JP3649846B2 - Organic photoconductive material and electrophotographic photoreceptor using the same - Google Patents

Description

【００１４】
一般式（１）、または（２）において、Ａは置換基を有していてもよいアルケニル基、または置換基を有していてもよいシクロアルケニル基を示し、Ｒ₁、及びＲ₂は水素原子、置換基を有していてもよいアルキル基、または置換基を有していてもよいアルケニル基を示す。Ｒ₃、Ｒ₄、Ｒ₁₁、及びＲ₁₂は水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、またはハロゲン原子を示す。Ｒ₅、Ｒ₆、Ｒ₁₃、及びＲ₁₄は水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、または置換基を有していてもよい複素環を示すが、Ｒ₅とＲ₆あるいはＲ₁₃とＲ₁₄が同時に水素原子になることはない。Ｒ₇、Ｒ₈、Ｒ₁₅、及びＲ₁₆は置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアラルキル基、置換基を有していてもよいアリール基、または置換基を有していてもよい複素環を示す。Ｒ₉、及びＲ₁₀は水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、または置換基を有していてもよい複素環を示すが、Ｒ₉、Ｒ₁₀が同時に水素原子になることはない。ｍ、ｎ、ｐ、及びｑは０〜２までの整数を示す。
【００１５】
ここでＡの具体例としては、ビニル基などのアルケニル基、または１−シクロヘキセニル基などのシクロアルケニル基を挙げることができる。また、Ａは置換基を有していてもよいが、その置換基の具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基などのアルキル基、フェニル基、ナフチル基などのアリール基などを挙げることができる。
【００１６】
また、Ｒ₁、及びＲ₂の具体例としては、水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基などのアルキル基、またはビニル基などのアルケニル基を挙げることができる。また、Ｒ₁、及びＲ₂は置換基を有していてもよいが、その置換基の具体例としては、フェニル基、ナフチル基などのアリール基、または上述のアルキル基などを挙げることができる。
【００１７】
またＲ₃、Ｒ₄、Ｒ₁₁、及びＲ₁₂の具体例としては、水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基などのアルキル基、メトキシ基、エトキシ基などのアルコキシ基、またはフッ素原子、塩素原子などのハロゲン原子などを挙げることができる。
【００１８】
また、Ｒ₅、Ｒ₆、Ｒ₁₃及びＲ₁₄の具体例としては、水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基などのアルキル基、フェニル基、ナフチル基などのアリール基、またはフリル基、チエニル基、インドリル基などの複素環を挙げることができる。また、Ｒ₅、Ｒ₆、Ｒ₁₃及びＲ₁₄は置換基を有していてもよいが、その置換基の具体例としては、メトキシ基、エトキシ基などのアルコキシ基、フェノキシ基、１−ナフチルオキシ基などのアリールオキシ基、フッ素原子、塩素原子などのハロゲン原子、上述のアルキル基、または上述のアリール基などを挙げることができる。
【００１９】
また、Ｒ₇、Ｒ₈、Ｒ₁₅及びＲ₁₆の具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基などのアルキル基、ビニル基などのアルケニル基、ベンジル基、１−ナフチルメチル基などのアルケニル基、フェニル基、ナフチル基などのアリール基、またはフリル基、チエニル基、インドリル基などの複素環を挙げることができる。また、Ｒ₇、Ｒ₈、Ｒ₁₅及びＲ₁₆は置換基を有していてもよいが、その置換基の具体例としては、メトキシ基、エトキシ基などのアルコキシ基、フッ素原子、塩素原子などのハロゲン原子、または上述のアルキル基などを挙げることができる。
【００２０】
またＲ₉、及びＲ₁₀の具体例としては、水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基などのアルキル基、フェニル基、ナフチル基などのアリール基、またはフリル基、チエニル基、インドリル基などの複素環などを挙げることができる。また、Ｒ₉、Ｒ₁₀は置換基を有していてもよいが、その置換基の具体例としては、メトキシ基、エトキシ基などのアルコキシ基、フッ素原子、塩素原子などのハロゲン原子、または上述のアルキル基などを挙げることができる。
【００２１】
【発明の実施の形態】
本発明の有機光導電性材料は、適度な結晶性を有しているために精製が容易であり、かつ結着剤との相溶性もよい。従って、感光体作製後、感光体表面で結晶化することなく、安定した被膜を形成することが可能である。
【００２２】
本発明にかかわる一般式（１）、または（２）で示される有機光導電性材料の具体例としては、以下に示すＣ−０１〜７７の構造を有するものが挙げられるが、これらに限定されるものではない。
【００２３】
【化３】

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【化９】

【００３０】
【化１０】

【００３１】
【化１１】

【００３２】
【化１２】

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【００３４】
【化１４】

【００３５】
【化１５】

【００３６】
本発明の一般式（１）、または（２）で示される有機光導電性材料を含有する感光層に含む電子写真感光体の形態は、そのいずれを用いることもできる。例えば、導電性支持体上に電荷発生物質、電荷輸送物質、及びフィルム形成性結着剤樹脂からなる感光層を設けたものがある。また、導電性支持体上に、電荷発生物質と結着剤樹脂からなる電荷発生層と、電荷輸送物質と結着剤樹脂からなる電荷輸送層を設けた積層型の感光体も知られている。電荷発生層と電荷輸送層はどちらが上層となっても構わない。また、必要に応じて導電性支持体と感光層の間に下引き層を、感光体表面にオーバーコート層を、積層型感光体の場合は電荷発生層と電荷輸送層との間に中間層を設けることもできる。本発明の化合物を用いて感光体を作製する支持体としては、金属製ドラム、金属板、導電性加工を施した紙やプラスチックフィルムのシート状、ドラム状あるいはベルト状の支持体などが使用される。
【００３７】
本発明の電子写真感光体は、一般式（１）、または（２）で示される有機光導電性材料及び電荷発生物質をそれぞれ１種類あるいは２種類以上含有することにより得られる。電荷発生物質には無機系電荷発生物質と有機系電荷発生物質があり、前者の例としては例えばセレン、セレン−テルル合金、セレン−ヒ素合金、硫化カドミウム、酸化亜鉛、アモルファスシリコンなどが挙げられる。有機系電荷発生物質の例としては、例えばメチルバイオレット、ブリリアントグリーン、クリスタルバイオレットなどのトリフェニルメタン系染料、メチレンブルーなどのチアジン染料、キニザリンなどのキノン染料、シアニン染料、アクリジン染料、ピリリウム色素、チアピリリウム色素、スクエアリウム色素、ペリノン系顔料、アントラキノン系顔料、ペリレン系顔料、金属含有あるいは無金属のフタロシアニン系顔料などが挙げられ、また、アゾ顔料も用いられる。
【００３８】
アゾ顔料としては、例えば特開昭４７−３７５４３号公報、特開昭５３−９５０３３号公報、特開昭５３−１３２３４７号公報、特開昭５３−１３３４４５号公報、特開昭５４−１２７４２号公報、特開昭５４−２０７３６号公報、特開昭５４−２０７３７号公報、特開昭５４−２１７２８号公報、特開昭５４−２２８３４号公報、特開昭５５−６９１４８号公報、特開昭５５−６９６５４号公報、特開昭５５−７９４４９号公報、特開昭５５−１１７１５１号公報、特開昭５６−４６２３７号公報、特開昭５６−１１６０３９号公報、特開昭５６−１１６０４０号公報、特開昭５６−１１９１３４号公報、特開昭５６−１４３４３７号公報、特開昭５７−６３５３７号公報、特開昭５７−６３５３８号公報、特開昭５７−６３５４１号公報、特開昭５７−６３５４２号公報、特開昭５７−６３５４９号公報、特開昭５７−６６４３８号公報、特開昭５７−７４７４６号公報、特開昭５７−７８５４２号公報、特開昭５７−７８５４３号公報、特開昭５７−９００５６号公報、特開昭５７−９００５７号公報、特開昭５７−９０６３２号公報、特開昭５７−１１６３４５号公報、特開昭５７−２０２３４９号公報、特開昭５８−４１５１号公報、特開昭５８−９０６４４号公報、特開昭５８−１４４３５８号公報、特開昭５８−１７７９５５号公報、特開昭５９−３１９６２号公報、特開昭５９−３３２５３号公報、特開昭５９−７１０５９号公報、特開昭５９−７２４４８号公報、特開昭５９−７８３５６号公報、特開昭５９−１３６３５１号公報、特開昭５９−２０１０６０号公報、特開昭６０−１５６４２号公報、特開昭６０−１４０３５１号公報、特開昭６０−１７９７４６号公報、特開昭６１−１１７５４号公報、特開昭６１−９０１６４号公報、特開昭６１−９０１６５号公報、特開昭６１−９０１６６号公報、特開昭６１−１１２１５４号公報、特開昭６１−２６９１６５号公報、特開昭６１−２８１２４５号公報、特開昭６１−５１０６３号公報、特開昭６２−２６７３６３号公報、特開昭６３−６８８４４号公報、特開昭６３−８９８６６号公報、特開昭６３−１３９３５５号公報、特開昭６３−１４２０６３号公報、特開昭６３−１８３４５０号公報、特開昭６３−２８２７４３号公報、特開昭６４−２１４５５号公報、特開昭６４−７８２５９号公報、特開平１−２００２６７号公報、特開平１−２０２７５７号公報、特開平１−３１９７５４号公報、特開平２−７２３７２号公報、特開平２−２５４４６７号公報、特開平３−９５５６１号公報、特開平３−２７８０６３号公報、特開平４−９６０６８号公報、特開平４−９６０６９号公報、特開平４−１４７２６５号公報、特開平５−１４２８４１号公報、特開平５−３０３２２６号公報、特開平６−３２４５０４号公報、特開平７−１６８３７９号公報などに記載の化合物が挙げられる。
【００３９】
また、これらのアゾ顔料に用いられるカプラー成分の構造は多岐に渡る。例えば特開昭５４−１７７３５号公報、特開昭５４−７９６３２号公報、特開昭５７−１７６０５５号公報、特開昭５９−１９７０４３号公報、特開昭６０−１３０７４６号公報、特開昭６０−１５３０５０号公報、特開昭６０−１０３０４８号公報、特開昭６０−１８９７５９号公報、特開昭６３−１３１１４６号公報、特開昭６３−１５５０５２号公報、特開平２−１１０５６９号公報、特開平４−１４９４４８号公報、特開平６−２７７０５号公報、特開平６−３４８０４７号公報などに記載の化合物が挙げられる。
【００４０】
上記アゾ顔料の具体例は以下に示すＢ−１〜４０に示す化合物と表１〜１４に示すカプラーとの組み合わせからなる全ての化合物を挙げることができるが、これらに限定されるものではない。また、これらの化合物と他の電荷発生物質を併用することも可能である。
【００４１】
【化１６】

