JP2004037835A - Electrophotographic photoreceptor, process cartridge having the electrophotographic photoreceptor, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which is free of light scattering and bleeding, has a high sensitivity and low residual potential and has good coatability in manufacturing, a processing cartridge having the electrophotographic photoreceptor, and an image forming apparatus. <P>SOLUTION: A photosensitive layer of the electrophotographic photoreceptor having the photosensitive layer on a substrate contains a resin obtained by mixing a charge transferable monomer which has reactive groups, and a charge transferable polymer. <P>COPYRIGHT: (C)2004,JPO

Description

【００１９】
上記一般式（１）において、Ｑは加水分解性基または水酸基を示し、加水分解性基をしては、メトキシ基、エトキシ基、メチルエチルケトオキシム基、ジエチルアミノ基、アセトキシ基、プロペノキシ基、プロポキシ基、ブトキシ基、メトキシエチル基等が挙げられ、より好ましくは−ＯＲ^１で示される。Ｒ^１は加水分解性基であるアルコキシ基あるいはアルコキシアルコキシ基を形成する基であり、炭素数が１〜６の整数であることが好ましく、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、メトキシエチル基等が挙げられる。Ｑとしては、式−ＯＲ^１であるアルコキシ基が好ましい。
【００２０】
Ｒ^２はケイ素原子に直接結合した一価炭化水素基であり、炭素数が１〜１５であることが好ましく、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、等が挙げられる。この他にビニル基、アリル基等のアルケニル基、フェニル基、トリル基等のアリール基が挙げられる。また、Ｒ^２が有してもよい置換基としてはフッ素等のハロゲン原子が挙げられ、ハロゲン置換一価炭化水素基としては、例えばトリフルオロプロピル基、ヘプタフルオロペンチル基、ノナフルオロヘキシル基等で代表されるフロロ炭化水素基等が挙げられる。
【００２１】
Ｒ^３はアルキレン基またはアリーレン基を示し、炭素数が１〜１８であることが好ましく、例えば、メチレン基、エチレン基、プロピレン基、シクロヘキシリデン基、フェニレン基、ビフェニレン基、ナフチレン基、更にはこれらが結合した基等が挙げられる。また、Ｒ^３が有してもよい置換基としてはメチル基、エチル基等のアルキル基、フェニル基のアリール基、フッ素原子塩素原子等のハロゲン原子が挙げられる。これらの中ではＲ^３が式−（ＣＨ_２）ｎ−（ｎは正の整数）で示されることが好ましい。
【００２２】
ｎは１〜１８であることが更に好ましいが、必ずしも直鎖状である必要はない。ｎが１９以上では電荷輸送性基Ａが運動しやすいため硬度が低下し、ケイ素原子に直接電荷輸送性基が結合していると立体障害等で安定性、物性に悪影響を与え易い。ｎは好ましくは２〜８である。また、１は正の整数を示すが、１〜５であることが好ましい。１が６以上では硬化反応において未反応基が残りやすいため電子写真特性等が低下し易い。
【００２３】
また、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る。以下に輸送する電荷が正孔である場合について説明する。この場合、前記一般式（１）で示される有機ケイ素変性電荷輸送性化合物及び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。
【００２４】
また、上記有機ケイ素変成電荷輸送性化合物は正孔輸送能として１ｘ１０^−７ｃｍ^２／Ｖｓｅｃ以上のドリフト移動度を有しているものが好ましい。１ｘ１０^−７ｃｍ^２／Ｖｓｅｃ以下では電子写真感光体として露光後、現像までに正孔が十分に移動できないために見かけ上感度が低減し、残留電位も高くなってしまう問題が発生する場合がある。
【００２５】
上記一般式（１）の電荷輸送性基Ａとしては、正孔輸送性を示すものであればいずれのものでもよく、その水素付加化合物（正孔輸送物質）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ー（ｐージエチルアミノスチリル）アントラセン、１，１−ビスー（４ー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ー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ーフェニルカルバゾール誘導体等が挙げられる。
【００２６】
正孔輸送性基Ａとしては、構造が下記一般式（２）で示されるものが好ましい。
【外８】

【００２７】
（Ｒ^４、Ｒ^５及びＲ^６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^４、Ｒ^５及びＲ^６は同一であっても異なっていてもよい。）
このように正孔輸送性基ＡはＲ^４、Ｒ^５及びＲ^６のうちの少なくとも１つの基の水素原子が除かれて形成された基である。
【００２８】
Ｒ^４、Ｒ^５及びＲ^６の構造の好ましい具体例を以下に示す。
【外９】

【００２９】
【外１０】

【００３０】
【外１１】

【００３１】
上記一般式（１）の有機ケイ素変成電荷輸送性化合物の合成方法としては、公知の方法、例えば、芳香族環にビニル基を有する化合物と置換基を有する水素化ケイ素化合物とから白金系触媒、或いは有機過酸化物等を触媒にヒドロシリル化反応を行うものが好適に用いられる。この場合に使用される白金触媒についてはとくに限定するものではなく、通常のヒドロシリル化反応、付加型シリコーンゴムに用いられている白金触媒であればよく、塩化白金、塩化白金酸、白金−オレフィン錯体、白金−フォスフィン錯体等が挙げられる。白金触媒の添加量に関しては特に制限するものではないが、残留触媒が特性に悪影響を与えないようにできる限り少量で用いることが望ましい。芳香族環にビニル基を有する化合物と置換基を有する水素化ケイ素化合物とから白金系触媒等により、付加反応により本発明の化合物を合成する場合にはビニル基のα位と反応する場合とβ位と反応する場合があり、一般には混合物が生じる。本発明においてはα位、β位のどちらに反応したのものも用いられるが、ケイ素原子と電荷輸送性基を結合している炭化水素基の炭素数が少ない場合には立体障害からはβ位に反応したものが好ましい。
【００３２】
有機過酸化物としては室温以上に半減期を示すものであればよく、特に、ラウリルパーオキシド等のアルキル過酸化物が水素引き抜きを起こしにくいことから好適に用いることができる。ビニル基を有しないものについては、芳香族環をホルミル化し、還元、脱水するか直接Ｗｉｔｔｉｇ反応によりビニル基を導入する方法等により、本発明の合成原料として用いることが可能である。
【００３３】
上記化合物の加水分解、重縮合には、必ずしも触媒が必要ではないが、通常ケイ素樹脂の加水分解、重縮合に用いられる触媒の使用を妨げるものではなく、加水分解、重縮合に要する時間、硬化温度等を考慮してジブチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫オクトエート等のアルキル錫有機酸塩等もしくはノルマルブチルチタネート等の有機チタン酸エステルから適宜選択される。
【００３４】
本発明においては、反応性基を有する正孔輸送性化合物の重合時に３次元架橋構造が形成されることにより、各元素間の運動や外部からの化合物の侵入が困難になることから、硬度や機械的強度が増大し、耐摩耗性が向上するのみでなく、帯電時に発生するアーク放電等の電気的な障害や化学物質等に対する耐久性も向上させることが可能となる。
【００３５】
本発明に用いられる電荷輸送性ポリマーとしては、溶剤可溶であって、乾燥後に正孔を輸送できるポリマーであればいずれのものでもよいが、例えば下記一般式（３）で表される構成単位を有するポリマーを用いることができる。
【外１２】

