JP3682119B2 - Electrophotographic photoreceptor - Google Patents
Electrophotographic photoreceptor Download PDFInfo
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- JP3682119B2 JP3682119B2 JP13751796A JP13751796A JP3682119B2 JP 3682119 B2 JP3682119 B2 JP 3682119B2 JP 13751796 A JP13751796 A JP 13751796A JP 13751796 A JP13751796 A JP 13751796A JP 3682119 B2 JP3682119 B2 JP 3682119B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、例えば電子写真感光体に関し、特に有機光導電材料を用いた電子写真感光体に係るものである。
【０００２】
【従来の技術】
電子写真感光体の光導電材料には、一般的に、セレン（Ｓｅ）、硫化カドミウム（ＣｄＳ）、酸化亜鉛（ＺｎＯ）、アモルファスシリコン（ａ−Ｓｉ）等の無機材料が使用されているが、かかる無機材料を用いた感光体は、暗所で例えば帯電ローラーにより帯電し、次いで、像露光を行い露光部のみの電荷を選択的に消失させて静電潜像を形成し、さらに、現像剤で可視化して画像形成するごとく利用されている。かかる電子写真感光体に要求される基本特性として、（１）暗所で適当な電位に帯電できること、（２）光照射により表面電荷を消失することができる機能を備えていること等であるが、前記無機材料は、各々長所、短所を有している。例えば、セレン（Ｓｅ）は、前記（１）、（２）の特性は十分満足するが、可撓性がなくフィルム状に加工することが難しく、また、熱や機械的衝撃に鋭敏であるため取扱いに注意を要する等の欠点がある。さらに、アモルファスシリコン（ａ−Ｓｉ）は製造条件が難しく、製造コストが高くなるという欠点がある。
【０００３】
このため、近年は、電子写真感光体として、有機光導電物質として知られるフタロシアニンやアゾ化合物を電荷発生層として用い、さらにヒドラゾン化合物等からなる電荷移動層を積層して構成される機能分離型の有機感光体が主流になっている。
【０００４】
【発明が解決しようとする課題】
ところで、従来より、かかる有機感光体の電荷移動層の結着樹脂としては、ビスフェノールＡ型ポリカーボネート樹脂が最も一般的に用いられている。
しかしながら、結着樹脂としてビスフェノールＡ型ポリカーボネート樹脂を用いて電荷移動層を形成した場合には、電荷移動剤を感光体に塗布する際に塗工液が安定しない等の欠点がある。このため、かかる欠点のない電荷移動層の材料が要望されている。
【０００５】
その一方で、最近は、近赤外域に波長を有する半導体レーザーを光源とするレーザープリンタ、ＬＥＤを光源とするＬＥＤプリンタの開発が盛んである。この分野に適用される電子写真感光体は、半導体レーザーの発振波長域及びＬＥＤの発光波長領域（６００〜８００ｎｍ）の波長の光に対して高い感度を有することが必要であるとともに、それに伴って帯電した電荷が光照射で消滅するまでの時間、即ちレスポンスタイムが速いことが感光体として求められる大きなファクターとなってきている。
【０００６】
そこで、このような課題を解決するため、種々の電荷移動剤及びその結着樹脂として種々の樹脂を用いた電子写真感光体が提案されている（例えば、特開平６−３８３８号公報、特開平６−１０２６８５号公報等参照）。
しかし、これらの電子写真感光体においても、光疲労及び機械的特性の点で満足のゆくものは得られていないのが現状である。
【０００７】
本発明は、このような従来の技術の課題を解決するためになされたもので、光疲労が小さく、かつ、機械的特性に優れ、しかも、塗工液の安定性の高い電子写真感光体を提供することを目的とするものである。
【０００８】
【課題を解決するための手段】
本発明者等は、前記課題を解決すべく鋭意研究を重ねた結果、感光層中に特定の構造の電荷移動剤と結着樹脂として特定の構造のポリカーボネート共重合体を用いた電子写真感光体が、前記従来の技術の問題点がなく、しかも長期間にわたって優れた機械的強度及び電子写真特性を維持することを見い出し、本発明を完成するに至った。
【０００９】
すなわち、請求項１に記載の発明は、導電性支持体上に少なくとも電荷発生剤と電荷移動剤と結着樹脂を有する感光層を形成した電子写真感光体において、該感光層中に結着樹脂として一般式〔Ｉ〕及び一般式〔ＩＩＩ〕で表される繰り返し単位からなるポリカーボネート共重合体と、電荷移動剤として式〔Ｖ〕で表されるブタジエン化合物とを含有することを特徴とする電子写真感光体である。
【化１９】
【化２０】
【化２１】
【化２２】
請求項２記載の発明は、導電性支持体上に少なくとも電荷発生剤と電荷移動剤と結着樹脂を有する感光層を形成した電子写真感光体において、該感光層中に結着樹脂として一般式〔Ｉ〕及び一般式〔ＩＩＩ〕で表される繰り返し単位からなるポリカーボネート共重合体と、電荷移動剤として式〔ＶＩ〕で表されるブタジエン化合物とを含有することを特徴とする。
【化２３】
【化２４】
【化２５】
【化２６】
請求項３記載の発明は、導電性支持体上に少なくとも電荷発生剤と電荷移動剤と結着樹脂を有する感光層を形成した電子写真感光体において、該感光層中に結着樹脂として一般式〔Ｉ〕及び一般式〔ＩＩＩ〕で表される繰り返し単位からなるポリカーボネート共重合体と、電荷移動剤として式〔ＶＩ〕で表されるブタジエン化合物と式〔ＶＩＩＩ〕で表されるヒドラゾン化合物の混合物とを含有することを特徴とする。
