JP3854452B2 - Diamine compound and electrophotographic photoreceptor using the same - Google Patents

Description

【００１１】
（式中、Ａｒ^１は置換基を含んでもよくかつ１〜３個のベンゼン環を含むアリレン基、置換基を含んでもよい２価の複素環基、置換基を含んでもよい炭素数１〜５のアルキレン基を示す。Ａｒ^２は置換基を含んでもよいアリール基、置換基を含んでもよい複素環基、置換基を含んでもよいアラルキル基、置換基を含んでもよい炭素数１〜５のアルキル基、置換基を含んでもよい炭素数１〜５のフルオロアルキル基、置換基を含んでもよい炭素数１〜５のパーフルオロアルキル基を示す。Ｒ^１は置換基を含んでもよい炭素数１〜３のアルキル基、置換基を含んでもよい炭素数１〜５のフルオロアルキル基、置換基を含んでもよい炭素数１〜５のパーフルオロアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のジアルキルアミノ基または水素原子を示す。ａは置換基を含んでもよい炭素数１〜３のアルキル基、置換基を含んでもよい炭素数１〜５のフルオロアルキル基、置換基を含んでもよい炭素数１〜５のパーフルオロアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のジアルキルアミノ基、ハロゲン原子または水素原子を示し、ｎは１〜４の整数を示す。ただしｎが２以上のとき、ａの各々は同一でも異なってもよく、互いに環を形成してもよい。Ｘは酸素、硫黄原子またはＮ−Ｒ^２を示し、Ｒ^２は置換基を含んでもよい炭素数１〜３のアルキル基、置換基を含んでもよい炭素数１〜５のフルオロアルキル基、置換基を含んでもよい炭素数１〜５のパーフルオロアルキル基を示す。）
【００１２】
本発明に従えば、今までにない新規なジアミン化合物を提供することができ、該ジアミン化合物は、広い共役系を有しているので、電子写真感光体の電荷移動物質として用いれば、電荷移動度を高くして電子写真感光体の残留電位特性を向上させることができる。
【００１３】
本発明は、導電性支持体上に設けられた感光層は、下記一般式（Ｉ）で示されるベンゾフラン、ベンゾチオフェンまたはインドール環を有するジアミン化合物を、電荷移動物質として含有することを特徴とする電子写真感光体である。
【００１４】
【化９】

【００１５】
（式中、Ａｒ^１は置換基を含んでもよくかつ１〜３個のベンゼン環を含むアリレン基、置換基を含んでもよい２価の複素環基、置換基を含んでもよい炭素数１〜５のアルキレン基を示す。Ａｒ^２は置換基を含んでもよいアリール基、置換基を含んでもよい複素環基、置換基を含んでもよいアラルキル基、置換基を含んでもよい炭素数１〜５のアルキル基、置換基を含んでもよい炭素数１〜５のフルオロアルキル基、置換基を含んでもよい炭素数１〜５のパーフルオロアルキル基を示す。Ｒ^１は置換基を含んでもよい炭素数１〜３のアルキル基、置換基を含んでもよい炭素数１〜５のフルオロアルキル基、置換基を含んでもよい炭素数１〜５のパーフルオロアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のジアルキルアミノ基または水素原子を示す。ａは置換基を含んでもよい炭素数１〜３のアルキル基、置換基を含んでもよい炭素数１〜５のフルオロアルキル基、置換基を含んでもよい炭素数１〜５のパーフルオロアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のジアルキルアミノ基、ハロゲン原子または水素原子を示し、ｎは１〜４の整数を示す。ただしｎが２以上のとき、ａの各々は同一でも異なってもよく、互いに環を形成してもよい。Ｘは酸素、硫黄原子またはＮ−Ｒ^２を示し、Ｒ^２は置換基を含んでもよい炭素数１〜３のアルキル基、置換基を含んでもよい炭素数１〜５のフルオロアルキル基、置換基を含んでもよい炭素数１〜５のパーフルオロアルキル基を示す。）
【００１６】
本発明に従えば、ジアミン化合物はバインダポリマとの相溶性にすぐれているので、感光層中に多量に含有させて電子写真感光体の光感度を向上させることができるとともに、ジアミン化合物は結晶として析出し難いので、電子写真感光体の繰返し使用時の特性を安定させることができ、高感度かつ高耐久性を有する有機質の電子写真感光体を提供することができる。また無機系のものに比べて無毒で資源的にも問題なく、透明性がよく、軽量で成膜性も優れ、正負の両帯電性を有し、感光体の製造も容易という有機系感光体の利点を備えている電子写真感光体を提供することができる。
【００１７】
また本発明は、前記ジアミン化合物が、下記一般式（ＩＩ）で示されることを特徴とする。
【００１８】
【化１０】

【００１９】
（式中、Ａｒ¹、Ｒ¹、Ｘ、ａおよびｎは一般式（Ｉ）において示したものと同義である。）
【００２０】
本発明に従えば、感光層中に多量に含有させて電子写真感光体の光感度を向上させ、電子写真感光体の繰返し使用時の特性を安定させることができ、高感度かつ高耐久性を有するとともに、無機系に比べて無毒で資源的にも問題なく、透明性がよく、軽量で成膜性も優れ、正負の両帯電性を有し、感光体の製造も容易という有機系感光体の利点を備えている電子写真感光体を提供することができる。
【００２１】
また本発明は、前記ジアミン化合物が、下記一般式（ＩＩＩ）で示されることを特徴とする。
【００２２】
【化１１】