【００３６】
上記一般式（３）においてＢは電荷輸送性を有する有機基を示す。Ｒ^７及びＲ^８は２価の有機基であり、同一であっても異なっていてもよい。
【００３７】
Ｒ^７及びＲ^８の構造の好ましい具体例を以下に示す。
【外１３】

【００３８】
最後にあげた例の場合の１種として、一般式（３）で示した構成単位は下記一般式（５）で示すことができる。
【外１４】

【００３９】
上記一般式（５）においてＢは電荷輸送性を有する有機基を示す。Ｒ^１０、Ｒ^１１は置換もしくは無置換の一価炭化水素基を示し、Ｒ^１０、Ｒ^１１は同一であっても違っても良い。Ｒ^１２は置換もしくは無置換のアルキレン基またはアリーレン基を示す。
【００４０】
上記一般式（５）で示される樹脂は、下記一般式（６）で示されるモノマーを加水分解、重縮合して得ることができる。
【外１５】

【００４１】
上記一般式（６）において、Ｑは加水分解性基または水酸基を示し、加水分解性基をしては、メトキシ基、エトキシ基、メチルエチルケトオキシム基、ジエチルアミノ基、アセトキシ基、プロペノキシ基、プロポキシ基、ブトキシ基、メトキシエチル基等が挙げられ、より好ましくは−ＯＲ^１で示される。Ｒ^１　加水分解性基であるアルコキシ基あるいはアルコキシアルコキシ基を形成する基であり、炭素数が１〜６の整数であることが好ましく、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、メトキシエチル基等が挙げられる。Ｑとしては、式−ＯＲ^１であるアルコキシ基が好ましい。
【００４２】
上記一般式（６）の電荷輸送性基Ｂとしては、上記一般式（１）で示した電荷輸送性モノマーと同極性の電荷を輸送できる能力を示すものであればいずれのものでもよく、輸送する電荷が正孔である場合には一般式（２）で示されるものが好ましい。また、相溶性の観点から、正孔輸送性基Ａと正孔輸送性基Ｂが類似構造をとることがより好ましい。
【００４３】
上記一般式（６）で示されるモノマーは上記一般式（１）で示したモノマーと同様の方法で合成可能である。
【００４４】
本発明の正孔輸送能を有する硬化性組成物をもちいて電子写真感光体を製造する例を下記に示す。
【００４５】
電子写真感光体の支持体としては支持対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。
【００４６】
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イ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。
【００４７】
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。
【００４８】
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、エチレンー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。
【００４９】
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。
【００５０】
機能分離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。
【００５１】
電荷発生材料としては、例えば、セレンーテルル、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、特にアゾ顔料およ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°および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。
【００５２】
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。
【００５３】
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。
【００５４】
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。
【００５５】
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。
【００５６】
次に、本発明のプロセスカートリッジ並びに電子写真装置について説明する。
【００５７】
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。
【００５８】
図において１はドラム状の本発明の電子写真感光体であり、軸２を中心に矢印方向に所定の周速度で回転駆動される。感光体１は、回転過程において、一次帯電手段３によりその周面に正または負の所定電位の均一帯電を受け、次いで、レーザービーム走査露光等の露光手段（不図示）からの露光光４を受ける。こうして感光体１の周面に静電潜像が順次形成されていく。
【００５９】
形成された静電潜像は、現像手段５によりトナー現像され、現像されたトナー現像像は不図示の給紙部から感光体１と転写手段６との間に感光体１の回転と同期取り出されて給紙された転写材７に、転写手段６により順次転写されていく。
【００６０】
像転写を受けた転写材７は、感光体面から分離されて像定着手段８へ導入されて像定着を受けることにより複写物（コピー）として装置外にプリントアウトされる。
【００６１】
像転写後の感光体１の表面は、クリーニング手段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。
【００６２】
本発明においては、上述の電子写真感光体１、一次帯電手段３、現像手段５及びクリーニング手段９等の構成要素のうち、複数のものをプロセスカートリッジとして一体に結合して構成し、このプロセスカートリッジを複写機やレーザービームプリンタ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２と共に一体に支持してカートリッジ化して、装置本体のレール１２等の案内手段を用いて装置本体に着脱可能なプロセスカートリッジ１１とすることができる。
【００６３】
また露光光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、センサーで画像を読みとり、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アレイの駆動等により照射される光である。
【００６４】
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。
【００６５】
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。
【００６６】
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２２０５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。
【００６７】
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。
【００６８】
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。
【００６９】
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。
【００７０】
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。
【００７１】
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。
【００７２】
【発明の実施の形態】
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反応性基を有する電荷輸送性モノマーは、例えば以下のようにして合成した。
【００７３】
（合成例１）
２、７ビス｛４’−〔２−（トリエトキシシリル）エチル〕ジフェニルアミノ｝−９、９ジメチルフルオレンの合成
トルエン４０ｍｌ、トリエトキシシラン９．９ｇ（６０ｍｍｏｌ）及びトリス（テトラメチルジビニルジシロキサン）二白金（０）のトルエン溶液０．０１８ｍｍｏｌを三つ口フラスコに取り、室温で撹拌しながら２、７、ビス（４’ビニルジフェニルアミノ）−９、９ジメチルフルオレン１６ｇ　のトルエン溶液２０ｍｌを滴下した。滴下終了後、７０℃で３時間撹拌を行った後、溶媒を減圧下で除き、淡黄色油状の２、７ビス｛４’−〔２−（トリエトキシシリル）エチル〕ジフェニルアミノ｝−９、９ジメチルフルオレンを得た。収量は２１．８ｇであった。
【００７４】
（合成例２）
Ｎ，Ｎ’−ビス｛４−〔２−（メチルジメトキシシシリル）エチル〕フェニル｝−Ｎ，Ｎ’−ビス−（フェニル）−ベンジジンの合成
トルエン４０ｍｌ、メチルジメトキシシラン４．０ｇ（３８ｍｍｏｌ）及びジクロロ（ｈ−シクロオクタ−１，５−ジエン）白金（ＩＩ）０．３４ｍｍｏｌを三つ口フラスコに取り、室温で撹拌しながらＮ，Ｎ’−ビス−４−（ビニルフェニル）−Ｎ，Ｎ’−ビス−（フェニル）ーベンジジン１５．７ｇのトルエン溶液２０ｍｌを滴下した。滴下終了後、７０℃で３時間撹拌を行った後、溶媒を減圧下で除去し、淡黄色油状のＮ，Ｎ’−ビス｛４−〔２−（メチルジメトキシシシリル）エチル〕フェニル｝−Ｎ，Ｎ’−ビス−（フェニル）−ベンジジンを得た。収量は１６．８ｇであった。
【００７５】
本発明に用いられる電荷輸送性ポリマーの前駆体モノマーは、例えば以下のようにして合成した。
【００７６】
（合成例３）
２、７ビス｛４’−〔２−（ジメチルメトキシシリル）エチル〕ジフェニルアミノ｝−９、９ジメチルフルオレンの合成
トルエン４０ｍｌ、ジメチルメトキシシラン５．４ｇ　（６０ｍｍｏｌ）及びトリス（テトラメチルジビニルジシロキサン）二白金（０）のトルエン溶液０．０１８ｍｍｏｌを三つ口フラスコに取り、室温で撹拌しながら２、７、ビス（４’ビニルジフェニルアミノ）−９、９ジメチルフルオレン１６ｇ　のトルエン溶液２０ｍｌを滴下した。滴下終了後、７０℃で３時間撹拌を行った後、溶媒を減圧下で除き、淡黄色油状の２、７ビス｛４’−〔２−（ジメチルメトキシシリル）エチル〕ジフェニルアミノ｝−９、９ジメチルフルオレンを得た。収量は１８．２ｇであった。
【００７７】
（合成例４）
Ｎ，Ｎ’−ビス｛４−〔２−（ジメチルアセトキシシリル）エチル〕フェニル｝−Ｎ，Ｎ’−ビス−（フェニル）ーベンジジンの合成
トルエン４０ｍｌ、ジメチルアセトキシシラン４．５ｇ　（３８ｍｍｏｌ）及びジクロロ（ｈ−シクロオクタ−１，５−ジエン）白金（ＩＩ）０．３４ｍｍｏｌを三つ口フラスコに取り、室温で撹拌しながらＮ，Ｎ’−ビス−４−（ビニルフェニル）−Ｎ，Ｎ’−ビス−（フェニル）ーベンジジン１５．７ｇのトルエン溶液２０ｍｌを滴下した。滴下終了後、７０℃で３時間撹拌を行った後、溶媒を減圧下で除去し、淡黄色油状のＮ，Ｎ’−ビス｛４−〔２−（ジメチルアセトキシシシリル）エチル〕フェニル｝−Ｎ，Ｎ’−ビス−（フェニル）−ベンジジンを得た。収量は１８．０ｇであった。
【００７８】
本発明に用いられる電荷輸送性ポリマーは、例えば以下のようにして合成した。
【００７９】
（合成例５）
合成例３で得られたモノマー１５．２ｇをトルエン２０ｍｌに溶解し、ジブチル錫ジラウレート０．１ｇを加え、室温で撹拌しながら水を０．４ｇを滴下した。滴下終了後、一週間加熱環流を行った。その後、室温まで冷却し、活性炭を加えて濾過した後、濾液を濃縮してトルエン／エタノールで再沈精製を行い、１０．１ｇのポリマーを得た。この化合物の分子量をＧＰＣにて測定したところＭｗ＝１．５×１０^４であった（スチレン換算）であった。
【００８０】
（合成例６）
合成例４で得られたモノマー１５．５ｇをトルエン２０ｍｌに溶解し、ジブチル錫ジアセテート０．０８ｇを加え、室温で撹拌しながら水を０．４ｇを滴下した。滴下終了後、一週間加熱環流を行った。その後、室温まで冷却し、活性炭を加えて濾過した後、濾液を濃縮してトルエン／エタノールで再沈精製を行い、１０．１ｇのポリマーを得た。この化合物の分子量をＧＰＣにて測定したところＭｗ＝１．８×１０^４であった（スチレン換算）であった。
【００８１】
（合成例７）
８．８％（ｗ／ｖ）の水酸化ナトリウム水溶液５８０ｍｌに、下記構造式のトリフェニルアミン構造を有する二価フェノール１９９．６ｇ及びハイドロサルファイト０．１ｇを加え溶解した。これにメチレンクロライド３６０ｍｌを加え、１５℃に保ちながら攪拌しつつ、ｐ−ｔ−ブチルフェノール（ＰＴＢＰ）２．０ｇを加え、ついでホスゲン５１ｇを６０分かけて吹き込んだ。
【外１６】