【化２７】
【化２８】
【化２９】
【化３０】
請求項４記載の発明は、導電性支持体上に少なくとも電荷発生剤と電荷移動剤と結着樹脂を有する感光層を形成した電子写真感光体において、該感光層中に結着樹脂として一般式〔Ｉ〕及び一般式〔ＩＩＩ〕で表される繰り返し単位からなるポリカーボネート共重合体と、電荷移動剤として式〔ＶＩ〕で表されるブタジエン化合物と式〔ＩＸ〕で表されるヒドラゾン化合物の混合物とを含有することを特徴とする。
【化３２】
【化３３】
【化３４】
【化３５】
【発明の実施の形態】
以下、本発明に係る電子写真感光体の実施の形態を図面を参照して詳細に説明する。
図１は、本発明に係る電子写真感光体の好ましい実施の形態の構成を示す断面図である。
【００１４】
図１に示すように、本発明は、例えば、導電性支持体１の上に電荷発生層２が形成され、その上に電荷移動層３が形成される負帯電型機能分離型２層構造の電子写真感光体に適用されるものである。この場合、電荷発生層２と電荷移動層３とにより感光層４が形成される。
【００１５】
本発明の電子写真感光体に用いられる導電性支持体１としては、公知のものなど各種のものを使用することができ、具体的には、例えば、アルミニウム、陽極酸化処理されたアルミニウム、ニッケル、銅、ステンレス、真ちゅう等、あるいは、プラスチック、プラスチック表面にアルミニウム、銅、ニッケル等の金属を蒸着又はめっきしたもの等を使用することができる。また、電子写真感光体の形状については、ドラム状、板状、シート状、ベルト状のものを使用することができる。
【００１６】
電荷発生層２は、少なくとも電荷発生剤を有するものであり、この電荷発生層２は、その下地となる導電性支持体１上に電荷発生剤を結着樹脂を用いて形成することができる。
【００１７】
電荷発生層２の形成方法としては、公知の方法等各種の方法を使用することができるが、電荷発生剤を結着樹脂とともに適当な溶媒により分散もしくは溶解した塗工液を、所定の下地となる導電性支持体１上に塗布し、乾燥させる方法を用いることができる。
また、真空蒸着により電荷発生層２を形成することもできる。
【００１８】
電荷発生剤としては、公知のものなど各種のものを使用することができ、具体的には、例えば、フタロシアニン系、ジスアゾ系、トリスアゾ系、多環キノン系、インジゴ系、ペリレン系、ベンズイミダゾール等の顔料又は染料やピリリウム塩等の有機材料やセレン、セレン−テルル、セレン−テルル−砒素、アモルファスシリコン等の無機材料を使用することができる。
【００１９】
また、電荷発生層２における結着樹脂としては、特に制限はなく公知のものなど各種のものを使用でき、具体的には、例えば、ポリスチレン、ポリ塩化ビニル、ポリ酢酸ビニル、塩ビ−酢ビ共重合体、ポリビニルアセタール、アルキド樹脂、アクリル樹脂、ポリアクリロニトリル、ポリカーボネート、ポリアミド、ポリケトン、ポリアクリロアミド、ブチラール樹脂などの熱硬化樹脂等を使用することができる。
【００２０】
なお、電荷発生層２における結着樹脂として、前記一般式〔Ｉ〕及び一般式〔ＩＩＩ〕で表される繰り返し単位からなるポリカーボネート共重合体を用いることもできる。
【００２１】
電荷移動層３は、少なくとも電荷移動剤を有するものであり、この電荷移動層３は、例えば、その下地となる電荷発生層２上に電荷移動剤を結着樹脂を用いて結着することにより形成することができる。電荷移動層３の形成方法としては、公知の方法等各種の方法を使用することができるが、通常の場合、電荷移動剤を結着樹脂とともに適当な溶媒により分散もしくは溶解した塗工液を、所定の下地となる電荷発生層２上に塗布し、乾燥させる方法を用いることができる。
【００２２】
本発明の電子写真感光体は、その感光層中、特に電荷移動層３中に結着樹脂として、以下に挙げる繰り返し単位からなるポリカーボネート共重合体（樹脂１〜１７）を含有する。但し、これらに限定されるものではなく、一般式〔Ｉ〕及び一般式〔ＩＩＩ〕で表される繰り返し単位であればよい。
【００２３】
【化３７】
【化３８】
【化３９】
【化４０】
【化４１】
【化４２】
【化４３】
【化４４】
【化４５】
【化４６】
【化４７】
【化４８】
【化４９】
【化５０】
【化５１】
【化５２】
【化５３】
なお、前記ポリカーボネート共重合体における繰り返し単位の組成比は、前記ポリカーボネート共重合体が合成しうる限り、特に限定されない。
【００４１】
電荷移動層３を構成する電荷移動剤としては、式〔Ｖ〕で表される１−ｐ−ジベンジルアミノフェニル−１−ｐ−ジエチルアミノフェニル−４，４−ジフェニル−１，３−ブタジエン、式〔ＶＩ〕で表される１，１−ビス（ｐ−ジエチルアミノフェニル）−４，４−ジフェニル−１，３ブタジエンを用いることが効果的である。
【化５４】
さらに、式〔ＶＩ〕で表される電荷移動剤に式〔ＶＩＩＩ〕で表されるｏ−メチル−ｐ−ジベンジルアミノベンズアルデヒド・ジフェニルヒドラゾン、式〔ＩＸ〕で表されるｏ−メチル−ｐ−ジフェニルアミノベンズアルデヒド・ジフェニルヒドラゾンで表されるヒドラゾンを含有させることもできる。
【化５６】
更に、上記ブタジエン化合物、ヒドラゾン化合物を含有させると同時に、公知の電子供与性物質又は電子受容性物質を含有させることができる。
【００４４】