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【００６１】
【表１４】

【００６２】
本発明において使用するフタロシアニン系顔料としては、それ自体公知のフタロシアニン及びその誘導体のいずれでも使用でき、具体的には、無金属フタロシアニン類、チタニルオキシフタロシアニン類、銅フタロシアニン類、アルミニウムフタロシアニン類、ジフェノキシゲルマニウムフタロシアニン類、ゲルマニウムフタロシアニン類、ガリウムフタロシアニン類、クロロガリウムフタロシアニン類、ブロモガリウムフタロシアニン類、クロロインジウムフタロシアニン類、ブロモインジウムフタロシアニン類、ヨードインジウムフタロシアニン類、マグネシウムフタロシアニン類、クロロアルミニウムフタロシアニン類、ブロモアルミニウムフタロシアニン類、スズフタロシアニン類、ジクロロスズフタロシアニン類、バナジルオキシフタロシアニン類、亜鉛フタロシアニン類、コバルトフタロシアニン類、ニッケルフタロシアニン類、ヒドロキシガリウムフタロシアニン類、ジヒドロキシガリウムフタロシアニン類、バリウムフタロシアニン類、ベリリウムフタロシアニン類、カドミウムフタロシアニン類、クロロコバルトフタロシアニン類、ジクロロチタニルフタロシアニン類、鉄フタロシアニン類、シリコンフタロシアニン類、鉛フタロシアニン類、白金フタロシアニン類、無金属ナフタロシアニン類、アルミニウムナフタロシアニン類、チタニルオキシナフタロシアニン類、ルテニウムフタロシアニン、パラジウムフタロシアニンなどが挙げられる。特にその中でも無金属フタロシアニン、チタニルオキシフタロシアニン、銅フタロシアニン、クロロアルミニウムフタロシアニン、クロロインジウムフタロシアニン、バナジルオキシフタロシアニン、ジフェノキシゲルマニウムフタロシアニン、クロロガリウムフタロシアニン、ヒドロキシガリウムフタロシアニンが本発明では好ましく用いられる。
【００６３】
また、フタロシアニン系顔料は結晶多型の化合物として知られ、各種結晶型のフタロシアニン系顔料が見出されている。これらの結晶型や製造方法に関する記述として、無金属フタロシアニンは、特公昭４９−４３３８号公報、特開昭５８−１８２６３９号公報、特開昭６０−１９１５１号公報、特開昭６２−４７０５４号公報、特開昭６２−１４３０５８号公報、特開昭６３−２８６８５７号公報、特開平１−１３８５６３号公報、特開平１−２３０５８１号公報、特開平２−２３３７６９号公報、更にはＪ．Ｐｈｙｓ．Ｃｈｅｍ．７２，３２３０（１９６８）に記載されているものを挙げることができる。
【００６４】
チタニルオキシフタロシアニンは、特開昭６１−２１７０５０号公報、特開昭６２−６７０９４号公報、特開昭６２−２２９２５３号公報、特開昭６３−３６４号公報、特開昭６３−３６５号公報、特開昭６３−３６６号公報、特開昭６３−３７１６３号公報、特開昭６３−８０２６３号公報、特開昭６３−１１６１５８号公報、特開昭６３−１９８０６７号公報、特開昭６３−２１８７６８号公報、特開昭６４−１７０６６号公報、特開平１−１２３８６８号公報、特開平１−１３８５６２号公報、特開平１−１５３７５７号公報、特開平１−１７２４５９号公報、特開平１−１７２４６２号公報、特開平１−１８９２００号公報、特開平１−２０４９６９号公報、特開平１−２０７７５５号公報、特開平１−２９９８７４号公報、特開平２−８２５６号公報、特開平２−９９９６９号公報、特開平２−１３１２４３号公報、特開平２−１６５１５６号公報、特開平２−１６５１５７号公報、特開平２−２１５８６６号公報、特開平２−２６７５６３号公報、特開平２−２９７５６０号公報、特開平３−３５０６４号公報、特開平３−５４２６４号公報、特開平３−８４０６８号公報、特開平３−９４２６４号公報、特開平３−１００６５８号公報、特開平１００６５９号公報、特開平３−１２３３５９号公報、特開平３−１９９２６８号公報、特開平３−２００７９０号公報、特開平３−２６９０６４号公報、特開平４−１４５１６６号公報、特開平４−１４５１６７号公報、特開平４−１５３２７３号公報、特開平４−１５９３７３号公報、特開平４−１７９９６４号公報、特開平５−２０２３０９号公報、特開平５−２７９５９２号公報、特開平５−２８９３８０号公報、特開平６−３３６５５４号公報、特開平７−８２５０３号公報、特開平７−８２５０５号公報、更には特開平８−１１０６４９号公報に記載されているものを挙げることができる。
【００６５】
また、銅フタロシアニンは、特公昭５２−１６６７号公報、特開昭５１−１０８８４７号公報、特開昭５５−６０９５８号公報に記載されているものや、更にはγ型、π型、χ型、ρ型などが知られておりこれらを挙げることができる。クロロアルミニウムフタロシアニンは、特開昭５８−１５８６４９号公報、特開昭６２−１３３４６２号公報、特開昭６２−１６３０６０号公報、特開昭６３−４３１５５号公報、更には特開昭６４−７０７６２号公報に、クロロインジウムフタロシアニンは特開昭５９−４４０５４号公報、特開昭６０−５９３５５号公報、特開昭６１−４５２４９号公報、更には特開平７−１３３７５号公報に、バナジルオキシフタロシアニンは、特開昭６３−１８３６１号公報、特開平１−２０４９６８号公報、特開平２６８７６３号公報、特開平３−２６９０６３号公報、更には特開平７−２４７４４２号公報に、ジフェノキシゲルマニウムフタロシアニンは、特開平４−３６０１５０号公報に、クロロガリウムフタロシアニンは、特開平５−１９４５２３号公報、更には特開平７−１０２１８３号公報に、ヒドロキシガリウムフタロシアニンは、特開平５−２６３００７号公報、更には特開平７−５３８９２号公報に記載されているものを挙げることができる。
【００６６】
本発明の一般式（１）、または（２）で示される有機光導電性材料を含む感光層を形成するために用いるフィルム形成性結着剤樹脂としては利用分野に応じて種々のものがあげられる。例えば複写用感光体の用途ではポリスチレン樹脂、ポリビニルアセタール樹脂、ポリスルホン樹脂、ポリカーボネート樹脂、酢ビ・クロトン酸共重合体樹脂、ポリエステル樹脂、ポリフェニレンオキサイド樹脂、ポリアリレート樹脂、アルキッド樹脂、アクリル樹脂、メタクリル樹脂、フェノキシ樹脂などが挙げられる。これらの中でも、ポリスチレン樹脂、ポリビニルアセタール樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアリレート樹脂などは感光体としての電位特性に優れている。また、これらの樹脂は、単独あるいは共重合体のいずれでもよく、またこれらを１種または２種以上を混合して用いることができる。これら結着剤樹脂の光導電性化合物に対して加える量は、２０〜１０００重量％が好ましく、５０〜５００重量％がより好ましい。