【００８２】
吹き込み終了後、激しく攪拌して、反応液を乳化させ、乳化後０．２ｍｌのトリエチルアミンを加え、約１時間攪拌し重合させた。重合液を水相と有機相に分離し、有機相をリン酸で中和し、洗液のｐＨが中性になるまで水洗を繰り返した後、イソプロパノール４７０ｍｌを加え、重合物を沈殿させた。沈殿物を濾過後、乾燥して下記構造式の重合体を得た。
【外１７】

【００８３】
（合成例８）
攪拌機、温度計、冷却器を備えたフラスコに、下記構造式
【外１８】

【００８４】
で表される１，４ービス（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、下記構造式
【外１９】

【００８５】
で表されるジビニルベンジジン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ー核磁気共鳴スペクトル分析（以下、１３Ｃ−ＮＭＲ）および２９Ｓｉー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２０】

【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イ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イ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イング法で塗工した。
【００９０】
ついで、合成例５で合成したポリマー２０部と合成例１で合成したモノマー６０部にトルエン１５０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イ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。
【００９１】
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／ｃｍ^２、残留電位が　２８Ｖと非常に良好であった。
【００９２】
本電子写真感光体をキヤノン製レーザービームプリンタＬＢＰ−ＳＸ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、５０００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。
【００９３】
（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。次いで、下記のトリアリールアミン化合物６部と、
【外２１】

【００９４】
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／ｃｍ^２、残留電位が−１２０Ｖと大きかった。
【００９５】
本電子写真感光体をキヤノン製レーザービームプリンタＬＢＰ−ＳＸ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およ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。
【００９６】
（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。
【００９７】
ついで、合成例６で合成したポリマー２０部と合成例２で合成したモノマー６０部をトルエン１５０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イ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。
【００９８】
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／ｃｍ^２、残留電位が　−２４Ｖと非常に良好であった。
【００９９】
本電子写真感光体を実施例２と同様のキヤノン製レーザービームプリンタを用い初期帯電−６００Ｖに設定して画像評価をおこなったところ、５０００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。
【０１００】
（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部およ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。
【０１０１】
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イ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。
【０１０２】
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イング法で塗工した。
【外２２】

【０１０３】
ついで、合成例５で合成したポリマー２０部と合成例１で合成したモノマー６０部にトルエン１５０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イ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。
【０１０４】
この電子写真感光体を−７００Ｖ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（−３５０Ｖまで帯電電位が減少するために必要な露光量）が０．６１μＪ／ｃｍ^２、残留電位が　−１９Ｖと非常に良好であった。
【０１０５】
本電子写真感光体をキヤ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−７００Ｖ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および干渉縞もなく、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。
【０１０６】
（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。
【０１０７】
次いで、下記のトリアリールアミン化合物６部と、
【外２３】

【０１０８】
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／ｃｍ^２、残留電位が−５８Ｖと大きかった。
【０１０９】
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。
【０１１０】
（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。
【０１１１】
ついで、合成例６で合成したポリマー２０部と合成例２で合成したモノマー６０部をトルエン１５０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イ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−７００Ｖ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０．５６μＪ／ｃｍ^２、残留電位が−１３Ｖと非常に良好であった。
【０１１２】
本電子写真感光体をキヤ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−７００Ｖ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および干渉縞もなく、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。
【０１１３】
（実施例５）
合成例５で合成したポリマーに替えて、ポリ［２，７−（９，９−ジオクチルフルオレン）］を使用した以外は、実施例３と同様にして実施例５の電子写真感光体を作成した。
【０１１４】
（実施例６）
合成例６で合成したポリマーに替えて、ポリ（４−メチルトリフェニルアミン）を使用した以外は、実施例４と同様にして実施例６の電子写真感光体を作成した。
【０１１５】
（実施例７）
合成例５で合成したポリマーに替えて、合成例７で合成したポリマーを使用した以外は、実施例３と同様にして実施例７の電子写真感光体を作成した。
【０１１６】
（実施例８）
合成例６で合成したポリマーに替えて、合成例８で合成したポリマーを使用した以外は、実施例４と同様にして実施例８の電子写真感光体を作成した。
【０１１７】
（実施例９）
合成例５で合成したポリマーに替えて、下記構造式で示されるポリマーを使用した以外は、実施例３と同様にして実施例９の電子写真感光体を作成した。
【外２４】