【００２３】
（式中、ｂは置換基を含んでもよい炭素数１〜３のアルキル基、置換基を含んでもよい炭素数が１〜５のフルオロアルキル基、置換基を含んでもよい炭素数が１〜５のパーフルオロアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のジアルキルアミノ基、ハロゲン原子または水素原子を示し、ｍは１〜４の整数を示す。ただしｍが２以上のとき、ｂの各々は同一でも異なってもよく、互いに環を形成してもよい。ｌは１〜５の整数を示す。Ｒ¹、ａ、Ｘ、ｎは一般式（Ｉ）において示したものと同義である。）
【００２４】
本発明に従えば、感光層中に多量に含有させて電子写真感光体の光感度を向上させ、電子写真感光体の繰返し使用時の特性を安定させることができ、高感度かつ高耐久性を有するとともに、無機系に比べて無毒で資源的にも問題なく、透明性がよく、軽量で成膜性も優れ、正負の両帯電性を有し、感光体の製造も容易という有機系感光体の利点を備えている電子写真感光体を提供することができる。
【００２５】
また本発明は、前記ジアミン化合物が、下記一般式（ＩＶ）で示されることを特徴とする。
【００２６】
【化１２】

【００２７】
（式中、Ｒ¹、Ｘ、ａ、ｂ、ｍおよびｎは一般式（ＩＩＩ）において示したものと同義である。）
本発明に従えば、感光層中に多量に含有させて電子写真感光体の光感度を向上させ、電子写真感光体の繰返し使用時の特性を安定させることができ、高感度かつ高耐久性を有するとともに、無機系に比べて無毒で資源的にも問題なく、透明性がよく、軽量で成膜性も優れ、正負の両帯電性を有し、感光体の製造も容易という有機系感光体の利点を備えている電子写真感光体を提供することができる。
【００２８】
また本発明は、前記ジアミン化合物が、下記一般式（Ｖ）で示されることを特徴とする。
【００２９】
【化１３】

【００３０】
（式中、ｃおよびｄは各々、置換基を含んでもよい炭素数１〜３のアルキル基、置換基を含んでもよい炭素数が１〜５のフルオロアルキル基、置換基を含んでもよい炭素数１〜５のパーフルオロアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のジアルキルアミノ基、ハロゲン原子または水素原子を示し、ｋおよびｊは各々１〜４の整数を示す。ただしｋおよびｊが２以上のとき、対応するｃおよびｄはそれぞれ同一でも異なってもよく、互いに環を形成してもよい。Ｒ¹、Ｘ、ａおよびｎは一般式（Ｉ）において示したものと同義である。）
【００３１】
本発明に従えば、感光層中に多量に含有させて電子写真感光体の光感度を向上させ、電子写真感光体の繰返し使用時の特性を安定させることができ、高感度かつ高耐久性を有するとともに、無機系に比べて無毒で資源的にも問題なく、透明性がよく、軽量で成膜性も優れ、正負の両帯電性を有し、感光体の製造も容易という有機系感光体の利点を備えている電子写真感光体を提供することができる。
【００３２】
また本発明は、前記ジアミン化合物が、下記一般式（ＶＩ）で示されることを特徴とする。
【００３３】
【化１４】

【００３４】
（式中、Ｒ¹、Ｘ、ａ、ｃ、ｄ、ｊ、ｋおよびｎは一般式（Ｖ）において示したものと同義である。）
【００３５】
本発明に従えば、感光層中に多量に含有させて電子写真感光体の光感度を向上させ、電子写真感光体の繰返し使用時の特性を安定させることができ、高感度かつ高耐久性を有するとともに、無機系に比べて無毒で資源的にも問題なく、透明性がよく、軽量で成膜性も優れ、正負の両帯電性を有し、感光体の製造も容易という有機系感光体の利点を備えている電子写真感光体を提供することができる。
【００３６】
また本発明は、前記感光層が、電荷発生物質を含有する電荷発生層と、前記電荷移動物質を含有する電荷移動層との積層構造から成ることを特徴とする。
【００３７】
本発明に従えば、前記ジアミン化合物を電荷移動層に含有することによって、高感度かつ高耐久性を有する積層型の電子写真感光体を提供することができる。
【００３８】
また本発明は、前記感光層が、電荷発生物質と前記電荷移動物質とを含有する単一層から成ることを特徴とする。
【００３９】
本発明に従えば、前記ジアミン化合物を電荷移動物質として電荷発生物質とともに、感光層に含有することによって、高感度かつ高耐久性を有する単層型の電子写真感光体を提供することができる。
【００４０】
また本発明は、前記導電性支持体と感光層との間に、中間層を設けたことを特徴とする。
【００４１】
本発明に従えば、中間層を設けることによって、導電性支持体を保護し、導電性支持体と感光層との接着性を高めて、感光層の塗工性を高め、導電性支持体から感光層への電荷注入を改善することができる。
【００４２】
また本発明は、前記電荷発生層上に前記電荷移動層が積層され、該電荷移動層はバインダポリマとして、ビニル化合物の重合体およびその共重合体、ポリエステル樹脂、ポリカーボネート樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリビニルブチラール樹脂、フェノキシ樹脂、セルロース樹脂、ウレタン樹脂、ならびにエポキシ樹脂から成る群から選ばれる少なくとも１種を含有することを特徴とする。
【００４３】
本発明に従えば、前記樹脂を感光層のバインダポリマとして用いることによって、耐磨耗性に優れる電子写真感光体を提供することができる。
【００４４】
【発明の実施の形態】
本発明によるジアミン化合物は、下記一般式（Ｉ）で示される。
【００４５】
【化１５】