電子供与性物質としては、例えばポリビニルカルバゾール、ハロゲン化ポリビニルカルバゾール、ポリビニルピレン、ポリビニルインドロキノキサリン、ポリビニルベンゾチオフェン、ポリビニルアントラセン、ポリビニルアクリジン、ポリビニルピラゾリン、ポリアセチレン、ポリチオフェン、ポリピロール、ポリフェニレン、ポリフェニレンビニレン、ポリイソチアナフテン、ポリアニリン、ポリジアセチレン、ポリヘプタジイエン、ポリピリジンジイル、ポリキノリン、ポリフェニレンスルフィド、ポリフェロセニレン、ポリペリナフチレン、ポリフタロシアニン等の導電性高分子化合物、低分子化合物として、アントラセン、ピレン、フェナントレン等の多環芳香族化合物、インドール、カルバゾール、イミダゾール、等の含窒素複素環化合物、フルオレノン、フルオレン、オキサジアゾール、オキサゾール、ピラゾリン、トリフェニルメタン、トリフェニルアミン、エナミン、上記以外のヒドラゾン、上記以外のブタジエン化合物などを使用することができる。
【００４５】
電子受容性物資としては、例えばトリニトロフルオレノン、テトラシアノエチレン、テトラシアノキノジメタン、キノン、ジフェノキノン、ナフトキノン、アントラキノン及びこれらの誘導体、及び特願平７−１８５５８３号に記載の特定のキノン誘導体、特願平７−２３４７３２号及び特願平７−３１９７１８号に記載の特定のジフェノキノン誘導体などを使用することができる。
【００４６】
また、本発明に係る電子写真感光体の場合、感光層の帯電時において、導電性支持体から感光層への自由電子の注入を阻止するとともに、感光層を導電性支持体に対して一体的に接着保持せしめる接着層としての作用を得るため、さらに、導電性支持体の凹凸による入射光の反射や画像の黒点、白点などを防止する目的で導電性支持体と感光層との間に中間層を設けてもよい。
【００４７】
本発明に係る電子写真感光体においては、導電性支持体と感光層との間に、接着機能、バリヤー機能、支持体表面の欠陥被覆機能などを持つ下引き層を設けてもよい。この下引き層としては、酸化アルミニウム、ポリエチレン樹脂、アクリル樹脂、エポキシ樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、ポリビニルブチラール樹脂、ポリアミド樹脂、ナイロン樹脂等を用いることができる。それらの下引き層は、単独の樹脂で構成しても良く、２種類以上の樹脂を混合して構成しても良い。また、樹脂中に金属酸化物やカーボンを分散させた下引き層を用いることもできる。
【００４８】
さらに、感光層の上に、ポリビニルホルマール樹脂、ポリカーボネート樹脂、フッ素樹脂、ポリウレタン樹脂、シリコーン樹脂等の有機薄膜や、シランカップリング剤の加水分解物で形態されるシロキサン構造体からなる薄膜を成膜して表面保護層を設けても良く、その場合には、感光体の耐久性が向上するので好ましい。この表面保護層は、耐久性向上以外の他の機能を向上させるために設けても良い。
【００４９】
【実施例】
以下、本発明に係る電子写真感光体の実施例を比較例とともに詳細に説明する。
〔実施例１〕
直径３０ｍｍのアルミニウムからなる円筒ドラム上に、結着樹脂としてポリビニルブチラールを用いたオキシチタニウムフタロシアニンの分散液を浸漬塗工により０．１μｍ塗布し、電荷発生層を形成する。
【００５０】
次いで、結着樹脂として繰り返し単位のモル比を一般式〔Ｉ〕／一般式〔ＩＩＩ〕＝０．１／０．９とした塩化メチレンを溶媒とする濃度０．５ｇ／ｄｌの溶媒の２０℃における還元粘度が０．７７ｄｌ／ｇである上記樹脂１３と、電荷移動剤として式〔Ｖ〕で表されるブタジエン化合物を、１．０／０．８の重量比でクロロホルムに溶解して塗工液を調製する。
【００５１】
そして、浸漬塗工によりこの塗工液を塗布した後、１００℃の温度下で１時間乾燥し、２０μｍの膜厚の電荷移動層を形成する。以上のような方法で電子写真感光体を作製した。
【００５２】
〔実施例２〕
実施例１で用いたポリカーボネート共重合体に代えて、繰り返し単位のモル比を一般式〔Ｉ〕／一般式〔ＩＩＩ〕＝０．５／０．５とした塩化メチレンを溶媒とする濃度０．５ｇ／ｄｌの溶媒の２０℃における還元粘度が０．７６ｄｌ／ｇである上記樹脂１３を結着樹脂に用い、それ以外は実施例１と同様の方法で電子写真感光体を作製した。
【００５３】
〔実施例３〕
実施例１で用いたポリカーボネート共重合体に代えて、繰り返し単位のモル比を一般式〔Ｉ〕／一般式〔ＩＩＩ〕＝０．８／０．２とした塩化メチレンを溶媒とする濃度０．５ｇ／ｄｌの溶媒の２０℃における還元粘度が０．７４ｄｌ／ｇである上記樹脂１３を結着樹脂に用い、それ以外は実施例１と同様の方法で電子写真感光体を作製した。
【００５４】
〔実施例４〕
実施例１の式〔Ｖ〕で表されるブタジエン化合物に代えて、式〔ＶＩ〕で表されるブタジエン化合物を電荷移動剤として用いた以外は実施例１と同様の方法で電子写真感光体を作製した。
【００５５】
〔実施例５〕
実施例１において、電荷移動剤として式〔Ｖ〕で表されるブタジエン化合物に代えて、式〔ＶＩ〕で表されるブタジエンと式〔ＶＩＩＩ〕で表されるヒドラゾン化合物を用い、ポリカーボネート共重合体／式〔ＶＩ〕／式〔ＶＩＩＩ〕＝１．０／０．１／１．０の重量比でクロロホルムに溶解し、実施例１と同様の方法で電子写真感光体を作製した。
【００５６】
〔実施例６〕
実施例１において、電荷移動剤として式〔Ｖ〕で表されるブタジエン化合物に代えて、式〔ＶＩ〕で表されるブタジエン化合物と式〔ＩＸ〕で表されるヒドラゾン化合物を用い、ポリカーボネート共重合体／式〔ＶＩ〕／式〔ＩＸ〕＝１．０／０．１／１．０の重量比でクロロホルムに溶解し、実施例１と同様の方法で電子写真感光体を作製した。
【００５７】
〔実施例７〕
電荷発生剤としてオキシチタニウムフタロシアニンを用い、これを真空度１．０×１０-6ｍｍＨｇの雰囲気中で加熱し、直径３０ｍｍのアルミニウムからなる円筒ドラム上に０．０８μｍの厚さに蒸着して電荷発生層を形成した以外は、実施例１と同様の方法により電荷移動層を形成して電子写真感光体を作製した。
