0079]
【Example】
Hereinafter, the present invention will be described with reference to examples. The resin used in the present invention was synthesized, for example, as follows.
[0080]
(Synthesis example 1)
In a flask equipped with a stirrer, thermometer and condenser, the formula:
[Outside 32]

[0081]
0.8 g (4 mmol) of 1,4-bis (dimethylsilyl) phenylene and 2 g of toluene represented by the following formulas are added, and while stirring these at 40 to 50 ° C., a complex solution of platinum and divinyltetramethylsiloxane is added. The amount was added such that the content of platinum metal itself in the system was 30 ppm. Then to this, the formula:
[Outside 33]

[0082]
A mixture of 2.1 g (4 mmol) of divinylbenzine and 8 g of toluene was added dropwise and stirred for 6 hours to carry out addition polymerization. Thereafter, volatiles were removed under reduced pressure to obtain 2.7 g of a reaction product solid at room temperature. The yield of this reaction product was 94%. The reaction product thus obtained was subjected to gel permeation chromatography (hereinafter, GPC) using toluene as a solvent, Fourier transform infrared spectroscopy (hereinafter, FT-IR), ¹³ C-nuclear magnetic resonance spectrum analysis (hereinafter, referred to as “FT-IR”). , ¹³ C-NMR) and ²⁹ Si-nuclear magnetic resonance spectroscopy (hereinafter referred to as ²⁹ Si-NMR) revealed that the polymer was an aromatic silicon-containing polymer represented by the following formula.
[Outside 34]

[0083]
(Synthesis example 2)
In a flask equipped with a stirrer, thermometer and condenser, the formula:
[Outside 35]

[0084]
1.7 g (8.7 mmol) of 1,4-bis (dimethylsilyl) phenylene and 3 g of toluene represented by the following formulas were added, and while stirring them at 50 ° C., a complex solution of platinum and divinyltetramethylsiloxane was added. The amount was added such that the content of platinum metal itself in the system was 30 ppm. Then to this, the formula:
[Outside 36]

[0085]
A mixture of 4.27 g (7.9 mmol) of divinylbenzidine and 10 g of toluene was added dropwise and heated for 2 hours. Subsequently, 0.43 g (2.9 mmol) of vinyltrimethoxysilane was added, and the mixture was further heated for 1 hour. Thereafter, volatile components were removed under reduced pressure to obtain 6 g of a reaction product solid at room temperature. The yield of this reaction product was 94%. When the reaction product thus obtained was analyzed by GPC, FT-IR, ¹³ C-NMR and ²⁹ Si-NMR, it was found to be an aromatic silicon-containing polymer represented by the following formula.
[Outside 37]