【００４６】
一般式（Ｉ）中、Ａｒ^１は置換基を含んでもよくかつ１〜３個のベンゼン環を含むアリレン基、置換基を含んでもよい２価の複素環基、置換基を含んでもよい炭素数１〜５のアルキレン基を示す。
【００４７】
Ａｒ^１ で示されるアリレン基の具体例としては、下記のものが挙げられる。

複素環基の具体例としては、ベンゾフリル、ベンゾチオフェニル、Ｎ−メチルインドリル、ベンゾチアゾリル、ベンゾオキサゾリルおよびＮ−エチルカルバゾリルなどが挙げられる。アルキル基の具体例としては、ｎ−プロピルおよびイソプロピルなどが挙げられる。
【００４８】
前記一般式（Ｉ）中、Ａｒ²は置換基を含んでもよいアリール基、置換基を含んでもよい複素環基、置換基を含んでもよいアラルキル基、置換基を含んでもよい炭素数１〜５のアルキル基、置換基を含んでもよい炭素数１〜５のフルオロアルキル基、置換基を含んでもよい炭素数１〜５のパーフルオロアルキル基を示す。
【００４９】
Ａｒ²の具体例としては、フェニル、トリル、アニシル、ナフチル、ピレニルおよびビフェニルなどのアリール基、ベンゾフリル、ベンゾチオフェニル、Ｎ−メチルインドリル、ベンゾチアゾリル、ベンゾオキサゾリルおよびＮ−エチルカルバゾリルなどの複素環基、ｎ−プロピルおよびイソプロピルなどのアルキル基が挙げられる。
【００５０】
前記一般式（Ｉ）中、Ｒ¹は置換基を含んでもよい炭素数１〜３のアルキル基、置換基を含んでもよい炭素数１〜５のフルオロアルキル基、置換基を含んでもよい炭素数１〜５のパーフルオロアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のジアルキルアミノ基または水素原子を示す。
【００５１】
Ｒ¹の具体例としては、メチル、エチル、ｎ−プロピルおよびイソプロピルなどのアルキル基、メトキシおよびエトキシなどのアルコキシ基、ジメチルアミノおよびジエチルアミノなどのジアルキルアミノ基などが挙げられる。
【００５２】
前記一般式（Ｉ）中、ａは置換基を含んでもよい炭素数１〜３のアルキル基、置換基を含んでもよい炭素数１〜５のフルオロアルキル基、置換基を含んでもよい炭素数１〜５のパーフルオロアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のジアルキルアミノ基、ハロゲン原子または水素原子を示し、ｎは１〜４の整数を示す。ただしｎが２以上のとき、ａの各々は同一でも異なってもよく、互いに環を形成してもよい。
【００５３】
ａの具体例としては、メチル、エチル、ｎ−プロピルおよびイソプロピルなどのアルキル基、メトキシ、エトキシ、ｎ−プロポキシおよびイソプロポキシなどのアルコキシ基、ジメチルアミノ、ジエチルアミノおよびイソプロピルアミノなどのジアルキルアミノ基、フッ素、塩素および臭素などのハロゲン原子などが挙げられる。一般的に電子供与性の置換基であるのが好ましい。
【００５４】
前記一般式（Ｉ）中、Ｘは酸素、硫黄原子またはＮ−Ｒ²を示し、Ｒ²は置換基を含んでもよい炭素数１〜３のアルキル基、置換基を含んでもよい炭素数１〜５のフルオロアルキル基、置換基を含んでもよい炭素数１〜５のパーフルオロアルキル基を示す。
【００５５】
Ｘの具体例としては、酸素、硫黄原子、Ｎ−メチル基およびＮ−エチル基などが挙げられる。
【００５６】
特に、一般式（Ｉ）で示されるジアミン化合物のうち、電子写真特性、原価および製造などの観点から優れたものとして、Ａｒ¹はフェニレン基、ビフェニレン基またはナフチレン基、Ａｒ²がフェニル基、ｐ−トリル基、ベンゾフリル基、ベンゾチオフェニル基またはＮ−メチルインドリル基、Ｒ¹およびａは水素原子、Ｘは酸素または硫黄原子であるものが挙げられる。
【００５７】
前記一般式（Ｉ）で示される本発明のジアミン化合物の具体的な例としては、たとえば以下の表１〜表３に示す構造を有するジアミン化合物が挙げられるが、これによって本発明のジアミン化合物が限定されるものではない。
【００５８】
【表１】