【００６７】
積層型感光体の場合、電荷発生層に含有されるこれらの樹脂は、電荷発生物質に対して１０〜５００重量％が好ましく、５０〜１５０重量％がより好ましい。樹脂の比率が高くなりすぎると電荷発生効率が低下し、また樹脂の比率が低くなりすぎると成膜性に問題が生じる。また、電荷輸送層に含有されるこれらの樹脂は、電荷輸送物質に対して２０〜１０００重量％が好ましく、５０〜５００重量％がより好ましい。樹脂の比率が高すぎると感度が低下し、また、樹脂の比率が低くなりすぎると繰り返し特性の悪化や塗膜の欠損を招くおそれがある。
【００６８】
これらの樹脂の中には、引っ張り、曲げ、圧縮などの機械的強度に弱いものがある。この性質を改良するために、可塑性を与える物質を加えることができる。具体的には、フタル酸エステル（例えばＤＯＰ、ＤＢＰなど）、リン酸エステル（例えばＴＣＰ、ＴＯＰなど）、セバシン酸エステル、アジピン酸エステル、ニトリルゴム、塩素化炭化水素などが挙げられる。これらの物質は、必要以上に添加すると電子写真特性の悪影響を及ぼすので、その割合は結着剤樹脂に対し２０重量％以下が好ましい。
【００６９】
その他、感光体中への添加物として酸化防止剤やカール防止剤など、塗工性の改良のためレベリング剤などを必要に応じて添加することができる。
【００７０】
一般式（１）、または（２）で示されるヒドラゾン化合物は更に他の電荷輸送物質と組み合わせて用いることができる。電荷輸送物質には正孔輸送物質と電子輸送物質がある。前者の例としては、例えば特公昭３４−５４６６号公報などに示されているオキサジアゾール類、特公昭４５−５５５号公報などに示されているトリフェニルメタン類、特公昭５２−４１８８号公報などに示されているピラゾリン類、特公昭５５−４２３８０号公報などに示されているヒドラゾン類、特開昭５６−１２３５４４号公報などに示されているオキサジアゾール類などを挙げることができる。一方、電子輸送物質としては、例えばクロラニル、テトラシアノエチレン、テトラシアノキノジメタン、２，４，７−トリニトロ−９−フルオレノン、２，４，５，７−テトラニトロ−９−フルオレノン、２，４，５，７−テトラニトロキサントン、２，４，８−トリニトロチオキサントン、１，３，７−トリニトロジベンゾチオフェン、１，３，７−トリニトロジベンゾチオフェン−５，５−ジオキシドなどがある。これらの電荷輸送物質は単独または２種以上組み合わせて用いることができる。
【００７１】
また、一般式（１）、または（２）で示されるヒドラゾン化合物と電荷移動錯体を形成し、更に増感効果を増大させる増感剤として、ある種の電子吸引性化合物を添加することもできる。この電子吸引性化合物としては例えば、２，３−ジクロロ−１，４−ナフトキノン、１−ニトロアントラキノン、１−クロロ−５−ニトロアントラキノン、２−クロロアントラキノン、フェナントレンキノンなどのキノン類、４−ニトロベンズアルデヒドなどのアルデヒド類、９−ベンゾイルアントラセン、インダンジオン、３，５−ジニトロベンゾフェノン、３，３′，５，５′−テトラニトロベンゾフェノンなどのケトン類、無水フタル酸、４−クロロナフタル酸無水物などの酸無水物、テレフタラルマロノニトリル、９−アントリルメチリデンマロノニトリル、４−ニトロベンザルマロノニトリル、４−（ｐ−ニトロベンゾイルオキシ）ベンザルマロノニトリルなどのシアノ化合物、３−ベンザルフタリド、３−（α−シアノ−ｐ−ニトロベンザル）フタリド、３−（α−シアノ−ｐ−ニトロベンザル）−４，５，６，７−テトラクロロフタリドなどのフタリド類などを挙げることができる。
【００７２】
本発明の有機光導電性材料は、感光体の形態に応じて上記の種々の添加物質と共に適当な溶剤中に溶解または分散し、その塗布液を先に述べた導電性支持体上に塗布し、乾燥して感光体を製造することができる。
【００７３】
塗布溶剤としてはクロロホルム、ジクロロエタン、ジクロロメタン、トリクロロエタン、トリクロロエチレン、クロロベンゼン、ジクロロベンゼンなどのハロゲン化炭化水素、ベンゼン、トルエン、キシレンなどの芳香族炭化水素、ジオキサン、テトラヒドロフラン、メチルセロソルブ、エチルセロソルブ、エチレングリコールジメチルエーテルなどのエーテル系溶剤、メチルエチルケトン、メチルイソブチルケトン、メチルイソプロピルケトン、シクロヘキサノンなどのケトン系溶剤、酢酸エチル、ギ酸メチル、メチルセロソルブアセテートなどのエステル系溶剤、Ｎ，Ｎ−ジメチルホルムアミド、アセトニトリル、Ｎ−メチルピロリドン、ジメチルスルホキシドなどの非プロトン性極性溶剤及びｎ−ブタノール、２−プロパノールなどのアルコール系溶剤などを挙げることができる。これらの溶剤は単独または２種以上の混合溶剤として使用することができる。
【００７４】
【実施例】
次に本発明を実施例により更に詳細に説明するが、本発明はこれらに何ら限定されるものではない。
【００７５】
【化２３】

【００７６】
合成例１ 例示化合物（Ｃ−０９）の合成
上記（３）で示されるアルデヒド体１．１６ｇ、及び１−メチル−１−フェニルヒドラジン０．４２ｇを溶かしたエタノール５０ｍｌ溶液に酢酸を５滴加え、８０℃で３時間加熱還流した。反応液を５００ｍｌの氷水に注ぎ込んで反応を停止し、酢酸エチルで有機成分を抽出した。分離した有機層を無水硫酸ナトリウムで乾燥し、減圧下溶媒を留去した。得られたオイル状物質をシリカゲルカラムクロマトグラフィーで精製して化合物（Ｃ−０９）を１．３８ｇ得た。融点１３５℃。
【００７７】
【化２４】

【００７８】
合成例２ 例示化合物（Ｃ−２１）の合成
上記（４）で示されるアルデヒド体１．５４ｇ、及び１−メチル−１−フェニルヒドラジン０．５３ｇを溶かしたエタノール５０ｍｌ溶液に酢酸を５滴加え、８０℃で３時間加熱還流した。反応液を５００ｍｌの氷水に注ぎ込んで反応を停止し、酢酸エチルで有機成分を抽出した。分離した有機層を無水硫酸ナトリウムで乾燥し、減圧下溶媒を留去した。得られたオイル状物質をシリカゲルカラムクロマトグラフィーで精製して化合物（Ｃ−２１）を１．３８ｇ得た。融点１１０℃。
【００７９】
【化２５】