【０１１８】
（実施例１０）
合成例６で合成したポリマーに替えて、下記構造式で示されるポリマーを使用した以外は、実施例４と同様にして実施例１０の電子写真感光体を作成した。
【外２５】

【０１１９】
（実施例１１）
合成例１で合成したモノマーに替えて、Ｎ，Ｎ’−ビス｛４−〔２−（トリエトキシシシリル）エチル〕フェニル｝−Ｎ，Ｎ’−ビス−（フェニル）−ベンジジンを使用した以外は、実施例９と同様にして実施例１１の電子写真感光体を作成した。
【０１２０】
（実施例１２）
合成例１で合成したモノマーに替えて、Ｎ，Ｎ’−ビス｛４−〔３−（メチルジメトキシシリル）プロピル〕フェニル｝−Ｎ，Ｎ’−ビス−（フェニル）−ベンジジンを使用した以外は、実施例１０と同様にして実施例１２の電子写真感光体を作成した。
【０１２１】
実施例５〜１２の電子写真感光体を実施例３の電子写真感光体と同様に評価したところ、初期及び耐久試験後も黒ポチ等の電荷注入および干渉縞もなく、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。
【０１２２】
【発明の効果】
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できる。
【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　レール
２００　原稿厚板
２０１　イメージスキャナ部
２０２　プリンタ部
２０３　原稿台ガラス
２０４　原稿
２０５　ハロゲンランプ
２０６，２０７　ミラー
２０８　赤外カットフィルター
２０９　レンズ
２１０　３ラインセンサ
２１１　信号処理部
２１２　レーザドライバ
２１３　半導体レーザー
２１４　ポリゴンミラー
２１５　ｆ−θレンズ
２１６　ミラー
２１７　感光体ドラム
２１８　回転現像機
２１９　マゼンタ現像機
２２０　シアン現像機
２２１　イエロー現像機
２２２　ブラック現像機
２２３　転写ドラム
２２４，２２５　用紙カセット
２２６　定着ユニット[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, poly (carbonate) Silicon) 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. 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 before, 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]
As a method for improving the above-listed problems, JP-A-11-015185 proposes a photoreceptor having a surface layer containing a resin obtained by polycondensing an organosilicon-modified hole-transporting compound as a monomer component. ing. However, in a solution containing only a monomer component in a solvent, it is difficult to obtain a solution viscosity, so that it may be difficult to obtain a sufficient film thickness.
[0013]
Further, when a polymer is added to increase the solution viscosity, there is a problem that the potential characteristics are worse than when no polymer is added.
[0014]
[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.
[0015]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, by using a coating liquid obtained by mixing a charge transporting monomer having a reactive group and a charge transporting polymer, the production The present inventors have found that the coating property at the time can be compatible with the surface properties and potential characteristics of the photoreceptor, and have reached the present invention.
[0016]
That is, the present invention relates to an electrophotographic photosensitive member having a photosensitive layer on a support, wherein the photosensitive layer of the electrophotographic photosensitive member is obtained by mixing a resin obtained by mixing a charge transporting monomer having a reactive group with a charge transporting polymer. It is characterized by containing.
[0017]
Further, the present invention is a process cartridge and an image forming apparatus having the above electrophotographic photosensitive member.
[0018]
BEST MODE FOR CARRYING OUT THE INVENTION
As the charge transporting monomer having a reactive group, a compound represented by the following general formula (1) can be used.
[Outside 7]

[0019]
In the general formula (1), Q represents a hydrolyzable group or a hydroxyl group, and the hydrolyzable group includes a methoxy group, an ethoxy group, a methylethylketoxime group, a diethylamino group, an acetoxy group, a propenoxy group, a propoxy group, Butoxy group, methoxyethyl group and the like, more preferably -OR ¹ Indicated by R ¹ Is a group forming an alkoxy group or an alkoxyalkoxy group that is a hydrolyzable group, and preferably has an integer of 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Examples include a hexyl group and a methoxyethyl group. Q is the formula -OR ¹ Is preferred.
[0020]
R ² Is a monovalent hydrocarbon group directly bonded to a silicon atom, and preferably has 1 to 15 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Other examples include alkenyl groups such as vinyl group and allyl group, and aryl groups such as phenyl group and tolyl group. Also, R ² Examples of the substituent which may have a halogen atom such as fluorine, and examples of the halogen-substituted monovalent hydrocarbon group include fluorotrifluoro groups, heptafluoropentyl groups, and nonafluorohexyl groups. And a hydrocarbon group.
[0021]
R ³ Represents an alkylene group or an arylene group, and preferably has 1 to 18 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, a cyclohexylidene group, a phenylene group, a biphenylene group, a naphthylene group, and further, And a bonded group. Also, R ³ Examples of the substituent which may have an alkyl group such as a methyl group and an ethyl group, an aryl group such as a phenyl group, and a halogen atom such as a fluorine atom and a chlorine atom. In these, R ³ Is the formula-(CH ₂ ) N- (n is a positive integer).
[0022]
n is more preferably 1 to 18, but does not necessarily have to be linear. When n is 19 or more, the charge-transporting group A easily moves, so that the hardness is lowered. When the charge-transporting group is directly bonded to the silicon atom, steric hindrance or the like tends to adversely affect stability and physical properties. n is preferably 2 to 8. Also, 1 represents a positive integer, preferably 1 to 5. If 1 is 6 or more, unreacted groups are likely to remain in the curing reaction, so that the electrophotographic properties and the like are likely to be reduced.
[0023]
The charge transporting property in the present invention refers to the ability to transport charges. The case where the charges to be transported are holes will be described below. In this case, the organosilicon-modified charge-transporting compound represented by the general formula (1) and the hydrogenated product of A preferably have an ionization potential of 6.2 eV or less, and particularly preferably have an ionization potential of 4.5 to 6.2 eV. Preferably, there is. 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).
[0024]
The above-mentioned organosilicon modified charge transporting compound has a hole transporting ability of 1 × 10 ^-7 cm ² Those having a drift mobility of / Vsec or more are preferable. 1x10 ^-7 cm ² If it is less than / Vsec, the holes may not move sufficiently after the exposure as an electrophotographic photoreceptor until development, so that the sensitivity may be apparently reduced and the residual potential may be increased.
[0025]
The charge transporting group A in the general formula (1) may be any one as long as it has a hole transporting property. Diazole derivatives, imidazole derivatives, triarylamine derivatives such as triphenylamine, 9- (p-diethylaminostyryl) anthracene, 1,1-bis (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, phenyl Hydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives, N-phenylcarbazole derivatives and the like.
[0026]
As the hole transporting group A, those having a structure represented by the following general formula (2) are preferable.
[Outside 8]