【００５９】
【表２】

【００６０】
【表３】

【００６１】
本発明による電子写真感光体は、感光層の電荷移動物質として、前記一般式（Ｉ）で示されるジアミン化合物を１種類以上含有する。該電子写真感光体の層構成は、以下に示すような種々の態様をとることができる。
【００６２】
図１は、電荷発生層上に電荷移動層を有する機能分離型感光層を有する電子写真感光体の一例を模式的に示す断面図である。導電性支持体１上に、感光層４として電荷発生物質２を主成分としてバインダポリマ中に分散させた電荷発生層５と、電荷移動物質３を主成分としてバインダポリマ中に分散させた電荷移動層６との積層から成る機能分離型感光体である。電荷発生層５の表面に電荷移動層６が形成され、この電荷移動層６の中に電荷移動物質３として、本発明によるジアミン化合物が含有される。
【００６３】
図２は、電荷移動層上に電荷発生層を有する機能分離型感光層である。図１と同様の電荷発生層５と、電荷移動層６との積層から成る機能分離型感光体であるが、図１とは逆に電荷移動層６の表面に電荷発生層５が形成され、この電荷移動層６中に電荷移動物質３として、本発明によるジアミン化合物が含有される。
【００６４】
図３は、分散型感光層を有する電子写真感光体の一例を模式的に示す断面図である。導電性支持体１上に、感光層４として電荷発生物質２と、電荷移動物質３とをバインダポリマ中に分散させた単層から成る単層型感光体の構成を示す。
【００６５】
図４は、図３の電子写真感光体において表面保護層７を有する例を示す断面図である。導電性支持体１と図３と同様の感光層１４上に表面保護層７を設け、単層から成る単層型感光体の構成を示す。
【００６６】
図５は、図１の電子写真感光体において中間層８を有する例を示す断面図である。導電性支持体１と図１と同様の感光層４との間に中間層８を設け、積層から成る機能分離型感光体の構成を示す。
【００６７】
図６は、図３の電子写真感光体において中間層８を有する例を示す断面図である。導電性支持体１と図３と同様の感光層１４との間に中間層８を設け、単層から成る単層型感光体の構成を示す。
【００６８】
前述のジアミン化合物を電子写真感光体に用いるには、種々の方法が考えられる。たとえば図１のようにキャリア発生効率の高い電荷発生層５と電荷移動層６とから成る積層構造の形態において、導電性支持体１上に増感染料、アゾ系顔料およびフタロシアニン系顔料を代表とする顔料を主体とする電荷発生層５を設ける。該電荷発生層５上に、前述のジアミン化合物を、必要に応じて酸化防止化合物や電子吸引性化合物を添加して、バインダポリマ中に溶解または分散させた電荷移動層を設けて成る積層型の機能分離型感光体とする。また前述のジアミン化合物と増感染料とを、必要に応じて化学増感剤や電子吸引性化合物を添加して、バインダポリマ中に溶解または分散させた塗布液を、図３のように導電性支持体１上に塗布して成る単層型感光体とする。このように本発明によるジアミン化合物は、これらのいずれの場合にも適用することが可能である。
【００６９】
前記バインダポリマとしては、利用分野に応じて種々のものが挙げられる。すなわち複写機用またはプリンタ用感光体の分野では、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、ポリフェニレンオキサイド樹脂、ポリエステル樹脂、アルキッド樹脂およびポリアリレート樹脂などが望ましい。これらの樹脂は、単独または２種以上混合して用いてもよい。特にポリスチレン樹脂、ポリカーボネート樹脂、ポリアリレート樹脂およびポリフェニレンオキサイド樹脂などは、体積抵抗値が１０¹³Ω以上で、被膜性および電位特性などにも優れている。
【００７０】
これらのバインダポリマの添加量は、前述のジアミン化合物に対して、重量比で０．２〜２０倍の割合が好ましく、より好ましくは０．５〜５倍の範囲である。０．２倍未満になるとジアミン化合物が感光体表面から析出してくるという欠点が生じ、２０倍を超えると著しく感度低下を招く。
【００７１】
印刷版に使用するためには、特にアルカリ性結合剤が必要である。アルカリ性結合剤とは、水もしくは水との混合系を含むアルコール性のアルカリ性溶剤に、可溶な酸性基を有する高分子物質である。可溶な酸性基としては、たとえば酸無水物基、カルボキシル基、フェノール性水酸基、スルホン酸基、スルホンアミド基およびスルホンイミド基などである。これらのアルカリ性結合剤は、通常、酸価が１００以上の高い値を持っていることが好ましい。酸価の大きな結合剤は、アルカリ性溶剤に易溶または容易に膨潤化する。そのような結合剤としては、たとえばスチレン：無水マレイン酸共重合体、酢酸ビニル：無水マレイン酸共重合体、酢酸ビニル：クロトン酸共重合体、メタクリル酸：メタクリル酸エステル共重合体、フェノール樹脂およびメタクリル酸：スチレン：メタクリル酸エステル共重合体などである。これらの樹脂は、光導電性有機物質に対して、複写機用感光体の場合と同程度の割合で加える。
【００７２】
前記増感染料としては、メチルバイオレット、クリスタルバイオレット、ナイトブルーおよびビクトリアブルーなどで代表されるトリフェニルメタン系染料、エリスロシン、ローダミンＢ、ローダミン３Ｒ、アクリジンオレンジおよびフラぺオシンなどに代表されるアクリジン染料、メチレンブルーおよびメチレングリーンなどに代表されるチアジン染料、カプリブルーおよびメルドラブルーなどに代表されるオキサジン染料、その他シアニン染料、スチリル染料、ピリリウム塩染料、ならびにチオピリリウム塩染料などがある。
【００７３】
また感光層において、光吸収によって極めて高い効率でキャリアを発生させる光導電性の顔料としては、各種金属フタロシアニン、無金属フタロシアニンおよびハロゲン化無金属フタロシアニンなどのフタロシアニン系顔料、ペリレンイミドおよびペリレン酸無水物などのペリレン酸顔料、ビスアゾ系顔料およびトリスアゾ系顔料などのアゾ系顔料、その他キナクリドン系顔料、ならびにアントラキノン系顔料などがある。特にキャリアを発生する顔料に、無金属フタロシアニン顔料、チタニルフタロシアニン顔料、フロレンやフロレノン環を含有するビスアゾ顔料、芳香族アミンから成るビスアゾ顔料、トリスアゾ顔料を用いたものは高い感度を示す優れた電子写真感光体を与える。