【００８０】
合成例３ 例示化合物（Ｃ−７０）の合成
上記（５）で示されるアルデヒド体２．００ｇ、及び１−メチル−１−フェニルヒドラジン０．７５ｇを溶かしたエタノール５０ｍｌ溶液に酢酸を５滴加え、８０℃で２時間加熱還流した。反応液を５００ｍｌの氷水に注ぎ込んで反応を停止し、酢酸エチルで有機成分を抽出した。分離した有機層を無水硫酸ナトリウムで乾燥し、減圧下溶媒を留去した。得られたオイル状物質をシリカゲルカラムクロマトグラフィーで精製して化合物（Ｃ−７０）を１．９１ｇ得た。融点１９２℃。
【００８１】
実施例１
アゾ顔料（Ｂ−１、Ｃｐ＝Ａ−２１）１重量部及びポリエステル樹脂（東洋紡製バイロン２００）１重量部をテトラヒドロフラン１００重量部と混合し、ペイントコンディショナー装置でガラスビーズと共に２時間分散した。こうして得た分散液を、アプリケーターにてアルミ蒸着ポリエステル上に塗布して乾燥し、膜厚約０．２μｍの電荷発生層を形成した。次に例示ヒドラゾン化合物（Ｃ−０３）を、ポリアリレート樹脂（ユニチカ製Ｕ−ポリマー）と１：１の重量比で混合し、ジクロロエタンを溶媒として１０重量％の溶液を作り、上記の電荷発生層の上にアプリケーターで塗布して膜厚約２０μｍの電荷輸送層を形成した。乾燥後にこの層を観察したところ、ヒドラゾン化合物の結晶析出は全く見られなかった。
【００８２】
この様にして作製した積層型感光体について、静電記録試験装置（川口電機製ＳＰ−４２８）を用いて電子写真特性の評価を行なった。
測定条件：印加電圧−６ｋＶ、スタティックNo.３（ターンテーブルの回転スピードモード：１０ｍ／ｍｉｎ）。その結果、帯電電位（Ｖ０）が−８０５Ｖ半減露光量（Ｅ1/2）が０．８ルックス・秒と高感度の値を示した。
【００８３】
更に同装置を用いて、帯電−除電（除電光：白色光で４００ルックス×１秒照射）を１サイクルとする繰返し使用に対する特性評価を行った。５０００回での繰返しによる帯電電位の変化を求めたところ、１回目の帯電電位（Ｖ０）−８０５Ｖに対し、５０００回目の帯電電位（Ｖ０）は−７９５Ｖであり、繰返しによる電位の低下がほとんどなく安定した特性を示した。また、１回目の半減露光量（Ｅ1/2）０．８ルックス・秒に対して５０００回目の半減露光量（Ｅ1/2）は０．８ルックス・秒と変化がなく優れた特性を示した。
【００８４】
実施例２〜４８
実施例１のアゾ顔料（Ｂ−１、Ｃｐ＝Ａ−２１）及び例示ヒドラゾン化合物（Ｃ−０３）の代わりに、それぞれ表１５、表１６に示すアゾ顔料及びヒドラゾン化合物を用いた他は、実施例１と同様にして感光体を作製してその特性を評価した。結果を表１５、表１６に示す。なおこれらの感光体においても実施例１と同様に、乾燥後にヒドラゾン化合物の結晶析出は全く認められなかった。
【００８５】
【表１５】

【００８６】
【表１６】

【００８７】
実施例４９
アゾ顔料（Ｂ−１、Ｃｐ＝Ａ−２１）１重量部とテトラヒドロフラン４０重量部を、ペイントコンディショナー装置でガラスビーズと共に８時間分散処理した。こうして得た分散液に、例示ヒドラゾン化合物（Ｃ−０３）を２．５重量部、ポリカーボネート樹脂（三菱ガス化学製ＰＣＺ−２００）１０重量部、テトラヒドロフラン６０重量部を加え、更にペイントコンディショナー装置で３０分間分散処理を行った後、アプリケーターにてアルミ蒸着ポリエステル上に塗布し、膜厚約１５μｍの感光層を形成した。乾燥後、この層を観察したところ、ヒドラゾン化合物の結晶析出は全く認められなかった。この感光体の電子写真特性を、実施例１と同様にして評価した。ただし、印加電圧のみ＋５ｋＶに変更した。その結果、１回目の帯電電位（Ｖ０）＋５１５Ｖ、半減露光量（Ｅ1/2）１．２ルックス・秒、５０００回繰り返し後の帯電電位（Ｖ０）＋４９５Ｖ、半減露光量（Ｅ1/2）１．２ルックス・秒と、高感度でしかも変化の少ない、優れた特性を示した。
【００８８】
実施例５０〜９６
実施例４９のアゾ顔料（Ｂ−１２、Ｃｐ＝Ａ−２１）及び例示ヒドラゾン化合物（Ｃ−０３）の代わりに、それぞれ表１７、表１８に示すアゾ顔料及びヒドラゾン化合物を用いた他は、実施例４９と同様にして感光体を作製してその特性を評価した。結果を表１７、表１８に示す。なお、これらの感光体においても、実施例４９と同様に、ヒドラゾン化合物の結晶析出は全く認められなかった。
【００８９】
【表１７】

【００９０】
【表１８】

【００９１】
実施例９７〜１０７
実施例１のアゾ顔料の代わりにＣｕＫα１．５４１オングストロームのＸ線に対するブラッグ角（２θ±０．２°）が、９．５°、９．７°、１１．７°、１５．０°、２３．５°、２４．１°、２７．３°に主要なピークを示すＸ線回折スペクトルを有するチタニルオキシフタロシアニン（Ｙ型チタニルオキシフタロシアニン）を、例示ヒドラゾン化合物（Ｃ−０３）の代わりにそれぞれ表１９に示すヒドラゾン化合物を用いた他は、実施例１と同様にして感光体を作製してその特性を評価した。結果を表１９に示す。また、これらの感光体においても実施例１と同様、ヒドラゾン化合物の結晶析出は全く認められなかった。
【００９２】
【表１９】

【００９３】
実施例１０８〜１１８
実施例４９のアゾ顔料の代わりにＹ型チタニルオキシフタロシアニンを、例示ヒドラゾン化合物（Ｃ−０３）の代わりにそれぞれ表２０に示すヒドラゾン化合物を用いた他は、実施例４９と同様にして感光体を作製してその特性を評価した。結果を表２０に示す。また、これらの感光体においても、実施例４９と同様、ヒドラゾン化合物の結晶析出は全く認められなかった。
【００９４】
【表２０】

【００９５】
【化２６】

【００９６】
比較例１
電荷輸送物質として例示ヒドラゾン化合物（Ｃ−０３）の代わりに上記に示す比較化合物（６）を用いた他は、実施例１と同様の操作で感光体を作製しようとしたところ比較化合物（６）は結晶性が高く、溶媒であるジクロロエタンに完全に溶解しなかった。この塗液を用いて作製した感光体の特性を評価した結果、帯電電位は（Ｖ０）−３３０Ｖ、半減露光量（Ｅ1/2）は２．８ルックス・秒と帯電電位の低下、並びに感度の低下がみられた。
【００９７】
【化２７】