【００５８】
〔比較例１〕
電荷移動剤として式〔Ｖ〕で表されるブタジエン化合物に代えて、式〔ＶＩＩＩ〕で表されるヒドラゾン化合物を用いた以外は、実施例１と同様の方法により電子写真感光体を作製した。
【００５９】
〔比較例２〕
実施例１のポリカーボネート共重合体に代えて、塩化メチレンを溶媒とする濃度０．５ｇ／ｄｌの溶媒の２０℃における還元粘度が０．７２ｄｌ／ｇであるビスフェノールＡ型ポリカーボネートを結着樹脂として用いた以外は、実施例１と同様の方法により電子写真感光体を作製した。
【００６０】
評価方法
〔光疲労の測定〕
電子写真感光体評価装置（山梨電子工業社製）を用い、実施例及び比較例によって作製された電子写真感光体を印加電圧−５ＫＶで帯電させ、波長λ＝７８０ｎｍ、露光光量２０ｅｒｇ/ｃｍ2の光を用いて電子写真感光体を露光したときの表面電位ＶR (−Ｖ)を測定した。
【００６１】
一方、実施例及び比較例によって作製された電子写真感光体に照度８００ｌｕｘの蛍光灯光を１０分間照射し、その後、前記電子写真感光体評価装置によりＶR1を測定し、光を照射する前のＶR との差(｜ＶR −ＶR1｜)を光疲労△ＶR（Ｖ）とした。その結果を表１に示す。
【００６２】
〔画像試験〕
実施例及び比較例によって作製された電子写真感光体をブラシ帯電方式により感光体を負に帯電し、ＬＥＤ露光、非磁性一成分現像方式、ブレードクリーニング方式により画像形成を行う電子写真装置に装着し、Ａ４用紙５０００枚の印字を行い、初期画像と５０００枚印字後の画像を比較した。その結果を表１に示す。この場合、判定は、○が良好、×は難があり実用不可とした。
【００６３】
〔膜減りの測定〕
上記画像試験において、印字前と５０００枚印字後の感光層の膜厚差△ｔ（μｍ）を測定した。その結果を表１に示す。
【００６４】
〔液安定性の評価〕
実施例及び比較例において調製された電荷移動層用の塗工液を１ケ月常温で放置し、塗工液のゲル化の有無を評価した。その結果を表１に示す。
この場合、判定は、変化のないものを○、ゲル化したものを×とした。
【００６５】
【表１】
【発明の効果】
表１から明らかなように、本発明の実施例の電子写真感光体は、光疲労がほとんど生ずることなく、また、画像試験の結果も良好であった。さらに、５０００枚印字した後においても、感光層表面の膜減りはごくわずかであった。
また、実施例の塗工液を１ケ月常温で放置してもゲル化するものはなく、液安定性も良好であった。
加えて、実施例１〜３において明らかなように、これらの効果は、電荷移動層の結着樹脂である一般式〔Ｉ〕及び一般式〔ＩＩＩ〕の繰り返し単位の共重合組成比を変化させても大きく変わることがなかった。
【００６７】
これに対し、電荷移動剤として式〔ＶＩＩＩ〕で表されるヒドラゾン化合物のみを用いた比較例１の場合は、光疲労が大きくなり、これに伴い、画像試験において濃度の低下が発生した。
【００６８】
一方、結着樹脂としてビスフェノールＡ型ポリカーボネート樹脂を用いた比較例２の場合は、感光層表面の膜減りがかなり大きくなるとともに、感光層表面にキズが生じ、その結果、画像試験において縦方向のすじが発生した。また、１ケ月放置した塗工液にゲル化が生じた。
【００６９】
以上述べたように、本発明によれば、光疲労が小さく、かつ、機械的特性に優れ、しかも、塗工液の安定性の高い電子写真感光体を得ることができた。
【図面の簡単な説明】
【図１】 本発明に係る電子写真感光体の好ましい実施の形態の構成を示す断面図である。
【符号の説明】
１・・・導電性支持体、２・・・電荷発生層、３・・・電荷移動層、４・・・感光層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotographic photoreceptor, for example, and particularly relates to an electrophotographic photoreceptor using an organic photoconductive material.
[0002]
[Prior art]
In general, inorganic materials such as selenium (Se), cadmium sulfide (CdS), zinc oxide (ZnO), and amorphous silicon (a-Si) are used for the photoconductive material of the electrophotographic photoreceptor. A photoreceptor using such an inorganic material is charged with, for example, a charging roller in a dark place, and then image exposure is performed to selectively eliminate the charge of only the exposed portion to form an electrostatic latent image. It is used every time it is visualized and imaged. The basic characteristics required for such an electrophotographic photosensitive member are (1) being able to be charged to an appropriate potential in a dark place, and (2) having a function of being able to eliminate surface charges by light irradiation. The inorganic materials each have advantages and disadvantages. For example, selenium (Se) sufficiently satisfies the characteristics (1) and (2), but is not flexible and difficult to process into a film, and is sensitive to heat and mechanical shock. There are drawbacks such as requiring care in handling. Furthermore, amorphous silicon (a-Si) has the disadvantages that the manufacturing conditions are difficult and the manufacturing cost is high.
[0003]
Therefore, in recent years, as an electrophotographic photosensitive member, a phthalocyanine or azo compound known as an organic photoconductive material is used as a charge generation layer, and a function separation type layered by stacking a charge transfer layer made of a hydrazone compound or the like. Organic photoreceptors are the mainstream.
[0004]
[Problems to be solved by the invention]
By the way, conventionally, bisphenol A type polycarbonate resin is most commonly used as a binder resin for the charge transfer layer of such an organic photoreceptor.
However, when a charge transfer layer is formed using a bisphenol A type polycarbonate resin as a binder resin, there is a disadvantage that the coating liquid is not stable when the charge transfer agent is applied to the photoreceptor. Therefore, there is a demand for a charge transfer layer material that does not have such a drawback.
[0005]
On the other hand, recently, development of a laser printer using a semiconductor laser having a wavelength in the near-infrared region as a light source and an LED printer using an LED as a light source has been active. The electrophotographic photosensitive member applied in this field is required to have high sensitivity to light having a wavelength in the oscillation wavelength range of the semiconductor laser and the light emission wavelength range (600 to 800 nm) of the LED, and accordingly. The time until the charged charge disappears by light irradiation, that is, a fast response time, has become a major factor required for a photoreceptor.
[0006]
In order to solve such problems, various types of charge transfer agents and electrophotographic photosensitive members using various resins as their binding resins have been proposed (for example, Japanese Patent Laid-Open Nos. 6-33838, 6-102685 etc.).