【００７４】
また前記増感染料をキャリア発生物質として用いてもよい。前述の染料は、単独で使用してもよいが、顔料を共存させることによってさらに高い効率でキャリアを発生させる場合が多い。
【００７５】
前述のような増感剤とは別に、繰返し使用に対しての残留電位の増加、帯電電位の低下および感度の低下などを防止する目的で、種々の化学物質を添加する必要が生じる場合がある。これらのための添加物質としては、１−クロルアントラキノン、ベンゾキノン、２，３−ジクロロナフトキノン、ナフトキノン、４，４’−ジニトロベンゾフェノン、４，４’−ジクロロベンゾフェノン、４−ニトロベンゾフェノン、４−ニトロベンザルマロンジニトリル、α−シアノ−β−（ｐ−シアノフェニル）アクリル酸エチル、９−アントラセニルメチルマロンジニトリル、１−シアノ−１−（ｐ−ニトロフェニル）−２−（ｐ−クロルフェニル）エチレンおよび２，７−ジニトロフルオレノンなどの電子吸引性化合物が挙げられる。その他、感光体中への添加物として、酸化防止剤、カール防止剤および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。
【００７６】
本発明によるジアミン化合物は、前述のような感光体の形態に応じて前述の種々の添加物質とともに、適当な溶剤中に溶解または分散して塗布液を調製し、その塗布液を導電性支持体１上に塗布して乾燥することによって、感光体を製造する。塗布液の溶剤としては、ベンゼン、トルエン、キシレンおよびモノクロルベンゼンなどの芳香族炭化水素、ジクロロメタンおよびジクロロエタンなどのハロゲン化炭化水素、テトラヒドロフラン、ジオキサン、ジメトキシメチルエーテル、ならびにジメチルホルムアミドなどの単独溶剤または２種以上の混合溶剤が挙げられる。これらの溶剤には、必要に応じてアルコール類、アセトニトリルおよびメチルエチルケトンなどの溶剤をさらに加えて使用することができる。
【００７７】
導電性支持体１と感光層４または１４との間に設ける中間層としては、アルミニウム陽極酸化膜、酸化アルミニウム、水酸化アルミニウムおよび酸化チタンなどの無機層を採用する。またポリビニルアルコール、ポリビニルブチラール、ポリビニルピロリドン、ポリアクリル酸、セルロース類、ゼラチン、デンプン、ポリウレタン、ポリイミド、ポリアミド、カゼインおよびＮ−メトキシメチル化ナイロンなどが用いられる。これらには酸化チタン、酸化スズおよび酸化アルミニウムなどの粒子を分散させてもよい。
【００７８】
なお導電性支持体１と感光層４または１４との間に設けられる中間層８は、保護機能や接着機能を付与し、塗工性を高め、さらには支持体から感光層への電荷注入改善を目的としている。このような材料としては、カゼイン、ポリビニルブチラール、ポリビニルアルコール、ニトロセルロース、エチレン−アクリル酸コポリマ、ポリアミド（ナイロン６、ナイロン６６、ナイロン６１０、共重合ナイロン、アルコキシメチル化ナイロンなど）、ポリウレタン、ゼラチン、酸化アルミニウム、酸化チタンなどが適当である。
【００７９】
以下、本発明によるジアミン化合物の製造例および本発明による電子写真感光体について、実施例に基づいて具体的に説明する。
【００８０】
（製造例１）
５−メチルベンゾフラン３３．０ｇ（３．３当量）にヨウ素２１．０ｇ（１．０当量）を加え、よく攪拌した溶液に硝酸１４．０ｍｌ（３．０当量）／水１４．０ｍｌ溶液を、氷冷下激しく撹拌しながら滴下した。滴下後、３０分還流して反応を完結させ、放冷した反応混合物にクロロホルム１００ｍｌを加えて、有機層を抽出した。その有機層を希ＮａＯＨ水溶液でよく洗浄した後、塩化カルシウムで乾燥した。溶媒を留去した後、減圧蒸留し、中間体である２−ヨード−５−メチルベンゾフランを得た。収率は６０％であった。
【００８１】
次に合成した２−ヨード−５−メチルベンゾフランを２２．４ｇ（４．１当量）およびベンジジン３．６８ｇ（１．０当量）、１８−クラウン−６−エーテル１．０６ｇ（０．２当量）、銅粉末５．１ｇ（４．０当量）、無水炭酸カリウム２２．１ｇ（８．０当量）をｏ−ジクロロベンゼン１５０ｍｌに混合し、３０時間、激しく加熱、撹拌、還流させた。反応終了後、熱時セライト濾過し、濾液を濃縮し、残渣をシリカゲルカラムクロマト（ｎ−へキサン／塩化メチレン＝３／７から塩化メチレンのみで溶出）により精製することによって目的のジアミン化合物（例示化合物Ｎｏ．３）９．２ｇを得た。収率は６５％であった。得られたジアミン化合物（例示化合物Ｎｏ．３）の¹Ｈ−ＮＭＲスペクトルは２．３０ｐｐｍ（ｓ，１２Ｈ，Ｍｅ）、６．８−７．７ｐｐｍ（ｍ，２４Ｈ，ベンゼンおよびベンゾフラン）を示した。また元素分析値は、Ｃ，８１．０％；Ｈ，５．１％；Ｎ，４．０％（計算値Ｃ，８１．８０％；Ｈ，５．１５％；Ｎ，３．９７％）を示し、目的化合物であることが確認できた。
【００８２】
（製造例２〜７）
例示化合物１，５，８，９，１０および２３のジアミン化合物を合成した。
【００８３】
先ず、ベンゾフランおよびＮ−メチルインドールを製造例１と同様の方法で合成し、２−ヨードベンゾフランおよびＮ−メチル−２−ヨードインドールを得た。２−ヨードベンゾフランおよびＮ−メチル−２−ヨードインドールの収率は、７０％および６２％であった。
【００８４】
次に、表４に示したヨーソ化合物とジアミノ化合物とを製造例１と同様の反応条件でウルマン反応を行い、目的のジアミン化合物を得た。合成の結果を表４に示す。¹Ｈ−ＮＭＲスペクトル、元素分析の結果より、いずれも目的の化合物が高収率で得られたことが確認できた。
【００８５】
【表４】