[0027]
(R ⁴ , R ⁵ And R ⁶ Is an organic group, at least one of which represents an aromatic hydrocarbon ring group or a heterocyclic group; ⁴ , R ⁵ And R ⁶ May be the same or different. )
Thus, the hole transporting group A is R ⁴ , R ⁵ And R ⁶ Is a group formed by removing a hydrogen atom from at least one of the groups.
[0028]
R ⁴ , R ⁵ And R ⁶ Preferred examples of the structure are shown below.
[Outside 9]

[0029]
[Outside 10]

[0030]
[Outside 11]

[0031]
As a method for synthesizing the organosilicon-modified charge-transporting compound of the general formula (1), known methods, for example, a platinum-based catalyst comprising a compound having a vinyl group on an aromatic ring and a silicon hydride compound having a substituent, Alternatively, a compound that performs a hydrosilylation reaction using an organic peroxide or the like as a catalyst is suitably used. The platinum catalyst used in this case is not particularly limited, and may be any platinum catalyst used in ordinary hydrosilylation reactions and addition-type silicone rubbers, such as platinum chloride, chloroplatinic acid, and platinum-olefin complexes. , A platinum-phosphine complex and the like. The amount of the platinum catalyst to be added is not particularly limited, but it is preferable to use the platinum catalyst in the smallest possible amount so as not to adversely affect the characteristics of the catalyst. When a compound of the present invention is synthesized by an addition reaction from a compound having a vinyl group on an aromatic ring and a silicon hydride compound having a substituent with a platinum-based catalyst or the like, when the compound reacts with the α-position of the vinyl group, May form a mixture. In the present invention, those reacting at either the α-position or the β-position may be used. However, when the number of carbon atoms in the hydrocarbon group bonding the silicon atom and the charge transporting group is small, the β-position may be sterically hindered. Are preferred.
[0032]
Any organic peroxides having a half-life at room temperature or higher may be used. In particular, alkyl peroxides such as lauryl peroxide can be suitably used because hydrogen extraction hardly occurs. Those having no vinyl group can be used as the raw material for synthesis of the present invention by, for example, a method in which an aromatic ring is formylated, reduced and dehydrated, or a method of directly introducing a vinyl group by a Wittig reaction.
[0033]
The hydrolysis and polycondensation of the above compounds do not necessarily require a catalyst, but usually do not hinder the hydrolysis of the silicon resin and the use of the catalyst used for the polycondensation. In consideration of the temperature and the like, it is appropriately selected from alkyltin organic acid salts such as dibutyltin diacetate, dibutyltin dilaurate and dibutyltin octoate, and organic titanates such as normal butyl titanate.
[0034]
In the present invention, a three-dimensional cross-linked structure is formed during the polymerization of the hole transporting compound having a reactive group, thereby making it difficult for movement between the elements or intrusion of the compound from the outside. The mechanical strength is increased, and not only the wear resistance is improved, but also the durability against electric obstacles such as arc discharge generated at the time of charging and chemical substances is improved.
[0035]
The charge transporting polymer used in the present invention may be any polymer that is soluble in a solvent and can transport holes after drying. For example, the structural unit represented by the following general formula (3) may be used. Can be used.
[Outside 12]

[0036]
In the general formula (3), B represents an organic group having a charge transporting property. R ⁷ And R ⁸ Is a divalent organic group, which may be the same or different.
[0037]
R ⁷ And R ⁸ Preferred examples of the structure are shown below.
[Outside 13]

[0038]
As one of the last-mentioned examples, the structural unit represented by the general formula (3) can be represented by the following general formula (5).
[Outside 14]

[0039]
In the general formula (5), B represents an organic group having a charge transporting property. R ¹⁰ , R ¹¹ Represents a substituted or unsubstituted monovalent hydrocarbon group; ¹⁰ , R ¹¹ May be the same or different. R ¹² Represents a substituted or unsubstituted alkylene group or an arylene group.
[0040]
The resin represented by the general formula (5) can be obtained by hydrolyzing and polycondensing a monomer represented by the following general formula (6).
[Outside 15]