However, even in these electrophotographic photosensitive members, no satisfactory one is obtained in terms of light fatigue and mechanical properties.
[0007]
The present invention has been made in order to solve the above-described problems of the prior art, and provides an electrophotographic photosensitive member with low light fatigue, excellent mechanical properties, and high stability of a coating solution. It is intended to provide.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have made an electrophotographic photoreceptor using a charge transfer agent having a specific structure and a polycarbonate copolymer having a specific structure as a binder resin in the photosensitive layer. However, it has been found that there is no problem with the above-described conventional technique and that excellent mechanical strength and electrophotographic characteristics are maintained over a long period of time, and the present invention has been completed.
[0009]
That is, the invention described in claim 1 is an electrophotographic photosensitive member in which a photosensitive layer having at least a charge generator, a charge transfer agent, and a binder resin is formed on a conductive support, and the binder resin is contained in the photosensitive layer. An electron comprising: a polycarbonate copolymer comprising repeating units represented by general formula [I] and general formula [III], and a butadiene compound represented by formula [V] as a charge transfer agent It is a photographic photoreceptor.
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The invention according to
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According to a third aspect of the present invention, there is provided an electrophotographic photosensitive member in which a photosensitive layer having at least a charge generating agent, a charge transfer agent, and a binder resin is formed on a conductive support. Mixture of polycarbonate copolymer comprising repeating units represented by [I] and general formula [III], butadiene compound represented by formula [VI] and hydrazone compound represented by formula [VIII] as a charge transfer agent It is characterized by containing.
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According to a fourth aspect of the present invention, there is provided an electrophotographic photosensitive member in which a photosensitive layer having at least a charge generator, a charge transfer agent, and a binder resin is formed on a conductive support. Mixture of polycarbonate copolymer comprising repeating units represented by [I] and general formula [III], butadiene compound represented by formula [VI] and hydrazone compound represented by formula [IX] as a charge transfer agent It is characterized by containing.
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DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the electrophotographic photosensitive member according to the present invention will be described in detail with reference to the drawings.
FIG. 1 is a sectional view showing the structure of a preferred embodiment of the electrophotographic photosensitive member according to the present invention.
[0014]
As shown in FIG. 1, the present invention has, for example, a negatively charged function separation type two-layer structure in which a
[0015]
As the conductive support 1 used in the electrophotographic photosensitive member of the present invention, various types such as known ones can be used. Specifically, for example, aluminum, anodized aluminum, nickel, Copper, stainless steel, brass, or the like, or plastic, a plastic surface obtained by evaporating or plating a metal such as aluminum, copper, or nickel can be used. As for the shape of the electrophotographic photosensitive member, a drum shape, a plate shape, a sheet shape, or a belt shape can be used.
[0016]
The
[0017]
As a method for forming the
Alternatively, the
[0018]
As the charge generating agent, various types such as known ones can be used. Specifically, for example, phthalocyanine type, disazo type, trisazo type, polycyclic quinone type, indigo type, perylene type, benzimidazole, etc. Inorganic materials such as selenium, selenium-tellurium, selenium-tellurium-arsenic, and amorphous silicon can be used.
[0019]
Further, the binder resin in the
[0020]
In addition, as the binder resin in the
[0021]
The charge transfer layer 3 has at least a charge transfer agent, and the charge transfer layer 3 is formed by, for example, binding the charge transfer agent on the
[0022]
The electrophotographic photoreceptor of the present invention contains a polycarbonate copolymer (resins 1 to 17) composed of the following repeating units as a binder resin in the photosensitive layer, particularly in the charge transfer layer 3. However, it is not limited to these, What is necessary is just a repeating unit represented by general formula [I] and general formula [III].
[0023]
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The composition ratio of the repeating units in the polycarbonate copolymer is not particularly limited as long as the polycarbonate copolymer can be synthesized.
[0041]
Examples of the charge transfer agent constituting the charge transfer layer 3 include 1-p-dibenzylaminophenyl-1-p-diethylaminophenyl-4,4-diphenyl-1,3-butadiene represented by the formula [V], a formula It is effective to use 1,1-bis (p-diethylaminophenyl) -4,4-diphenyl-1,3 butadiene represented by [VI].
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Further, the charge transfer agent represented by the formula [VI] may be o-methyl-p-dibenzylaminobenzaldehyde / diphenylhydrazone represented by the formula [VIII], o-methyl-p- represented by the formula [IX]. A hydrazone represented by diphenylaminobenzaldehyde / diphenylhydrazone may be contained.
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Furthermore, a known electron-donating substance or electron-accepting substance can be contained simultaneously with the inclusion of the butadiene compound and hydrazone compound.