【００８６】
（実施例１〜４および比較例）
図１に示した電荷移動層６に含有される電荷移動物質３として、例示化合物Ｎｏ．１，Ｎｏ．５，Ｎｏ．１３もしくはＮｏ．２１に示したジアミン化合物、または従来公知の電荷移動物質である４−（ジエチルアミノ）−ベンズアルデヒド−Ｎ，Ｎ−ジフェニルヒドラゾンを比較例として用い、各々を含有させた積層構造の感光層４を形成して、実施例１〜４および比較例の５種類の電子写真感光体を作製した。
【００８７】
アルミ蒸着のポリエステルフィルム（膜厚８０μｍ）を導電性支持体１とし、その上に下記構造式（ＶＩＩ）で示されるビスアゾ顔料をフェノキシ樹脂（ユニオンカーバイド製：ＰＫＨＨ）の１％テトラヒドロフラン（ＴＨＦ）溶液中に、重量比で樹脂と同量加えた。次いでペイントコンディショナ（レッドデビル社製）の中で直径１．５ｍｍのガラスビーズとともに約２時間分散し、ドクターブレイド法によって塗布、乾燥して顔料層である電荷発生層５を形成した。乾燥後の膜厚は０．２μｍであった。
【００８８】
【化１６】

【００８９】
形成した電荷発生層５の上に、本発明によるジアミン化合物の例示化合物Ｎｏ．１，Ｎｏ．５，Ｎｏ．１３，Ｎｏ．２１または４−（ジエチルアミノ）−ベンズアルデヒド−Ｎ，Ｎ−ジフェニルヒドラゾンを１ｇと、ポリアリレート樹脂（ユニチカ製：Ｕ−１００）１．２ｇをテトラヒドロフランに溶かした溶液（１５％）をスキージングドクターによって塗布した。このように乾燥膜厚２５μｍの樹脂−ジアミン化合物固溶相である電荷移動層６を形成し、実施例１〜４および比較例の５種類の積層型電子写真感光体を作製した。
【００９０】
作製した積層型電子写真感光体の電子写真特性は、静電記録紙試験装置（ＳＰ−４２８：川口電気社製）によって評価した。加電圧：−６ｋＶおよびスタティック：Ｎｏ．３の測定条件で、白色光照射（照射光：５ルックス）によって−７００Ｖから−１０００Ｖに減衰させるために要する露光量Ｅ₁₀₀（ルックス・秒）および初期電位Ｖ₀（−ボルト）を測定し、その値を表５に示した。また同装置を用いて、加電−除電（除電光：４０ルックスの白色光を１秒照射）を１サイクルとして１万回同様の操作を行った後の露光量Ｅ₁₀₀（ルックス・秒）および初期電位Ｖ₀（−ボルト）を測定し、Ｅ₁₀₀およびＶ₀の変化を調べた。
【００９１】
【表５】

【００９２】
表５から、本発明によるジアミン化合物は、従来化合物と比較して感度繰返し特性が良好であることが判った。
【００９３】
（実施例５）
図５に示した電荷移動層６に含有される電荷移動物質３として、例示化合物Ｎｏ．８に示したジアミン化合物を含有させた積層構造の感光層４を形成して、電子写真感光体を製造した。
【００９４】
アルミ蒸着のポリエステルフィルムを導電性支持体１とし、該導電性支持体１上に酸化チタン２．１ｇと共重合ナイロン３．９ｇ（ＣＭ８０００：東レ社製）をメチルアルコール３２．９ｇとジクロロエタン６１．１ｇの混合溶剤に溶解した溶液を塗布、乾燥して、膜厚１μｍの中間層８を形成した。この中間層８の上に下記構造式（ＶＩＩＩ）で示されるＸ型無金属フタロシアニン（ファストゲンブルー８１２０：大日本インキ社製）０．４ｇを塩化ビニル：酢酸ビニル共重合体樹脂（エスレックスＭ：積水化学社製）０．３ｇを溶かした酢酸エチル溶液３０ｍｌ中に加え、ペイントコンディショナ中で約２０分間分散した。分散液をドクターブレイド法によって塗布し、乾燥後の膜厚が０．４μｍになるように電荷発生層５を形成した。
【００９５】
【化１７】