[0041]
In the general formula (6), Q represents a hydrolyzable group or a hydroxyl group, and the hydrolyzable group includes methoxy, ethoxy, methylethylketoxime, diethylamino, acetoxy, propenoxy, propoxy, Butoxy group, methoxyethyl group and the like, more preferably -OR ¹ Indicated by R ¹ It is a group that forms an alkoxy group or an alkoxyalkoxy group that is a hydrolyzable group, and preferably has an integer of 1 to 6 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl Group, methoxyethyl group and the like. Q is the formula -OR ¹ Is preferred.
[0042]
The charge transporting group B of the general formula (6) may be any one as long as it has the ability to transport charges of the same polarity as the charge transporting monomer represented by the general formula (1). When the charge to be generated is a hole, the charge represented by the general formula (2) is preferable. Further, from the viewpoint of compatibility, it is more preferable that the hole transporting group A and the hole transporting group B have a similar structure.
[0043]
The monomer represented by the general formula (6) can be synthesized by the same method as the monomer represented by the general formula (1).
[0044]
An example of producing an electrophotographic photosensitive member using the curable composition having a hole transporting ability of the present invention will be described below.
[0045]
As the support of the electrophotographic photosensitive member, the support itself has conductivity, 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
[0046]
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 insulating fine particles may be coated on the surface and used. The content of the conductive fine particles is used so that the volume resistance is sufficiently low. ¹⁰ It is added so as to have a resistance of Ωcm or less. More preferably 1 × 10 ⁸ It is used below Ωcm.
[0047]
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.
[0048]
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.
[0049]
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
[0050]
The function-separated type photosensitive layer will be described. The photosensitive layer has a configuration in which a charge transport layer is laminated on a charge generation layer and a configuration in which a charge generation layer is laminated on a charge transport layer.
[0051]
As the charge generating material, for example, selenium-tellurium, pyrylium-based dye, thiopyrylium-based dye, phthalocyanine-based pigment, anthantrone-based pigment, dibenzpyrenequinone-based pigment, pyranthrone-based pigment, azo-based pigment, indigo-based pigment, quinacridone-based pigment, Cyanine 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.
[0052]
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.
[0053]
The resin of the present invention can be used as a charge transporting layer or a surface protective layer having a hole transporting ability.
[0054]
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.
[0055]
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.
[0056]
Next, the process cartridge and the electrophotographic apparatus of the present invention will be described.
[0057]
FIG. 1 shows a schematic configuration of a first example of an image forming apparatus having the process cartridge of the present invention.
[0058]
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. The photoreceptor 1 receives a uniform charge of a predetermined positive or negative potential on the peripheral surface thereof by the primary charging means 3 during the rotation process, and then applies exposure light 4 from 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.
[0059]
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.
[0060]
The transfer material 7 having undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing, thereby being printed out of the apparatus as a copy.
[0061]
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.
[0062]
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, the process cartridge 11 can be integrally supported together with the primary charging means 2 to form a cartridge, and the process cartridge 11 can be attached to and detached from the apparatus main body using guide means such as the rail 12 of the apparatus main body.
[0063]
When the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 reads reflected light or transmitted light from an original, or reads an image with a sensor and converts it into a signal. Light emitted by driving the LED array or the like.
[0064]
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.
[0065]
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.
[0066]
In the image scanner unit 201, reference numeral 200 denotes a document thick plate, a document 204 on a document table glass 203 is irradiated with light of a halogen lamp 2205 passing through an infrared cut filter 208, and reflected light from the document 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.
[0067]
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.
[0068]
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 the photosensitive drum 217 via the polygon mirror 214, the f-θ lens 215, and the mirror 216.
[0069]
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.
[0070]
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.
[0071]
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.
[0072]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described with reference to examples. The charge transporting monomer having a reactive group used in the present invention was synthesized, for example, as follows.
[0073]
(Synthesis example 1)
Synthesis of 2,7 bis {4 '-[2- (triethoxysilyl) ethyl] diphenylamino} -9,9 dimethylfluorene
40 ml of toluene, 9.9 g (60 mmol) of triethoxysilane and 0.018 mmol of a toluene solution of tris (tetramethyldivinyldisiloxane) diplatinum (0) are placed in a three-necked flask, and 2,7, bis 20 ml of a toluene solution of 16 g of (4'vinyldiphenylamino) -9,9 dimethylfluorene was added dropwise. After completion of the dropwise addition, the mixture was stirred at 70 ° C. for 3 hours, and then the solvent was removed under reduced pressure, and pale yellow oily 2,7bis {4 ′-[2- (triethoxysilyl) ethyl] diphenylamino} -9, 9 dimethylfluorene was obtained. The yield was 21.8 g.
[0074]
(Synthesis example 2)
Synthesis of N, N'-bis {4- [2- (methyldimethoxysilyl) ethyl] phenyl} -N, N'-bis- (phenyl) -benzidine
40 ml of toluene, 4.0 g (38 mmol) of methyldimethoxysilane and 0.34 mmol of dichloro (h-cycloocta-1,5-diene) platinum (II) are placed in a three-necked flask, and stirred at room temperature for N, N′-. 20 ml of a toluene solution of 15.7 g of bis-4- (vinylphenyl) -N, N′-bis- (phenyl) -benzidine was added dropwise. After completion of the dropwise addition, the mixture was stirred at 70 ° C. for 3 hours, and then the solvent was removed under reduced pressure to give pale yellow oily N, N′-bis {4- [2- (methyldimethoxysilyl) ethyl] phenyl}-. N, N'-bis- (phenyl) -benzidine was obtained. The yield was 16.8 g.
[0075]
The precursor monomer of the charge transporting polymer used in the present invention was synthesized, for example, as follows.
[0076]
(Synthesis example 3)
Synthesis of 2,7 bis {4 '-[2- (dimethylmethoxysilyl) ethyl] diphenylamino} -9,9 dimethylfluorene
40 ml of toluene, 5.4 g (60 mmol) of dimethylmethoxysilane and 0.018 mmol of a toluene solution of tris (tetramethyldivinyldisiloxane) diplatinum (0) are placed in a three-necked flask, and 2,7, bis 20 ml of a toluene solution of 16 g of (4'vinyldiphenylamino) -9,9 dimethylfluorene was added dropwise. After completion of the dropwise addition, the mixture was stirred at 70 ° C. for 3 hours, and then the solvent was removed under reduced pressure to give pale yellow oily 2,7bis {4 ′-[2- (dimethylmethoxysilyl) ethyl] diphenylamino} -9, 9 dimethylfluorene was obtained. The yield was 18.2 g.
[0077]
(Synthesis example 4)
Synthesis of N, N'-bis {4- [2- (dimethylacetoxysilyl) ethyl] phenyl} -N, N'-bis- (phenyl) -benzidine
40 ml of toluene, 4.5 g (38 mmol) of dimethylacetoxysilane and 0.34 mmol of dichloro (h-cycloocta-1,5-diene) platinum (II) are placed in a three-necked flask, and stirred at room temperature for N, N′-. 20 ml of a toluene solution of 15.7 g of bis-4- (vinylphenyl) -N, N′-bis- (phenyl) -benzidine was added dropwise. After completion of the dropwise addition, the mixture was stirred at 70 ° C. for 3 hours, and then the solvent was removed under reduced pressure to give pale yellow oily N, N′-bis {4- [2- (dimethylacetoxysilyl) ethyl] phenyl}-. N, N'-bis- (phenyl) -benzidine was obtained. The yield was 18.0 g.
[0078]
The charge transporting polymer used in the present invention was synthesized, for example, as follows.
[0079]
(Synthesis example 5)
15.2 g of the monomer obtained in Synthesis Example 3 was dissolved in 20 ml of toluene, 0.1 g of dibutyltin dilaurate was added, and 0.4 g of water was added dropwise with stirring at room temperature. After the completion of the dropwise addition, heating and reflux were performed for one week. Thereafter, the mixture was cooled to room temperature, filtered after adding activated carbon, and the filtrate was concentrated and purified by reprecipitation with toluene / ethanol to obtain 10.1 g of a polymer. When the molecular weight of this compound was measured by GPC, Mw = 1.5 × 10 ⁴ (Styrene conversion).
[0080]
(Synthesis example 6)
15.5 g of the monomer obtained in Synthesis Example 4 was dissolved in 20 ml of toluene, 0.08 g of dibutyltin diacetate was added, and 0.4 g of water was added dropwise with stirring at room temperature. After the completion of the dropwise addition, heating and reflux were performed for one week. Thereafter, the mixture was cooled to room temperature, filtered after adding activated carbon, and the filtrate was concentrated and purified by reprecipitation with toluene / ethanol to obtain 10.1 g of a polymer. When the molecular weight of this compound was measured by GPC, Mw = 1.8 × 10 ⁴ (Styrene conversion).
[0081]
(Synthesis example 7)
In 580 ml of an aqueous 8.8% (w / v) sodium hydroxide solution, 199.6 g of dihydric phenol having a triphenylamine structure represented by the following structural formula and 0.1 g of hydrosulfite were added and dissolved. To this was added 360 ml of methylene chloride, 2.0 g of pt-butylphenol (PTBP) was added while stirring at 15 ° C., and 51 g of phosgene was blown in over 60 minutes.
[Outside 16]

[0082]
After the completion of the blowing, the mixture was vigorously stirred to emulsify the reaction solution. After the emulsification, 0.2 ml of triethylamine was added, and the mixture was stirred and polymerized for about 1 hour. The polymerization liquid was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and water washing was repeated until the pH of the washing liquid became neutral. Then, 470 ml of isopropanol was added to precipitate a polymer. The precipitate was filtered and dried to obtain a polymer having the following structural formula.
[Outside 17]

[0083]
(Synthesis example 8)
In a flask equipped with a stirrer, thermometer and cooler, the following structural formula
[Outside 18]

[0084]
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 them at 40 to 50 ° C., a complex solution of platinum and divinyltetramethylsiloxane is added to the system. It was added in such an amount that the content of platinum metal itself in it became 30 ppm. Then, the following structural formula
[Outside 19]