[0044]
Examples of the electron donating substance include polyvinyl carbazole, halogenated polyvinyl carbazole, polyvinyl pyrene, polyvinyl indoloquinoxaline, polyvinyl benzothiophene, polyvinyl anthracene, polyvinyl acridine, polyvinyl pyrazoline, polyacetylene, polythiophene, polypyrrole, polyphenylene, polyphenylene vinylene, poly Conductive polymer compounds such as isothianaphthene, polyaniline, polydiacetylene, polyheptadiene, polypyridinediyl, polyquinoline, polyphenylene sulfide, polyferrocenylene, polyperinaphthylene, and polyphthalocyanine, and low molecular weight compounds such as anthracene and pyrene , Nitrogen-containing compounds such as polycyclic aromatic compounds such as phenanthrene, indole, carbazole, imidazole, etc. Ring compounds, fluorenone, fluorene, oxadiazole, oxazole, pyrazoline, triphenylmethane, triphenylamine, enamine, hydrazone other than the above, the use of such a butadiene compound other than the above.
[0045]
Examples of the electron-accepting material include trinitrofluorenone, tetracyanoethylene, tetracyanoquinodimethane, quinone, diphenoquinone, naphthoquinone, anthraquinone and derivatives thereof, and a specific quinone derivative described in Japanese Patent Application No. 7-185583, Specific diphenoquinone derivatives described in Japanese Patent Application No. 7-234732 and Japanese Patent Application No. 7-319718 can be used.
[0046]
In the electrophotographic photoreceptor according to the present invention, when the photosensitive layer is charged, injection of free electrons from the conductive support to the photosensitive layer is prevented and the photosensitive layer is integrated with the conductive support. In order to obtain an action as an adhesive layer that is adhered and held on the surface of the conductive support, the conductive support is also provided between the conductive support and the photosensitive layer for the purpose of preventing reflection of incident light due to the unevenness of the conductive support and black and white spots of the image. An intermediate layer may be provided.
[0047]
In the electrophotographic photosensitive member according to the present invention, an undercoat layer having an adhesion function, a barrier function, a defect covering function on the support surface, and the like may be provided between the conductive support and the photosensitive layer. As the undercoat layer, aluminum oxide, polyethylene resin, acrylic resin, epoxy resin, polycarbonate resin, polyurethane resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, polyamide resin, nylon resin, or the like can be used. These undercoat layers may be composed of a single resin or a mixture of two or more kinds of resins. An undercoat layer in which a metal oxide or carbon is dispersed in a resin can also be used.
[0048]
Furthermore, a thin film made of an organic thin film such as polyvinyl formal resin, polycarbonate resin, fluororesin, polyurethane resin, or silicone resin or a siloxane structure formed from a hydrolyzate of a silane coupling agent is formed on the photosensitive layer. Then, a surface protective layer may be provided. In that case, the durability of the photoreceptor is improved, which is preferable. This surface protective layer may be provided in order to improve functions other than the durability improvement.
[0049]
【Example】
Examples of the electrophotographic photosensitive member according to the present invention will be described below in detail together with comparative examples.
[Example 1]
On a cylindrical drum made of aluminum having a diameter of 30 mm, a dispersion of oxytitanium phthalocyanine using polyvinyl butyral as a binder resin is applied by dip coating to a thickness of 0.1 μm to form a charge generation layer.
[0050]
Next, 20 ° C. of a solvent having a concentration of 0.5 g / dl using methylene chloride as a solvent in which the molar ratio of repeating units as the binder resin is represented by the general formula [I] / general formula [III] = 0.1 / 0.9 The resin 13 having a reduced viscosity of 0.77 dl / g and the butadiene compound represented by the formula [V] as a charge transfer agent dissolved in chloroform at a weight ratio of 1.0 / 0.8 Prepare the solution.
[0051]
And after apply | coating this coating liquid by dip coating, it dries at 100 degreeC temperature for 1 hour, and forms a charge transfer layer with a film thickness of 20 micrometers. An electrophotographic photosensitive member was produced by the method as described above.
[0052]
[Example 2]
Instead of the polycarbonate copolymer used in Example 1, a concentration of methylene chloride with a molar ratio of repeating units of the general formula [I] / general formula [III] = 0.5 / 0.5 in a solvent of 0. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the resin 13 having a reduced viscosity of 0.76 dl / g at 20 ° C. in a solvent of 5 g / dl was used as the binder resin.
[0053]
Example 3
In place of the polycarbonate copolymer used in Example 1, the concentration of the repeating units in the molar ratio of repeating units of general formula [I] / general formula [III] = 0.8 / 0.2 in methylene chloride as the solvent An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the resin 13 having a reduced viscosity at 20 ° C. of 5 g / dl at 20 ° C. of 0.74 dl / g was used as the binder resin.
[0054]
Example 4
In place of the butadiene compound represented by the formula [V] in Example 1, a butadiene compound represented by the formula [VI] was used as a charge transfer agent, and an electrophotographic photoreceptor was prepared in the same manner as in Example 1. Produced.
[0055]
Example 5
In Example 1, instead of the butadiene compound represented by the formula [V] as the charge transfer agent, a butadiene represented by the formula [VI] and a hydrazone compound represented by the formula [VIII] were used, and a polycarbonate copolymer / Formula [VI] / Formula [VIII] = 1.0 / 0.1 / 1.0 was dissolved in chloroform at a weight ratio to prepare an electrophotographic photoreceptor in the same manner as in Example 1.