[0086]
(Example 1)
To an aluminum cylinder having an outer diameter of 30 mm obtained by drawing, 167 parts of a phenolic resin (trade name: Plyofen, manufactured by Dainippon Ink and Chemicals, Inc.) dissolved in 100 parts of methyl cellosolve was added to a barium sulfate superconductive material. A dispersion in which 200 parts of fine particles (primary particle size: 50 nm) and 3 parts of silicone resin particles having an average particle size of 2 μm were dispersed was applied by a dip coating method, and a conductive layer having a dried film thickness of 15 μm was formed.
[0087]
A solution obtained by dissolving 5 parts of alcohol-soluble copolymerized nylon (trade name: Amilan CM-8000, manufactured by Toray Industries, Inc.) in 95 parts of methanol was applied onto the conductive layer by a coating method. After drying at 80 ° C. for 10 minutes, an undercoat layer having a thickness of 0.5 μm was formed.
[0088]
Next, strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.9 ° of the Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction were obtained as the dispersion for the charge generation layer. 5 parts of the oxytitanyl phthalocyanine pigment was added to a solution prepared by dissolving 2 parts of polyvinyl benzal (a degree of benzalization of 75% or more) in 95 parts of cyclohexanone, and dispersed by a sand mill for 2 hours.
[0089]
The dispersion was dipped on the undercoat layer formed previously so that the film thickness after drying was 0.2 μm, and applied by a coating method.
[0090]
Next, 20 parts of the resin synthesized in Synthesis Example 1 was added to 30 parts of toluene and dissolved, and the resultant was immersed on the charge generation layer and applied by a coating method. After drying at 120 ° C. for 3 hours, a transparent and uniform charge transport layer having a thickness of 20 μm was formed. The electrophotographic photoreceptor was charged to -600 V, and electrophotographic characteristics were measured using light having a wavelength of 680 nm. As a result, E1 / 2 (exposure required to reduce the charging potential to -300 V) was 0.17 J. / Cm 2, and the residual potential was −28 V, which was very good.
[0091]
This electrophotographic photoreceptor was initially modified using a modified machine of Canon Laser Beam Printer LBP-8IV ((1 / e2) modified to have an irradiation spot diameter of 63.5 μm in the sub-scanning direction and 20 μm in the main scanning direction). When the image was evaluated by setting the charging to -600 V, the image was not deteriorated even after the durability test of 4000 sheets, and the reproducibility of one pixel of the highlight portion in the input signal corresponding to 600 dpi was sufficient.
(Comparative Example 1)
In the same manner as in Example 1, up to the charge generation layer was formed.
[0092]
Next, 6 parts of the following triarylamine compound:
[Outside 38]

[0093]
A charge transport layer solution prepared by dissolving 6 parts of a polycarbonate resin (trade name: Z200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in 70 parts of chlorobenzene is applied onto the charge generation layer of Example 2 by a dip coating method. Then, a charge transport layer having a thickness of 20 μm after drying was formed. The electrophotographic photosensitive member was charged to -600 V, and electrophotographic characteristics were measured using light having a wavelength of 680 nm. As a result, E1 / 2 (exposure amount required to reduce the charging potential to -300 V) was 0.38 J. / Cm2, and the residual potential was as large as -120V.