[0085]
A mixture of 2.1 g (4 mmol) of divinylbenzidine 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 is subjected to gel permeation chromatography (hereinafter, GPC) using toluene as a solvent, Fourier transform infrared spectroscopy (hereinafter, FT-IR), 13C-nuclear magnetic resonance spectrum analysis (hereinafter, referred to as When analyzed by 13 C-NMR) and 29 Si-nuclear magnetic resonance spectrum analysis (hereinafter, 29 Si-NMR), it was found to be an aromatic silicon-containing polymer represented by the following formula.
[Outside 20]

[0086]
(Example 1)
To an aluminum cylinder having an outer diameter of 30 mm obtained by a drawing process, 167 parts of a phenol resin (trade name: Plyofen, manufactured by Dainippon Ink and Chemicals, Inc.) was dissolved in 100 parts of methyl cellosolve. A dispersion in which 200 parts of fine particles (primary particle diameter: 50 nm) and 3 parts of silicone resin particles having an average particle diameter of 2 μm were dispersed was applied by a dipping coating method, and a conductive layer having a dried film thickness of 15 μm was formed.
[0087]
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 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]
This 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]
Then, a solution prepared by dissolving 20 parts of the polymer synthesized in Synthesis Example 5 and 150 parts of toluene in 60 parts of the monomer synthesized in Synthesis Example 1 in addition to 150 parts of toluene was immersed on the charge generation layer and coated 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.
[0091]
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 as very good as 28 V.
[0092]
The electrophotographic photoreceptor was initially remodeled using a remodeled Canon laser beam printer LBP-SX ((1 / e2) remodeled 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 5000 sheets, and the reproducibility of one pixel of a highlight portion in an input signal equivalent to 600 dpi was sufficient.
[0093]
(Comparative Example 1)
In the same manner as in Example 1, up to the charge generation layer was formed. Next, 6 parts of the following triarylamine compound:
[Outside 21]

[0094]
A solution for a charge transport layer in which 6 parts of a polycarbonate resin (trade name: Z200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) is dissolved in 70 parts of chlorobenzene is applied on 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. / Cm ² And the residual potential was as large as -120V.
[0095]
The electrophotographic photoreceptor was initially remodeled using a remodeled Canon laser beam printer LBP-SX ((1 / e2) resized to have an irradiation spot diameter of 63.5 μm in the sub-scanning direction and 40 μm in the main scanning direction). Image evaluation was performed with the charging set to -600 V. After 4000 sheets of durability tests, interference fringes and black spots were observed, and the reproducibility of one pixel in a highlight portion in an input signal equivalent to 600 dpi was insufficient and uneven. was there.
[0096]
(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.
[0097]
Then, a solution prepared by adding 20 parts of the polymer synthesized in Synthesis Example 6 and 60 parts of the monomer synthesized in Synthesis Example 2 to 150 parts of toluene and dissolving the solution was immersed on the charge generation layer and coated 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.
[0098]
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 as very good as -24V.
[0099]
The image of the electrophotographic photoreceptor was evaluated at an initial charge of -600 V using the same Canon laser beam printer as in Example 2. The image was not deteriorated even after a durability test of 5000 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.
[0100]
(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.
[0101]
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 coating method. After drying at 80 ° C. for 10 minutes, an undercoat layer having a thickness of 1 μm was formed.
[0102]
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. This 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 22]

[0103]
Then, a solution prepared by dissolving 20 parts of the polymer synthesized in Synthesis Example 5 and 150 parts of toluene in 60 parts of the monomer synthesized in Synthesis Example 1 in addition to 150 parts of toluene was immersed on the charge generation layer and coated 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.
[0104]
The electrophotographic photoreceptor was charged to -700 V, and the electrophotographic characteristics were measured using light having a wavelength of 680 nm. As a result, E1 / 2 (the amount of exposure necessary to reduce the charging potential to -350 V) was 0.61 μJ. / Cm ² And the residual potential was very good at -19V.
[0105]
This electrophotographic photoreceptor was set to an initial charge of -700 V by an evaluation machine modified to have a Canon digital full-color copying machine CLC-500 having 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 at the initial stage and after the 100,000 sheet durability test, there was no charge injection such as black spots and no interference fringes, an image output with excellent uniformity was obtained, and the gradation reproducibility was 256 gradations at 400 dpi. It was extremely good.
[0106]
(Comparative Example 2)
In the same manner as in Example 3, a charge generation layer was formed.
[0107]
Next, 6 parts of the following triarylamine compound:
[Outside 23]

[0108]
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. / Cm ² And the residual potential was as large as -58V.
[0109]
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.
[0110]
(Example 4)
In the same manner as in Example 3, a charge generation layer was formed.
[0111]
Subsequently, a solution prepared by adding 20 parts of the polymer synthesized in Synthesis Example 6 and 60 parts of the monomer synthesized in Synthesis Example 2 to 150 parts of toluene and dissolving the same was immersed in the above-mentioned charge generation layer and coated 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 -700 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 0.56 μJ. / Cm ² And the residual potential was very good at -13V.
[0112]
This electrophotographic photoreceptor was set to an initial charge of -700 V by an evaluation machine modified to have a Canon digital full-color copying machine CLC-500 having 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 at the initial stage and after the 100,000 sheet durability test, there was no charge injection such as black spots and no interference fringes, an image output with excellent uniformity was obtained, and the gradation reproducibility was 256 gradations at 400 dpi. It was extremely good.
[0113]
(Example 5)
An electrophotographic photoreceptor of Example 5 was prepared in the same manner as in Example 3 except that poly [2,7- (9,9-dioctylfluorene)] was used instead of the polymer synthesized in Synthesis Example 5. .
[0114]
(Example 6)
An electrophotographic photoreceptor of Example 6 was prepared in the same manner as in Example 4, except that poly (4-methyltriphenylamine) was used instead of the polymer synthesized in Synthesis Example 6.
[0115]
(Example 7)
An electrophotographic photosensitive member of Example 7 was prepared in the same manner as in Example 3, except that the polymer synthesized in Synthesis Example 7 was used instead of the polymer synthesized in Synthesis Example 5.
[0116]
(Example 8)
An electrophotographic photosensitive member of Example 8 was prepared in the same manner as in Example 4, except that the polymer synthesized in Synthesis Example 8 was used instead of the polymer synthesized in Synthesis Example 6.
[0117]
(Example 9)
An electrophotographic photoreceptor of Example 9 was prepared in the same manner as in Example 3, except that a polymer represented by the following structural formula was used instead of the polymer synthesized in Synthesis Example 5.
[Outside 24]

[0118]
(Example 10)
An electrophotographic photoreceptor of Example 10 was prepared in the same manner as in Example 4, except that a polymer represented by the following structural formula was used instead of the polymer synthesized in Synthesis Example 6.
[Outside 25]