[0056]
Example 6
In Example 1, instead of the butadiene compound represented by the formula [V] as the charge transfer agent, a butadiene compound represented by the formula [VI] and a hydrazone compound represented by the formula [IX] were used. An electrophotographic photosensitive member was prepared in the same manner as in Example 1 by dissolving in chloroform at a weight ratio of coalescence / formula [VI] / formula [IX] = 1.0 / 0.1 / 1.0.
[0057]
Example 7
Oxytitanium phthalocyanine is used as a charge generator, which is heated in an atmosphere with a vacuum degree of 1.0 × 10 −6 mmHg and deposited on a cylindrical drum made of aluminum with a diameter of 30 mm to a thickness of 0.08 μm. An electrophotographic photosensitive member was produced by forming a charge transfer layer by the same method as in Example 1 except that the generation layer was formed.
[0058]
[Comparative Example 1]
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the hydrazone compound represented by the formula [VIII] was used in place of the butadiene compound represented by the formula [V] as the charge transfer agent.
[0059]
[Comparative Example 2]
Instead of the polycarbonate copolymer of Example 1, a bisphenol A type polycarbonate having a reduced viscosity at 20 ° C. of 0.72 dl / g in a solvent having a concentration of 0.5 g / dl using methylene chloride as a solvent is used as a binder resin. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that.
[0060]
Evaluation method (measurement of light fatigue)
Using an electrophotographic photosensitive member evaluation apparatus (manufactured by Yamanashi Denshi Kogyo Co., Ltd.), the electrophotographic photosensitive member produced according to the example and the comparative example is charged with an applied voltage of −5 KV, and the wavelength λ = 780 nm and the exposure light quantity is 20 erg / cm 2 . The surface potential V R (−V) when the electrophotographic photosensitive member was exposed to light was measured.
[0061]
On the other hand, the electrophotographic photosensitive member produced according to the example and the comparative example was irradiated with fluorescent lamp light having an illuminance of 800 lux for 10 minutes, and then V R1 was measured by the electrophotographic photosensitive member evaluation apparatus, and V before irradiation with light. The difference from R (| V R −V R1 |) was defined as light fatigue ΔV R (V). The results are shown in Table 1.
[0062]
[Image test]
The electrophotographic photosensitive member produced according to the examples and comparative examples is mounted on an electrophotographic apparatus in which the photosensitive member is negatively charged by a brush charging method and image formation is performed by LED exposure, a non-magnetic one-component developing method, and a blade cleaning method. Then, 5000 sheets of A4 paper were printed, and the initial image was compared with the image after printing 5000 sheets. The results are shown in Table 1. In this case, the determination was that ○ was good and × was difficult and impractical.
[0063]
[Measurement of film loss]
In the above image test, the film thickness difference Δt (μm) of the photosensitive layer before printing and after printing 5000 sheets was measured. The results are shown in Table 1.
[0064]
[Evaluation of liquid stability]
The coating solution for charge transfer layer prepared in Examples and Comparative Examples was allowed to stand at room temperature for 1 month, and the presence or absence of gelation of the coating solution was evaluated. The results are shown in Table 1.
In this case, the determination was made ◯ when there was no change and x when it was gelled.
[0065]
[Table 1]
【The invention's effect】
As is apparent from Table 1, the electrophotographic photosensitive member of the example of the present invention hardly caused light fatigue, and the result of the image test was good. Furthermore, even after printing 5000 sheets, the film loss on the surface of the photosensitive layer was negligible.
Further, even when the coating liquids of the examples were left at room temperature for 1 month, there was no gelation and the liquid stability was good.
In addition, as is apparent from Examples 1 to 3, these effects change the copolymer composition ratio of the repeating units of the general formula [I] and the general formula [III], which are binder resins of the charge transfer layer. But it didn't change much.
[0067]
On the other hand, in the case of Comparative Example 1 using only the hydrazone compound represented by the formula [VIII] as the charge transfer agent, the light fatigue was increased, and accordingly, a decrease in density occurred in the image test.
[0068]
On the other hand, in the case of Comparative Example 2 using bisphenol A type polycarbonate resin as the binder resin, the film loss on the surface of the photosensitive layer becomes considerably large, and the surface of the photosensitive layer is scratched. A streak occurred. Further, gelation occurred in the coating solution left for one month.
[0069]
As described above, according to the present invention, it is possible to obtain an electrophotographic photosensitive member that is small in light fatigue, excellent in mechanical characteristics, and highly stable in coating solution.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a configuration of a preferred embodiment of an electrophotographic photosensitive member according to the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Conductive support body, 2 ... Charge generation layer, 3 ... Charge transfer layer, 4 ... Photosensitive layer
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13751796A JP3682119B2 (en) | 1996-05-08 | 1996-05-08 | Electrophotographic photoreceptor |
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|---|---|---|---|
| JP13751796A JP3682119B2 (en) | 1996-05-08 | 1996-05-08 | Electrophotographic photoreceptor |
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