[0094]
The electrophotographic photoreceptor was initially modified using a remodeled machine of Canon Laser Beam Printer LBP-8IV ((1 / e2) was remodeled to have an irradiation spot diameter of 63.5 μm in the sub-scanning direction and 40 μm in the main scanning direction). When the image was evaluated with the charging set to -600 V, interference fringes and black spots were observed after the durability test of 4000 sheets, and the reproducibility of one pixel of a highlight portion in an input signal equivalent to 600 dpi was insufficient and uneven. was there.
[0095]
(Example 2)
On a similar aluminum cylinder as in Example 1, 167 parts of a phenolic resin (trade name: Plyofen, manufactured by Dainippon Ink and Chemicals, Inc.) was dissolved in 100 parts of methyl cellosolve, and conductive barium sulfate ultrafine particles (primary) were dissolved. A dispersion of 200 parts (particle size: 50 nm) was applied by dipping and coating so that the film thickness after drying was 10 μm. An undercoat layer having a thickness of 1 μm and a charge generation layer having a thickness of 0.2 μm were formed on this conductive support in the same manner as in Example 2.
[0096]
Next, 20 parts of the resin synthesized in Synthesis Example 2 was added to 30 parts of toluene and dissolved, and the resultant was immersed on the charge generation layer and applied by a coating method. After drying at 120 ° C. for 3 hours, a transparent and uniform charge transport layer having a thickness of 20 μm was formed. The electrophotographic photosensitive member was charged to -600 V, and electrophotographic characteristics were measured using light having a wavelength of 680 nm. As a result, E1 / 2 (exposure amount required to reduce the charging potential to -300 V) was 0.16 J. / Cm 2 and the residual potential was −24 V, which was very good.
[0097]
Image evaluation was performed on this electrophotographic photoreceptor using the same Canon-made laser beam printer as in Example 2 at an initial charge of -500 V. The image was not deteriorated even after a durability test of 4000 sheets, and was equivalent to 600 dpi. The reproducibility of one pixel of the highlight portion in the input signal of (1) was also sufficient.
[0098]
(Example 3)
On an aluminum cylinder having an outer diameter of 80 mm, 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of phenol resin, 30 parts of methyl cellosolve, 30 parts of methanol, and silicone oil (polymethylsiloxane) (Polyoxyalkylene copolymer, weight average molecular weight 3000) 0.002 parts of a conductive layer paint prepared by dispersing and adjusting for 2 hours with a sand mill using 1 mm glass beads was applied, and dried at 140 ° C for 30 minutes. A conductive layer having a thickness of 20 μm was formed.
[0099]
Next, a solution prepared by dissolving 5 parts of alcohol-soluble copolymerized nylon (trade name: Amilan CM-8000, manufactured by Toray Industries, Inc.) in 95 parts of methanol was applied by a dip coating method. After drying at 80 ° C. for 10 minutes, an undercoat layer having a thickness of 1 μm was formed.
[0100]
Next, as a charge generation layer, 5 parts of the following bisazo pigment was added to a solution prepared by dissolving 2 parts of polyvinyl benzal (degree of benzalization of 75% or more) in 95 parts of cyclohexanone, and dispersed by a sand mill for 20 hours. The dispersion was dipped on the undercoat layer formed previously so that the film thickness after drying was 0.2 μm, and applied by a coating method.
[Outside 39]