【００９８】
比較例２
電荷輸送物質として例示ヒドラゾン化合物（Ｃ−０３）の代わりに上記に示す比較化合物（７）を用いた他は、実施例１と同様の操作で感光体を作製しようとしたところ比較化合物（７）は結晶性が高く、溶媒であるジクロロエタンに完全に溶解しなかった。この塗液を用いて作製した感光体の特性を評価した結果、帯電電位は（Ｖ０）−２９０Ｖ、半減露光量（Ｅ1/2）は３．３ルックス・秒と帯電電位の低下、並びに感度の低下がみられた。
【００９９】
比較例３
電荷輸送物質として例示ヒドラゾン化合物（Ｃ−０３）の代わりに上記に示す比較化合物（６）を用いた他は、実施例４９と同様の操作で感光体を作製しようとしたところ比較化合物（６）は結晶性が高く、溶媒であるテトラヒドロフランに完全に溶解しなかった。この塗液を用いて作製した感光体の特性を評価した結果、帯電電位は（Ｖ０）＋２００Ｖ、半減露光量（Ｅ1/2）は３．５ルックス・秒と帯電電位の低下、並びに感度の低下がみられた。
【０１００】
比較例４
電荷輸送物質として例示ヒドラゾン化合物（Ｃ−０３）の代わりに上記に示す比較化合物（７）を用いた他は、実施例４９と同様の操作で感光体を作製しようとしたところ比較化合物（７）は結晶性が高く、溶媒であるテトラヒドロフランに完全に溶解しなかった。この塗液を用いて作製した感光体の特性を評価した結果、帯電電位は（Ｖ０）＋１３０Ｖ、半減露光量（Ｅ1/2）は４．１ルックス・秒と帯電電位の低下、並びに感度の低下がみられた。
【０１０１】
【発明の効果】
以上から明らかなように、本発明の有機光導電性材料を用いれば高感度で高耐久性を有し、安定した被膜を形成することが可能な優れた電子写真感光体を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic photoconductive material and an electrophotographic photosensitive member using the same.
[0002]
[Prior art]
In recent years, the use of electrophotography is not limited to the field of copying machines, but has spread to fields where photographic technology has been used in the past, such as printing plate materials, slide films, and microfilms, and lasers, LEDs, and CRTs are used as light sources. Applications to high-speed printers are also being considered. Recently, applications of photoconductive materials other than electrophotographic photoreceptors, such as electrostatic recording elements, sensor materials, EL elements, etc., have begun to be studied. Accordingly, the demand for photoconductive materials and electrophotographic photoreceptors using the same is becoming high and wide. To date, inorganic photoconductive substances such as selenium, cadmium sulfide, zinc oxide, and silicon are known as electrophotographic photoreceptors, and have been widely studied and put into practical use. These inorganic materials have many advantages and at the same time have various drawbacks. For example, selenium has the disadvantages that the production conditions are difficult and that it is easily crystallized by heat or mechanical impact, and cadmium sulfide and zinc oxide have difficulty in moisture resistance and durability. Silicon has been pointed out to be insufficiently charged and difficult to manufacture. Furthermore, selenium and cadmium sulfide have toxicity problems.
[0003]
In contrast, organic photoconductive materials have good film-forming properties, excellent flexibility, light weight, good transparency, and design of photoreceptors over a wide range of wavelengths by appropriate sensitization methods. Therefore, its practical application is gradually attracting attention.
[0004]
By the way, a photoreceptor used in electrophotographic technology generally requires the following as a basic property. That is, (1) high chargeability to corona discharge in the dark, (2) little leakage (dark decay) of the obtained charge in the dark, and (3) charged charge due to light irradiation. (4) Residual charge after light irradiation is small.
[0005]
However, to date, many studies have been made on photoconductive polymers such as polyvinyl carbazole as organic photoconductive substances. However, these films do not always have sufficient film properties, flexibility, and adhesive properties. It is difficult to say that it has sufficient basic properties as a photoreceptor.
[0006]
On the other hand, for organic low-molecular photoconductive compounds, a photoconductor excellent in mechanical strength such as film property, adhesiveness, and flexibility can be obtained by selecting a binder used for forming the photoconductor. However, it is difficult to find a compound suitable for maintaining high sensitivity characteristics.
[0007]
In order to improve such points, organic photoreceptors having higher sensitivity characteristics have been developed by sharing the charge generation function and the charge transport function with different substances. The feature of such photoconductors, which are called function-separated types, is that a material suitable for each function can be selected from a wide range, and a photoconductor having an arbitrary performance can be easily produced. Has been promoted.
[0008]
Among these, various substances such as phthalocyanine pigments, squalium dyes, azo pigments, and perylene pigments have been studied as substances responsible for the charge generation function, and among them, azo pigments can have various molecular structures and are high in price. It has been widely researched because of its expectation of charge generation efficiency, and its practical application is also progressing. However, in this azo pigment, the relationship between the molecular structure and the charge generation efficiency is still unclear. The reality is that we are exploring optimal structures by accumulating vast amounts of synthetic research, but sufficiently satisfy the basic properties and high durability requirements for the photoreceptors listed above. Things have not been obtained yet.
[0009]
On the other hand, there are a hole transport material and an electron transport material as the materials responsible for the charge transport function. Various materials such as hydrazone compounds and stilbene compounds as hole transport materials and 2,4,7-trinitro-9-fluorenone and diphenoquinone derivatives as electron transport materials have been studied and are in practical use. The fact is that we are searching for the optimal structure by accumulating a huge amount of synthetic research. In fact, many improvements have been made so far, but a product that sufficiently satisfies the basic properties and high durability required for the photosensitive member described above has not been obtained.
[0010]
As described above, various improvements have been made in the production of electrophotographic photosensitive members, but they sufficiently satisfy the basic properties and high durability required for the photosensitive members listed above. Is not yet available.
[0011]
[Problems to be solved by the invention]
The object of the present invention is to be used for an electrophotographic photosensitive member and a sensor material, an EL element, an electrostatic recording element, etc. that have a high charging potential, a high sensitivity, and can exhibit stable performance without changing various characteristics even when used repeatedly. It is to provide a possible organic photoconductive material.
[0012]
[Means for Solving the Problems]
As a result of researches on photoconductive materials to achieve the above object, the present inventors have found that an organic photoconductive material having a specific structure is effective, and have reached the present invention. The organic photoconductive material having a specific structure is a hydrazone compound represented by the following general formula (1) or (2).
[0013]
[Chemical formula 2]

[0014]
In the general formula (1) or (2), A represents an alkenyl group which may have a substituent or a cycloalkenyl group which may have a substituent, and R ₁ and R ₂ represent hydrogen. An atom, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent is shown. R ₃ , R ₄ , R ₁₁ , and R _{12 each} represent a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a halogen atom. R ₅ , R ₆ , R ₁₃ , and R ₁₄ may have a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Although it represents a heterocyclic ring, R ₅ and R ₆ or R ₁₃ and R ₁₄ are not simultaneously hydrogen atoms. R ₇ , R ₈ , R ₁₅ , and R ₁₆ are optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted aralkyl groups, substituted The aryl group which may have a group, or the heterocyclic ring which may have a substituent is shown. R ₉ and R ₁₀ represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic ring which may have a substituent, R ₉ and R ₁₀ are not hydrogen atoms at the same time. m, n, p, and q represent an integer of 0-2.
[0015]
Here, specific examples of A include an alkenyl group such as a vinyl group or a cycloalkenyl group such as a 1-cyclohexenyl group. A may have a substituent. Specific examples of the substituent include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and an aryl group such as a phenyl group and a naphthyl group. Examples include groups.
[0016]
Specific examples of R ₁ and R ₂ include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, or an alkenyl group such as a vinyl group. R ₁ and R ₂ may have a substituent, and specific examples of the substituent include an aryl group such as a phenyl group and a naphthyl group, or the above-described alkyl group. .
[0017]
Specific examples of R ₃ , R ₄ , R ₁₁ and R ₁₂ include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, an n-propyl group and an isopropyl group, an alkoxy group such as a methoxy group and an ethoxy group, Or halogen atoms, such as a fluorine atom and a chlorine atom, etc. can be mentioned.
[0018]
Specific examples of R ₅ , R ₆ , R ₁₃ and R ₁₄ include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, an n-propyl group and an isopropyl group, an aryl group such as a phenyl group and a naphthyl group, Or heterocyclic rings, such as a furyl group, a thienyl group, an indolyl group, can be mentioned. R ₅ , R ₆ , R ₁₃ and R ₁₄ may have a substituent. Specific examples of the substituent include alkoxy groups such as a methoxy group and an ethoxy group, a phenoxy group, and 1-naphthyl. Examples thereof include an aryloxy group such as an oxy group, a halogen atom such as a fluorine atom and a chlorine atom, the above-described alkyl group, and the above-described aryl group.
[0019]
Specific examples of R ₇ , R ₈ , R ₁₅ and R ₁₆ include methyl groups, ethyl groups, n-propyl groups, alkyl groups such as isopropyl groups, alkenyl groups such as vinyl groups, benzyl groups, and 1-naphthyl. An alkenyl group such as a methyl group, an aryl group such as a phenyl group and a naphthyl group, or a heterocyclic ring such as a furyl group, a thienyl group, and an indolyl group can be given. R ₇ , R ₈ , R ₁₅ and R ₁₆ may have a substituent. Specific examples of the substituent include alkoxy groups such as a methoxy group and an ethoxy group, a fluorine atom, and a chlorine atom. And the above-described alkyl groups.
[0020]
Specific examples of R ₉ and R ₁₀ include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, an aryl group such as a phenyl group and a naphthyl group, a furyl group, and a thienyl group. And a heterocyclic ring such as an indolyl group. R ₉ and R ₁₀ may have a substituent. Specific examples of the substituent include an alkoxy group such as a methoxy group and an ethoxy group, a halogen atom such as a fluorine atom and a chlorine atom, or the above-mentioned examples. And the like.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Since the organic photoconductive material of the present invention has appropriate crystallinity, it can be easily purified and has good compatibility with the binder. Therefore, it is possible to form a stable film without crystallization on the surface of the photoconductor after the photoconductor is manufactured.
[0022]
Specific examples of the organic photoconductive material represented by the general formula (1) or (2) according to the present invention include those having the following structures of C-01 to 77, but are not limited thereto. It is not something.
[0023]
[Chemical 3]

[0024]
[Formula 4]

[0025]
[Chemical formula 5]

[0026]
[Chemical 6]

[0027]
[Chemical 7]