【００９６】
形成した電荷発生層５上に、本発明によるジアミン化合物である例示化合物Ｎｏ．８を、重量比５０％で含有したポリアリレート層である電荷移動層６を積層し、中間層８、電荷発生層５および電荷移動層６の３層から成る感光体を作製した。
【００９７】
作製した感光体の７８０ｎｍの光を用いて電位半減に要したエネルギ（Ｅ₅₀）および初期電位（−Ｖ₀）を求めたところ、Ｖ₀＝−７２０（ボルト）およびＥ₅₀＝０．２０（μＪ）で、非常に高感度かつ高帯電性の感光体であった。
【００９８】
またレーザプリンタ（ＷＤ−５８０Ｐ：シャープ社製）を改造し、ドラム部に作製した感光体を張付け、連続空コピー（Non Copy Aging）を１万回行った後、その初期電位低下および感度低下の度合いも調べた。その結果、Ｖ₀＝−７１０（ボルト）およびＥ₅₀＝０．２１（μＪ）で、第１回目と比べてほとんど値の変動は見られなかった。
【００９９】
（実施例６〜９）
図３に示した電荷移動物質３として、例示化合物Ｎｏ．３，Ｎｏ．９，Ｎｏ．１９およびＮｏ．２３に示したジアミン化合物の各々を含有させた単一層の感光層４を形成して、実施例６〜９の４種類の電子写真感光体を製造した。
【０１００】
アルミ基盤表面をアルマイト加工（アルマイト層：７μｍ）した導電性支持体１上に本発明によるジアミン化合物の例示化合物Ｎｏ．３，Ｎｏ．９，Ｎｏ．１９またはＮｏ．２３を１ｇ、下記構造式（ＩＸ）で示されるポリカーボネート樹脂１．１ｇ、Ｎ，Ｎ−３，５−キシリル−３，４，９，１０−ペリレンテトラカルボキシルイミド０．１５ｇおよび紫外線吸収剤０．０５ｇを塩化メチレンに溶かした溶液を調製した。このときイミド化合物は一部分散状態であった。調製した溶液をアプリケータによって塗布し、乾燥膜厚２０μｍの単層型感光体を得た。
【０１０１】
【化１８】

【０１０２】
得られた感光体の電子写真特性は、静電記録紙試験装置によって評価した。測定条件は、加電圧：５．５ｋＶおよびスタティック：Ｎｏ．３であった。白色光照射によって＋７００Ｖから＋１００Ｖに減衰させるために要する露光量Ｅ₁₀₀（ルックス・秒）を測定し、その値を表６に示した。また一万回の空コピーテストを行い、感度（Ｅ₁₀₀）の低下の度合いも表６に示した。
【０１０３】
【表６】

【０１０４】
表６から、本発明によるジアミン化合物を用いた感光体は、正帯電においても優れた感度および繰返し特性を有することが判った。
【０１０５】
【発明の効果】
以上のように本発明によれば、今までにない新規なジアミン化合物を提供することができ、該ジアミン化合物は、広い共役系を有しているので、電子写真感光体の電荷移動物質として用いれば、電荷移動度を高くして電子写真感光体の残留電位特性を向上させることができる。
【０１０６】
また本発明によれば、前記ジアミン化合物を含有することによって、高感度で高耐久性を有する有機質の電子写真感光体であって、無機系のものに比べて無毒で資源的にも問題なく、透明性がよく、軽量で成膜性も優れ、正負の両帯電性を有し、感光体の製造も容易という有機系感光体の利点を備えているとともに、繰返し使用でも光感度の低下がほとんど起こらないという優れた特性を備えている電子写真感光体を提供することができる。
【図面の簡単な説明】
【図１】電荷発生層上に電荷移動層を有する機能分離型感光層を有する電子写真感光体の一例を模式的に示す断面図である。
【図２】電荷移動層上に電荷発生層を有する機能分離型感光層である。
【図３】分散型感光層を有する電子写真感光体の一例を模式的に示す断面図である。
【図４】図３の電子写真感光体において表面保護層７を有する例を示す断面図である。
【図５】図１の電子写真感光体において中間層８を有する例を示す断面図である。
【図６】図３の電子写真感光体において中間層８を有する例を示す断面図である。
【符号の説明】
１ 導電性支持体
２ 電荷発生物質
３ 電荷移動物質
４，１４ 感光層
５ 電荷発生層
６ 電荷移動層
７ 表面保護層
８ 中間層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member containing a diamine compound as a charge transfer material in a photosensitive layer provided on a conductive support.
[0002]
[Prior art]
Since the electrophotographic technology can obtain a high-quality image in an immediate manner, it has recently been used not only in the field of copying machines but also in the field of various printers, and its application range is expanding. In the field of electrophotographic photoreceptors (hereinafter also simply referred to as “photoreceptors”), the photoconductive materials have long been inorganic materials such as selenium, arsenic, selenium alloys, selenium-tellurium alloys, cadmium sulfide, and zinc oxide. Material was used. However, in recent years, instead of such inorganic materials, organic photoreceptors mainly composed of organic photoconductive materials having advantages such as pollution-free, good film formability and ease of production have been developed. It became so.
[0003]
Among organic photoconductors, a so-called multilayer type photoconductor was devised, in which two layers of a charge generation layer composed of a charge generation material and a charge transfer layer composed of a charge transfer material were sequentially laminated, and became the mainstream of research. Yes. That is, in the multilayer photoreceptor, by combining a charge generation material capable of forming a desired charge generation layer with high efficiency and a charge transfer material capable of forming a desired charge transfer layer with high efficiency,
1. A higher sensitivity photoconductor can be obtained,
2. A wide range of materials can be selected to provide a highly safe photoconductor.
3. High productivity of coating and relatively advantageous in terms of cost
From the point of view, it has become the mainstream of photoconductors. In addition, a printing machine having a high printing durability and a high-speed performance such as a total printing number of 200,000 or more and a one-minute copying speed of 70 or more is commercially available.
[0004]
As described above, some organic laminated photoreceptors that have been put to practical use have excellent performance, but most of them have various problems related to the production of the photoreceptor in pursuit of the performance. The current situation is still having points.
[0005]
Among those specific problems, some of those related to charge transfer materials are listed.
1. Low compatibility with the binder,
2. That crystals are likely to precipitate,
3. Sensitivity changes occur when used repeatedly,
4). Poor chargeability and repeatability,
5). Poor residual potential characteristics,
Etc.
[0006]
The typical ones of these charge transfer materials can be classified according to their structural characteristics. First, the arylene group (mostly a mere phenylene group in the early stages of development) was the central host nucleus. The hydrazone system (JP-A-54-59143), stilbene / styryl system (JP-A-58-198043) and triarylamine system (Japanese Patent Publication No. 58-32372) have been energetically studied. It was. Subsequently, a series of compounds having a monocyclic heterocyclic ring system in the central mother nucleus, phenothiazine, triazole, quinoxaline, oxadiazole, oxazole, pyrazoline, dihydronicotinamide, indoline and semicarbazone Compounds have been developed. Recently, pyrene derivatives, naphthalene derivatives, terphenyl derivatives (Japanese Patent Laid-Open No. 7-48324) and the like having a condensed polycyclic hydrocarbon system in the central mother nucleus have been developed.
[0007]
[Problems to be solved by the invention]
Despite the fact that many organic compounds have been developed as charge transfer materials as described above, there are no organic compounds that satisfy all the above-mentioned problems. In the present situation, a material that sufficiently satisfies mechanical strength and high durability has not yet been obtained.
[0008]
An object of the present invention is to provide a novel benzofuran, benzothiophene, or diamine compound having an indole ring, and a highly sensitive and highly durable electrophotographic photoreceptor using the diamine compound as a charge transfer material.
[0009]
[Means for Solving the Problems]
The present invention is a diamine compound represented by the following general formula (I).
[0010]
[Chemical 8]