[0101]
Next, 20 parts of the resin synthesized in Synthesis Example 1 was added to 30 parts of toluene and dissolved, and the resultant was immersed on the charge generation layer and applied by a coating method. After drying at 120 ° C. for 3 hours, a transparent and uniform charge transport layer having a thickness of 20 μm was formed.
[0102]
The electrophotographic photosensitive member was charged to -600 V, and electrophotographic characteristics were measured using light having a wavelength of 680 nm. As a result, E1 / 2 (exposure amount required to reduce the charging potential to -250 V) was 0.55 J. / Cm 2 and the residual potential was −18 V, which was very good.
[0103]
This electrophotographic photoreceptor was set to an initial charge of -600 V by an evaluation machine modified so that the irradiation spot diameter was 63.5 μm in the sub-scanning direction and 20 μm in the main scanning direction using a Canon full-color copier CLC-500. After the initial and 100,000-sheet durability tests, there was no charge injection such as black dots and no interference fringes, an image output with excellent uniformity was obtained, and tone reproducibility was 256 tones at 400 dpi. It was extremely good.
[0104]
(Comparative Example 2)
In the same manner as in Example 3, a charge generation layer was formed.
[0105]
Next, 6 parts of the following triarylamine compound:
[Outside 40]

[0106]
A charge transport layer solution prepared by dissolving 6 parts of a polycarbonate resin (trade name: Z200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in 70 parts of chlorobenzene is applied onto the charge generation layer of Example 2 by a dip coating method. Then, a charge transport layer having a thickness of 20 μm after drying was formed. The electrophotographic photosensitive member was charged to -600 V, and electrophotographic characteristics were measured using light having a wavelength of 680 nm. As a result, E1 / 2 (exposure amount required for decreasing the charging potential to -300 V) was 1.5 J. / Cm2 and the residual potential was as large as -58V.
[0107]
When the image of this electrophotographic photosensitive member was evaluated in the same manner as in Example 3, a good image could not be obtained because a large amount of black spots and the like were generated after the durability test of 20,000 sheets.
[0108]
(Example 4)
In the same manner as in Example 3, a charge generation layer was formed.
[0109]
Next, 20 parts of the resin synthesized in Synthesis Example 2 was added to 30 parts of toluene and dissolved, and the resultant was immersed on the charge generation layer and applied by a coating method. After drying at 120 ° C. for 3 hours, a transparent and uniform charge transport layer having a thickness of 20 μm was formed. The electrophotographic photosensitive member was charged to -600 V, and electrophotographic characteristics were measured using light having a wavelength of 680 nm. As a result, E1 / 2 (exposure amount required for decreasing the charging potential to -300 V) was 0.52 J. / Cm 2 and the residual potential was −12 V, which was very good.
[0110]
This electrophotographic photoreceptor was set to an initial charge of -500 V by an evaluation machine modified to have a Canon full-color copier CLC-500 having an irradiation spot diameter of 63.5 μm in the sub-scanning direction and 20 μm in the main scanning direction. After the initial and 100,000-sheet durability tests, there was no charge injection such as black dots and no interference fringes, an image output with excellent uniformity was obtained, and tone reproducibility was 256 tones at 400 dpi. It was extremely good.
[0111]
【The invention's effect】
As described above, according to the present invention, there is provided an electrophotographic photosensitive member having no light scattering or bleed, having high sensitivity and a low residual potential, and having good coatability at the time of production, and the electrophotographic photosensitive member. A process cartridge and an image forming apparatus can be provided.
[Brief description of the drawings]
FIG. 1 is a diagram illustrating a schematic configuration of a first example of an image forming apparatus of the present invention.
FIG. 2 is a diagram illustrating a schematic configuration of a second example of the image forming apparatus of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Electrophotographic photosensitive member 2 of this invention 2 Axis 3 Primary charging means 4 Image exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Image fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means

Claims (8)

An electrophotographic photosensitive member having a photosensitive layer on a support is characterized in that the photosensitive layer of the electrophotographic photosensitive member contains a resin having a structural unit represented by the following general formula (1).
[Outside 1]

(A represents a hole transporting group; B represents an alkylene group having 2 to 6 carbon atoms. R ¹ represents a substituted or unsubstituted monovalent monovalent having 1 to 10 carbon atoms containing no aliphatic unsaturated bond. R ¹ may be the same or different, and R ² represents a substituted or unsubstituted divalent hydrocarbon group having 2 to 10 carbon atoms or an alkyleneoxyalkylene group, and x represents 1 (Y and z are integers of 0 or more, but (y + z) is an integer of 2 or more.) 2. The electrophotographic photosensitive member according to claim 1, wherein A is a charge transporting group, and the ionization potential of the A residue is in the range of 4.5 to 6.2 eV. A is the following formula (2)
[Outside 2]

(R ² , R ³ , R ⁴ and R ⁵ are organic groups, at least one of which represents an aromatic hydrocarbon ring group or a heterocyclic group, and R ² , R ³ , R ⁴ and R ⁵ are the same R ⁶ represents an aromatic hydrocarbon ring group.)
The electrophotographic photoreceptor according to claim 1, wherein 4. The photosensitive layer according to claim 1, wherein the photosensitive layer comprises at least two layers: a charge transport layer containing a resin obtained by polymerizing the organosilicon-modified hole transport compound represented by the general formula (1) and a charge generation layer. The electrophotographic photoreceptor according to any one of the above. 6. The electrophotographic photoconductor according to claim 5, wherein the charge generation layer contains oxytitanyl phthalocyanine. A crystal in which the oxytitanyl phthalocyanine has characteristic peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° at Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction. The electrophotographic photosensitive member according to claim 5, which is in the form of: The electrophotographic photosensitive member, and at least one unit selected from the group consisting of a charging unit, a developing unit and a cleaning unit are integrally supported, and the electrophotographic photosensitive member is supported in a process cartridge detachably mountable to an image forming apparatus main body. An electrophotographic photosensitive member having a photosensitive layer on a body, wherein the photosensitive layer of the electrophotographic photosensitive member contains a resin represented by the general formula (1). In an image forming apparatus having an electrophotographic photosensitive member, a charging unit, an exposing unit, a developing unit, and a transfer unit, the electrophotographic photosensitive member is an electrophotographic photosensitive member having a photosensitive layer on a support, and the electrophotographic photosensitive member is Wherein the photosensitive layer contains a resin represented by the general formula (1).

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