[0028]
[Chemical 8]

[0029]
[Chemical 9]

[0030]
[Chemical Formula 10]

[0031]
Embedded image

[0032]
Embedded image

[0033]
Embedded image

[0034]
Embedded image

[0035]
Embedded image

[0036]
Any of the electrophotographic photoreceptors included in the photosensitive layer containing the organic photoconductive material represented by the general formula (1) or (2) of the present invention can be used. For example, there is one in which a photosensitive layer made of a charge generation material, a charge transport material, and a film-forming binder resin is provided on a conductive support. There is also known a laminated type photoreceptor in which a charge generation layer made of a charge generation material and a binder resin and a charge transport layer made of a charge transport material and a binder resin are provided on a conductive support. . Either the charge generation layer or the charge transport layer may be an upper layer. If necessary, an undercoat layer is provided between the conductive support and the photosensitive layer, an overcoat layer is provided on the surface of the photosensitive member, and in the case of a laminated type photosensitive member, an intermediate layer is provided between the charge generation layer and the charge transporting layer. Can also be provided. As a support for producing a photoreceptor using the compound of the present invention, a metal drum, a metal plate, a sheet of paper or plastic film subjected to conductive processing, a drum-like or belt-like support, and the like are used. The
[0037]
The electrophotographic photoreceptor of the present invention can be obtained by containing one or more organic photoconductive materials and charge generating materials represented by the general formula (1) or (2). The charge generation material includes an inorganic charge generation material and an organic charge generation material. Examples of the former include selenium, selenium-tellurium alloy, selenium-arsenic alloy, cadmium sulfide, zinc oxide, and amorphous silicon. Examples of organic charge generating materials include triphenylmethane dyes such as methyl violet, brilliant green and crystal violet, thiazine dyes such as methylene blue, quinone dyes such as quinizarin, cyanine dyes, acridine dyes, pyrylium dyes, thiapyrylium dyes , Squalium dyes, perinone pigments, anthraquinone pigments, perylene pigments, metal-containing or metal-free phthalocyanine pigments, and azo pigments are also used.
[0038]
Examples of the azo pigment include JP-A-47-37543, JP-A-53-95033, JP-A-53-132347, JP-A-53-133445, and JP-A-54-12742. JP-A-54-20736, JP-A-54-20737, JP-A-54-21728, JP-A-54-22834, JP-A-55-69148, JP-A-55. JP-A-69654, JP-A-55-79449, JP-A-55-117151, JP-A-56-46237, JP-A-56-1116039, JP-A-56-11640, JP-A-56-119134, JP-A-56-143437, JP-A-57-63537, JP-A-57-63538, JP-A-57-63541 JP-A-57-63542, JP-A-57-63549, JP-A-57-66438, JP-A-57-74746, JP-A-57-78542, JP-A-57- 78543, JP-A-57-90056, JP-A-57-90057, JP-A-57-90632, JP-A-57-116345, JP-A-57-202349, Japanese Laid-Open Patent Publication Nos. 58-4151, 58-90644, 58-144358, 58-177955, 59-19662, 59-33253 JP, 59-71059, 59-72448, 59-78356, 59-136351, 59-201060. JP, 60-15642, JP 60-14351, JP 60-179746, JP 61-11754, JP 61-90164, JP JP 61-90165, JP 61-90166, JP 61-112154, JP 61-269165, 61-281245, 61-51063 JP, 62-267363, JP 63-68844, JP 63-89866, JP 63-139355, JP 63-142033, JP 63 -183450, JP-A 63-282743, JP-A 64-21455, JP-A 64-78259, JP-A 1-200267, JP-A 1-2 No. 02757, JP-A-1-319754, JP-A-2-72372, JP-A-2-254467, JP-A-3-95561, JP-A-3-27863, JP-A-4-96068. JP-A-4-96069, JP-A-4-147265, JP-A-5-142841, JP-A-5-303226, JP-A-6-324504, JP-A-7-168379, etc. And the compounds described in the above.
[0039]
Moreover, the structure of the coupler component used in these azo pigments varies widely. For example, JP-A-54-17735, JP-A-54-79632, JP-A-57-176055, JP-A-59-97043, JP-A-60-130746, JP-A-60- -153050, JP-A-60-103048, JP-A-60-189759, JP-A-63-131146, JP-A-63-155052, JP-A-2-11069, Examples thereof include compounds described in Kaihei 4-149448, JP-A-6-27705, JP-A-6-348047, and the like.
[0040]
Specific examples of the azo pigments include, but are not limited to, all compounds composed of combinations of the compounds shown in B-1 to 40 shown below and couplers shown in Tables 1 to 14. It is also possible to use these compounds in combination with other charge generation materials.
[0041]
Embedded image

[0042]
Embedded image

[0043]
Embedded image

[0044]
Embedded image

[0045]
Embedded image

[0046]
Embedded image

[0047]
Embedded image

[0048]
[Table 1]

[0049]
[Table 2]

[0050]
[Table 3]

[0051]
[Table 4]

[0052]
[Table 5]

[0053]
[Table 6]

[0054]
[Table 7]

[0055]
[Table 8]

[0056]
[Table 9]

[0057]
[Table 10]

[0058]
[Table 11]

[0059]
[Table 12]

[0060]
[Table 13]

[0061]
[Table 14]