[0119]
(Example 11)
Except that N, N'-bis {4- [2- (triethoxysilyl) ethyl] phenyl} -N, N'-bis- (phenyl) -benzidine was used instead of the monomer synthesized in Synthesis Example 1. In the same manner as in Example 9, the electrophotographic photosensitive member of Example 11 was produced.
[0120]
(Example 12)
Except for using N, N′-bis {4- [3- (methyldimethoxysilyl) propyl] phenyl} -N, N′-bis- (phenyl) -benzidine instead of the monomer synthesized in Synthesis Example 1. The electrophotographic photoreceptor of Example 12 was produced in the same manner as in Example 10.
[0121]
When the electrophotographic photoreceptors of Examples 5 to 12 were evaluated in the same manner as the electrophotographic photoreceptor of Example 3, there was no charge injection such as black spots or interference fringes even after the initial and endurance tests. An output was obtained, and the gradation reproducibility was very good at 256 gradations at 400 dpi.
[0122]
【The invention's effect】
It is possible to provide an electrophotographic photoreceptor which is free from light scattering and bleed, has high sensitivity and low residual potential, and has good coatability during production, and a process cartridge and an image forming apparatus having the electrophotographic photoreceptor.
[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]
1. Electrophotographic photoreceptor of the present invention
2 axes
3 Primary charging means
4 Image exposure light
5 Developing means
6 transfer means
7 Transfer material
8 Image fixing means
9 Cleaning means
10 Pre-exposure light
11 Process cartridge
12 rails
200 original plate
201 Image Scanner
202 Printer section
203 Platen glass
204 manuscript
205 Halogen lamp
206, 207 mirror
208 infrared cut filter
209 lens
210 3-line sensor
211 signal processing unit
212 Laser Driver
213 Semiconductor laser
214 polygon mirror
215 f-θ lens
216 mirror
217 Photoconductor drum
218 Rotary developing machine
219 Magenta developing machine
220 cyan developing machine
221 Yellow developing machine
222 black developing machine
223 Transfer drum
224,225 paper cassette
226 Fixing unit

Claims (22)

An electrophotographic photosensitive member having a photosensitive layer on a support, wherein the photosensitive layer of the electrophotographic photosensitive member contains a resin obtained by mixing a charge transporting monomer having a reactive group and a charge transporting polymer. Electrophotographic photoreceptor. The electrophotographic photoreceptor according to claim 1, wherein the charge transporting monomer has a triphenylamine skeleton. The structure of the charge transporting monomer is represented by the following general formula (1)
[Outside 1]

(A represents a charge-transporting monovalent organic group, Q represents a hydrolyzable group or a hydroxyl group, R ² represents a substituted or unsubstituted monovalent hydrocarbon group, and R ³ represents a substituted or unsubstituted group. And m represents an integer of 1 to 3, and 1 represents a positive integer.) The resin obtained by curing an organosilicon-modified charge-transporting compound represented by the formula: The electrophotographic photoreceptor according to claim 1, wherein: The electrophotographic photoreceptor according to any one of claims 1 to 3, wherein the charge transporting polymer has a triphenylamine skeleton as a partial structure. R ² is a monovalent hydrocarbon group having 1 to 15 carbon atoms or a halogen-substituted monovalent hydrocarbon group, R ³ is represented by — (CH ₂ ) n − (n is an integer of 1 to 18), and 1 is 5. The electrophotographic photoreceptor according to claim 3, wherein the electrophotographic photoreceptor is an integer of 1 to 5. The electrophotographic photosensitive member according to any one of claims 3-5 wherein Q is represented by -OR 1 ^{(R 1} is an alkyl group or an alkoxyalkyl group.). The electrophotographic photosensitive member according to claim 6, wherein R1 has ¹ to 6 carbon atoms. A is the following general formula (2)
[Outside 2]

(R ⁴ , R ⁵ and R ⁶ are organic groups, at least one of which represents an aromatic hydrocarbon ring group or a heterocyclic group, and R ⁴ , R ⁵ and R ⁶ are the same or different. May be.)
The electrophotographic photoreceptor according to claim 3, wherein The electrophotographic photoreceptor according to any one of claims 1 to 8, wherein the charge transporting monomer having a reactive group has an ionization potential of 4.5 to 6.2 eV. 9. The electrophotographic photoreceptor according to claim 1, wherein the charge transporting monomer having a reactive group has a drift mobility of 1 × 10 ⁻⁷ cm ² / Vsec or more. The electrophotographic photosensitive member according to any one of claims 1 to 10, wherein the charge transporting polymer has a triphenylamine skeleton. The charge transporting polymer has the following general formula (3)
[Outside 3]

(B represents an organic group having a charge transporting property. R ⁷ and R ⁸ are divalent organic groups, and may be the same or different.) The electrophotographic photoreceptor according to any one of claims 1 to 11, wherein The charge transporting polymer is represented by the following general formula (4)
[Outside 4]

(B represents an organic group having a charge transporting property; R ⁷ and R ⁸ are divalent organic groups, which may be the same or different; R ⁹ is a monovalent organic group) The electrophotographic photoreceptor according to any one of claims 1 to 11, comprising the structural unit shown below. The charge transporting polymer is represented by the following general formula (5)
[Outside 5]

(B represents an organic group having a charge transporting property. R ¹⁰ and R ¹¹ represent a substituted or unsubstituted monovalent hydrocarbon group, and R ¹⁰ and R ¹¹ may be the same or different. R ¹² Represents a substituted or unsubstituted alkylene group or an arylene group.) The electrophotographic photoreceptor according to any one of claims 1 to 11, wherein R ^{10, R 11} is a monovalent hydrocarbon group or a halogen-substituted monovalent hydrocarbon group having 1 to 15 carbon ^{atoms, R 12} is - represented by _(CH 2) n- _(n is 1 to 18 integer) The electrophotographic photoreceptor according to claim 1. The charge transporting polymer is represented by the following general formula (6)
[Outside 6]

(B represents an organic group having a charge transporting property; R ¹⁹ represents an alkylene group having 2 to 6 carbon atoms. R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ^{18 each} represent an aliphatic unsaturated group Represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms containing no bond, and R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ may be the same or different R ²⁰ represents a substituted or unsubstituted divalent hydrocarbon group having 2 to 10 carbon atoms or an alkyleneoxyalkylene group, x is an integer of 1 or more, and y and z are integers of 0 or more. , (Y + z) is an integer of 2 or more.). 17. The electrophotographic photoreceptor according to claim 1, wherein B is a charge transporting group, and the ionization potential of the B residue is in the range of 4.5 to 6.2 eV. The photosensitive layer comprises at least two layers of a charge transport layer and a charge generation layer containing a resin obtained by mixing a charge transport monomer having a condensation reactive group and a charge transport polymer. The electrophotographic photosensitive member according to the above. 19. The electrophotographic photoconductor according to claim 18, 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 a Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction. 20. The electrophotographic photoreceptor according to claim 19, which is in the form. 21. A charging unit for charging the electrophotographic photosensitive member according to claim 1, a developing unit for developing the electrophotographic photosensitive member on which an electrostatic latent image is formed with toner, and a transfer. A process cartridge which is integrally supported together with at least one means selected from the group consisting of a cleaning means for recovering toner remaining on a photoreceptor after a process, and is detachable from an electrophotographic apparatus main body. An electrophotographic photosensitive member according to any one of claims 1 to 21, a charging device for charging the electrophotographic photosensitive member, an exposure device for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, and an electrostatic device. In an image forming apparatus having developing means for developing an electrophotographic photosensitive member on which a latent image is formed with toner and transfer means for transferring a toner image on a transfer material, the electrophotographic photosensitive member forms a photosensitive layer on a support. Image forming, wherein the surface layer of the electrophotographic photosensitive member contains a resin obtained by mixing a charge transporting monomer having a condensation reactive group and a charge transporting polymer. apparatus.

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