[0062]
As the phthalocyanine pigment used in the present invention, any of phthalocyanines known per se and derivatives thereof can be used. Specifically, metal-free phthalocyanines, titanyloxyphthalocyanines, copper phthalocyanines, aluminum phthalocyanines, diphenoxy Germanium phthalocyanines, germanium phthalocyanines, gallium phthalocyanines, chlorogallium phthalocyanines, bromogallium phthalocyanines, chloroindium phthalocyanines, bromoindium phthalocyanines, iodoindium phthalocyanines, magnesium phthalocyanines, chloroaluminum phthalocyanines, bromoaluminum phthalocyanines , Tin phthalocyanines, dichlorotin phthalocyanines, vanadyloxy Tarocyanines, zinc phthalocyanines, cobalt phthalocyanines, nickel phthalocyanines, hydroxygallium phthalocyanines, dihydroxygallium phthalocyanines, barium phthalocyanines, beryllium phthalocyanines, cadmium phthalocyanines, chlorocobalt phthalocyanines, dichlorotitanyl phthalocyanines, iron phthalocyanines Silicon phthalocyanines, lead phthalocyanines, platinum phthalocyanines, metal-free naphthalocyanines, aluminum naphthalocyanines, titanyloxynaphthalocyanines, ruthenium phthalocyanines, palladium phthalocyanines, and the like. Among these, metal-free phthalocyanine, titanyloxyphthalocyanine, copper phthalocyanine, chloroaluminum phthalocyanine, chloroindium phthalocyanine, vanadyloxyphthalocyanine, diphenoxygermanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine are preferably used in the present invention.
[0063]
Moreover, phthalocyanine pigments are known as crystalline polymorphic compounds, and various crystalline phthalocyanine pigments have been found. As a description of these crystal types and production methods, metal-free phthalocyanines are disclosed in JP-B-49-4338, JP-A-58-182639, JP-A-60-19151, and JP-A-62-47054. JP-A-62-143058, JP-A-63-286857, JP-A-1-138563, JP-A-1-230581, JP-A-2-233769, and J. Org. Phys. Chem. 72 , 3230 (1968).
[0064]
Titanyloxyphthalocyanine is disclosed in JP-A-61-217050, JP-A-62-267094, JP-A-62-229253, JP-A-63-364, JP-A-63-365, JP-A 63-366, JP-A 63-37163, JP-A 63-80263, JP-A 63-116158, JP-A 63-198067, JP-A 63- No. 218768, JP-A 64-17066, JP-A 1-123868, JP-A 1-1138562, JP-A 1-153757, JP-A 1-172459, JP-A 1-172462. No. 1, JP-A-1-189200, JP-A-1-204969, JP-A-1-207755, JP-A-1-299874, -8256, JP-A-2-99969, JP-A-2-131243, JP-A-2-165156, JP-A-2-165157, JP-A-2-215866, JP-A-2-267563. No. 2, JP-A-2-297560, JP-A-3-35064, JP-A-3-54264, JP-A-3-84068, JP-A-3-94264, JP-A-3-100168. Japanese Patent Laid-Open Nos. Hei 100699, Hei 3-123359, Hei 3-199268, Hei 3-200790, Hei 3-269064, Hei 4-145166, Hei 4 -145167, JP-A-4-153273, JP-A-4-159373, JP-A-4-179964, Japanese Laid-Open Patent Publication No. 5-202309, Japanese Laid-Open Patent Publication No. 5-279592, Japanese Laid-Open Patent Publication No. 5-289380, Japanese Laid-Open Patent Publication No. 6-336554, Japanese Laid-Open Patent Publication No. 7-82503, Japanese Laid-Open Patent Publication No. 7-82505, and more Examples thereof include those described in Kaihei 8-110649.
[0065]
Further, copper phthalocyanine includes those described in JP-B-52-1667, JP-A-51-108847, JP-A-55-60958, and γ-type, π-type, χ-type, ρ type and the like are known and can be mentioned. Chloroaluminum phthalocyanine is disclosed in JP-A-58-158649, JP-A-62-133462, JP-A-62-163060, JP-A-63-43155, and further JP-A-64-70762. In the publication, chloroindium phthalocyanine is disclosed in JP 59-44054 A, JP 60-59355 A, JP 61-45249 A, and further in JP 7-13375 A. JP-A-63-18361, JP-A-1-204968, JP-A-268763, JP-A-3-269663, and further JP-A-7-247442, diphenoxygermanium phthalocyanine 4-360150 discloses chlorogallium phthalocyanine as disclosed in JP-A-5-194. 23 JP, even in JP-A-7-102183, hydroxygallium phthalocyanine, JP-A-5-263007, JP-even can be exemplified those described in JP-A-7-53892.
[0066]
Various film-forming binder resins may be used depending on the field of application to form a photosensitive layer containing the organic photoconductive material represented by the general formula (1) or (2) of the present invention. It is done. For example, in the use of photoconductors for copying, polystyrene resin, polyvinyl acetal resin, polysulfone resin, polycarbonate resin, vinyl acetate / crotonic acid copolymer resin, polyester resin, polyphenylene oxide resin, polyarylate resin, alkyd resin, acrylic resin, methacrylic resin And phenoxy resin. Among these, polystyrene resin, polyvinyl acetal resin, polycarbonate resin, polyester resin, polyarylate resin, and the like are excellent in potential characteristics as a photoreceptor. These resins may be either single or copolymer, and these may be used alone or in combination of two or more. The amount of the binder resin added to the photoconductive compound is preferably 20 to 1000% by weight, and more preferably 50 to 500% by weight.
[0067]
In the case of a multilayer photoreceptor, these resins contained in the charge generation layer are preferably 10 to 500% by weight, more preferably 50 to 150% by weight, based on the charge generation material. If the resin ratio is too high, the charge generation efficiency is lowered, and if the resin ratio is too low, there is a problem in film formability. In addition, these resins contained in the charge transport layer are preferably 20 to 1000% by weight, more preferably 50 to 500% by weight with respect to the charge transport material. If the ratio of the resin is too high, the sensitivity is lowered, and if the ratio of the resin is too low, the repeated characteristics may be deteriorated or the coating film may be lost.
[0068]
Some of these resins are weak in mechanical strength such as pulling, bending, and compression. To improve this property, a plasticizing substance can be added. Specific examples include phthalic acid esters (for example, DOP and DBP), phosphoric acid esters (for example, TCP and TOP), sebacic acid esters, adipic acid esters, nitrile rubber, and chlorinated hydrocarbons. When these substances are added more than necessary, the electrophotographic characteristics are adversely affected, and therefore the ratio is preferably 20% by weight or less based on the binder resin.
[0069]
In addition, a leveling agent or the like can be added as necessary to improve the coatability, such as an antioxidant or an anti-curl agent, as additives in the photoreceptor.
[0070]
The hydrazone compound represented by the general formula (1) or (2) can be used in combination with another charge transporting substance. Charge transport materials include hole transport materials and electron transport materials. Examples of the former include, for example, oxadiazoles shown in Japanese Patent Publication No. 34-5466, triphenylmethanes shown in Japanese Patent Publication No. 45-555, and Japanese Patent Publication No. 52-4188. And the like, hydrazones shown in JP-B-55-42380, oxadiazoles shown in JP-A-56-123544, and the like. On the other hand, examples of the electron transport material include chloranil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 1,3,7-trinitrodibenzothiophene, 1,3,7-trinitrodibenzothiophene-5,5-dioxide. These charge transport materials can be used alone or in combination of two or more.
[0071]
In addition, a certain electron-withdrawing compound can be added as a sensitizer that forms a charge transfer complex with the hydrazone compound represented by the general formula (1) or (2) and further enhances the sensitizing effect. . Examples of the electron-withdrawing compound include quinones such as 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 1-chloro-5-nitroanthraquinone, 2-chloroanthraquinone, phenanthrenequinone, and 4-nitro. Aldehydes such as benzaldehyde, ketones such as 9-benzoylanthracene, indandione, 3,5-dinitrobenzophenone, 3,3 ', 5,5'-tetranitrobenzophenone, phthalic anhydride, 4-chloronaphthalic anhydride, etc. Acid anhydrides, terephthalalmalononitrile, 9-anthrylmethylidenemalononitrile, 4-nitrobenzalmalononitrile, cyano compounds such as 4- (p-nitrobenzoyloxy) benzalmalononitrile, 3-benzalphthalide, 3 -(Α-cyano-p-ni Robenzaru) phthalide, 3- (alpha-cyano -p- Nitorobenzaru) -4,5,6,7 such phthalides such as tetrachloro phthalide can be cited.
[0072]
The organic photoconductive material of the present invention is dissolved or dispersed in an appropriate solvent together with the above various additives depending on the form of the photoreceptor, and the coating solution is applied onto the conductive support described above. The photosensitive member can be manufactured by drying.
[0073]
Coating solvents include halogenated hydrocarbons such as chloroform, dichloroethane, dichloromethane, trichloroethane, trichloroethylene, chlorobenzene and dichlorobenzene, aromatic hydrocarbons such as benzene, toluene and xylene, dioxane, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether. Ether solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, cyclohexanone and other ketone solvents, ethyl acetate, methyl formate, methyl cellosolve acetate and other ester solvents, N, N-dimethylformamide, acetonitrile, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide, and n-butanol and 2-propanol Or the like can be mentioned alcohol-based solvent. These solvents can be used alone or as a mixed solvent of two or more.
[0074]
【Example】
EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to these at all.
[0075]
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[0076]
Synthesis Example 1 Synthesis of Exemplified Compound (C-09) Five drops of acetic acid were added to 50 ml of ethanol in which 1.16 g of the aldehyde compound represented by (3) above and 0.42 g of 1-methyl-1-phenylhydrazine were dissolved, The mixture was heated to reflux at 80 ° C. for 3 hours. The reaction solution was poured into 500 ml of ice water to stop the reaction, and organic components were extracted with ethyl acetate. The separated organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained oily substance was purified by silica gel column chromatography to obtain 1.38 g of compound (C-09). Melting point 135 ° C.
[0077]
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[0078]
Synthesis Example 2 Synthesis of Exemplary Compound (C-21) Five drops of acetic acid were added to 50 ml of ethanol in which 1.54 g of the aldehyde compound represented by the above (4) and 0.53 g of 1-methyl-1-phenylhydrazine were dissolved. The mixture was heated to reflux at 80 ° C. for 3 hours. The reaction solution was poured into 500 ml of ice water to stop the reaction, and organic components were extracted with ethyl acetate. The separated organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained oily substance was purified by silica gel column chromatography to obtain 1.38 g of compound (C-21). Melting point 110 ° C.
[0079]
Embedded image

[0080]
Synthesis Example 3 Synthesis of Exemplified Compound (C-70) 5 drops of acetic acid was added to a solution of aldehyde 2.00 g shown in (5) above and 0.75 g of 1-methyl-1-phenylhydrazine in 50 ml of ethanol. The mixture was heated to reflux at 80 ° C. for 2 hours. The reaction solution was poured into 500 ml of ice water to stop the reaction, and organic components were extracted with ethyl acetate. The separated organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained oily substance was purified by silica gel column chromatography to obtain 1.91 g of compound (C-70). 192 ° C.
[0081]
Example 1
1 part by weight of an azo pigment (B-1, Cp = A-21) and 1 part by weight of a polyester resin (Toyobo Byron 200) were mixed with 100 parts by weight of tetrahydrofuran, and dispersed with glass beads in a paint conditioner device for 2 hours. The dispersion thus obtained was applied onto an aluminum vapor-deposited polyester with an applicator and dried to form a charge generation layer having a thickness of about 0.2 μm. Next, the exemplified hydrazone compound (C-03) is mixed with polyarylate resin (U-polymer manufactured by Unitika) at a weight ratio of 1: 1 to make a 10% by weight solution using dichloroethane as a solvent, and the charge generation layer described above. A charge transport layer having a film thickness of about 20 μm was formed by coating with an applicator. When this layer was observed after drying, no crystal precipitation of the hydrazone compound was observed.
[0082]
The laminated photoconductors thus produced were evaluated for electrophotographic characteristics using an electrostatic recording test apparatus (SP-428 manufactured by Kawaguchi Electric).
Measurement conditions: applied voltage -6 kV, static No. 3 (turn table rotation speed mode: 10 m / min). As a result, the charging potential (V0) was -805 V and the half exposure amount (E1 / 2) was 0.8 lux.sec.
[0083]
Further, using the same apparatus, the characteristics were evaluated for repeated use with one cycle of charge-static elimination (static elimination light: 400 lux × 1 second irradiation with white light). When the change of the charging potential by repeating 5000 times was obtained, the charging potential (V0) of 5000 times was −795V with respect to the charging potential (V0) −805V of the first time, and there was almost no decrease in potential due to repetition. It showed stable characteristics. In addition, the first half exposure (E1 / 2) was 0.8 lux · second, and the 5000 half exposure (E1 / 2) was 0.8 lux · second. .
[0084]
Examples 2-48
Except that the azo pigments and hydrazone compounds shown in Table 15 and Table 16 were used in place of the azo pigments (B-1, Cp = A-21) and the exemplified hydrazone compound (C-03) of Example 1, Photoconductors were prepared in the same manner as in Example 1 and their characteristics were evaluated. The results are shown in Tables 15 and 16. In these photoreceptors, as in Example 1, no crystal precipitation of the hydrazone compound was observed after drying.
[0085]
[Table 15]

[0086]
[Table 16]

[0087]
Example 49
One part by weight of an azo pigment (B-1, Cp = A-21) and 40 parts by weight of tetrahydrofuran were dispersed with a glass bead for 8 hours in a paint conditioner device. To the dispersion thus obtained, 2.5 parts by weight of the exemplified hydrazone compound (C-03), 10 parts by weight of a polycarbonate resin (PCZ-200 manufactured by Mitsubishi Gas Chemical) and 60 parts by weight of tetrahydrofuran were added, and further 30 by a paint conditioner device. After carrying out a dispersion treatment for a minute, it was applied onto an aluminum vapor-deposited polyester with an applicator to form a photosensitive layer having a thickness of about 15 μm. When this layer was observed after drying, no crystal precipitation of the hydrazone compound was observed. The electrophotographic characteristics of this photoreceptor were evaluated in the same manner as in Example 1. However, only the applied voltage was changed to +5 kV. As a result, the first charging potential (V0) + 515V, half exposure amount (E1 / 2) 1.2 lux · second, the charging potential after repeating 5000 times (V0) + 495V, half exposure amount (E1 / 2) 1. Excellent characteristics with high sensitivity and little change of 2 lux / second.
[0088]
Examples 50-96
Except for using the azo pigments and hydrazone compounds shown in Table 17 and Table 18 in place of the azo pigments (B-12, Cp = A-21) of Example 49 and the exemplified hydrazone compound (C-03), respectively, A photoreceptor was prepared in the same manner as in Example 49, and its characteristics were evaluated. The results are shown in Tables 17 and 18. In these photoreceptors, as in Example 49, no crystal precipitation of the hydrazone compound was observed.
[0089]
[Table 17]

[0090]
[Table 18]

[0091]
Examples 97-107
Instead of the azo pigment of Example 1, the Bragg angle (2θ ± 0.2 °) with respect to X-ray of CuKα1.541 Å is 9.5 °, 9.7 °, 11.7 °, 15.0 °, 23 Titanyloxyphthalocyanine (Y-type titanyloxyphthalocyanine) having X-ray diffraction spectra having main peaks at .5 °, 24.1 °, and 27.3 ° is used instead of the exemplified hydrazone compound (C-03). A photoconductor was prepared in the same manner as in Example 1 except that the hydrazone compound shown in No. 19 was used, and its characteristics were evaluated. The results are shown in Table 19. Also in these photoreceptors, as in Example 1, no hydrazone compound crystal precipitation was observed.
[0092]
[Table 19]

[0093]
Examples 108-118
A photoreceptor was prepared in the same manner as in Example 49 except that Y-type titanyloxyphthalocyanine was used instead of the azo pigment of Example 49, and the hydrazone compound shown in Table 20 was used instead of the exemplified hydrazone compound (C-03). It was fabricated and its characteristics were evaluated. The results are shown in Table 20. Also in these photoreceptors, as in Example 49, no crystal precipitation of the hydrazone compound was observed.
[0094]
[Table 20]

[0095]
Embedded image

[0096]
Comparative Example 1
A photoconductor was prepared by the same operation as in Example 1 except that the comparative compound (6) shown above was used in place of the exemplified hydrazone compound (C-03) as the charge transporting material. Was highly crystalline and did not completely dissolve in the solvent dichloroethane. As a result of evaluating the characteristics of the photoconductor prepared using this coating liquid, the charging potential was (V0) -330V, the half exposure amount (E1 / 2) was 2.8 lux · sec, the charging potential decreased, and the sensitivity A decrease was observed.
[0097]
Embedded image

[0098]
Comparative Example 2
A photoconductor was prepared by the same operation as in Example 1 except that the comparative compound (7) shown above was used in place of the exemplified hydrazone compound (C-03) as the charge transporting material. Was highly crystalline and did not completely dissolve in the solvent dichloroethane. As a result of evaluating the characteristics of a photoconductor prepared using this coating solution, the charged potential was (V0) -290 V, the half exposure amount (E1 / 2) was 3.3 lux.sec. A decrease was observed.
[0099]
Comparative Example 3
A photoconductor was prepared in the same manner as in Example 49 except that the comparative compound (6) shown above was used instead of the exemplified hydrazone compound (C-03) as the charge transport material. Was highly crystalline and did not completely dissolve in the solvent tetrahydrofuran. As a result of evaluating the characteristics of the photoconductor produced using this coating solution, the charged potential was (V0) +200 V, the half exposure amount (E1 / 2) was 3.5 lux.sec. Was seen.
[0100]
Comparative Example 4
A photoconductor was prepared in the same manner as in Example 49 except that the comparative compound (7) shown above was used instead of the exemplified hydrazone compound (C-03) as the charge transporting material. Was highly crystalline and did not completely dissolve in the solvent tetrahydrofuran. As a result of evaluating the characteristics of the photoconductor produced using this coating liquid, the charging potential was (V0) +130 V, the half exposure amount (E1 / 2) was 4.1 lux · sec, and the charging potential was lowered and the sensitivity was lowered. Was seen.
[0101]
【The invention's effect】
As is apparent from the above, the use of the organic photoconductive material of the present invention can provide an excellent electrophotographic photosensitive member having high sensitivity and high durability and capable of forming a stable film. .

Claims (3)

An organic photoconductive material comprising a hydrazone compound represented by the following general formula (1) or (2):

(In General Formula (1) or (2), A represents an alkenyl group which may have a substituent, or a cycloalkenyl group which may have a substituent, and R ₁ and R ₂ are A hydrogen atom, an optionally substituted alkyl group, or an optionally substituted alkenyl group, wherein R ₃ , R ₄ , R ₁₁ , and R ₁₂ have a hydrogen atom or a substituent; And an optionally substituted alkyl group, an optionally substituted alkoxy group, or a halogen atom, wherein R ₅ , R ₆ , R ₁₃ , and R ₁₄ may be a hydrogen atom or a substituent. A good alkyl group, an optionally substituted aryl group, or an optionally substituted heterocycle, wherein R ₅ and R ₆ or R ₁₃ and R ₁₄ are simultaneously hydrogen atoms; not _{.R 7, R 8, R 15} , and R ₁₆ is an alkyl group which may have a substituent An alkenyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic ring which may have a substituent R ₉ and R ₁₀ represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic ring which may have a substituent. , R ₉ and R ₁₀ are not hydrogen atoms at the same time, m, n, p and q are integers from 0 to 2.) An electrophotographic photosensitive member comprising a photosensitive layer containing an organic photoconductive material represented by the above general formula (1) or (2) on a conductive support. 3. The photosensitive layer contains a charge generation material and a charge transport material, and the charge transport material is an organic photoconductive material represented by the general formula (1) or (2). Electrophotographic photoreceptor.