[0011]
(Wherein Ar¹May contain substituentsIncluding 1 to 3 benzene ringsAn arylene group, a divalent heterocyclic group which may contain a substituent, and an alkylene group having 1 to 5 carbon atoms which may contain a substituent are shown. Ar²May contain an aryl group that may contain a substituent, a heterocyclic group that may contain a substituent, an aralkyl group that may contain a substituent, an alkyl group having 1 to 5 carbon atoms that may contain a substituent, or a substituent. A C1-C5 fluoroalkyl group and a C1-C5 perfluoroalkyl group which may contain a substituent are shown. R¹Is an alkyl group having 1 to 3 carbon atoms which may contain a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, a perfluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, carbon A C1-C3 alkoxy group, a C1-C3 dialkylamino group, or a hydrogen atom is shown. a is an alkyl group having 1 to 3 carbon atoms which may contain a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, a perfluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, An alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom is shown, and n is an integer of 1 to 4. However, when n is 2 or more, each of a may be the same or different and may form a ring with each other. X is oxygen, sulfur atom or N—R²R²Represents an alkyl group having 1 to 3 carbon atoms which may contain a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, or a perfluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent. . )
[0012]
According to the present invention, an unprecedented novel diamine compound can be provided. Since the diamine compound has a wide conjugated system, if used as a charge transfer material of an electrophotographic photoreceptor, charge transfer The residual potential characteristics of the electrophotographic photosensitive member can be improved by increasing the degree.
[0013]
The present invention is characterized in that a photosensitive layer provided on a conductive support contains a benzofuran, benzothiophene or diamine compound having an indole ring represented by the following general formula (I) as a charge transfer material. An electrophotographic photoreceptor.
[0014]
[Chemical 9]

[0015]
(Wherein Ar¹May contain substituentsIncluding 1 to 3 benzene ringsAn arylene group, a divalent heterocyclic group which may contain a substituent, and an alkylene group having 1 to 5 carbon atoms which may contain a substituent are shown. Ar²May contain an aryl group that may contain a substituent, a heterocyclic group that may contain a substituent, an aralkyl group that may contain a substituent, an alkyl group having 1 to 5 carbon atoms that may contain a substituent, or a substituent. A C1-C5 fluoroalkyl group and a C1-C5 perfluoroalkyl group which may contain a substituent are shown. R¹Is an alkyl group having 1 to 3 carbon atoms which may contain a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, a perfluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, carbon A C1-C3 alkoxy group, a C1-C3 dialkylamino group, or a hydrogen atom is shown. a is an alkyl group having 1 to 3 carbon atoms which may contain a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, a perfluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, An alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom is shown, and n is an integer of 1 to 4. However, when n is 2 or more, each of a may be the same or different and may form a ring with each other. X is oxygen, sulfur atom or N—R²R²Represents an alkyl group having 1 to 3 carbon atoms which may contain a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, or a perfluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent. . )
[0016]
According to the present invention, since the diamine compound is excellent in compatibility with the binder polymer, it can be incorporated in a large amount in the photosensitive layer to improve the photosensitivity of the electrophotographic photosensitive member, and the diamine compound as a crystal. Since it is difficult to deposit, the characteristics of the electrophotographic photosensitive member during repeated use can be stabilized, and an organic electrophotographic photosensitive member having high sensitivity and high durability can be provided. Organic photoreceptors that are non-toxic and resource-free compared to inorganic ones, have good transparency, are lightweight, have excellent film-forming properties, have both positive and negative chargeability, and are easy to manufacture. It is possible to provide an electrophotographic photosensitive member having the following advantages.
[0017]
The present invention is characterized in that the diamine compound is represented by the following general formula (II).
[0018]
[Chemical Formula 10]

[0019]
(Wherein Ar¹, R¹, X, a and n have the same meanings as those shown in formula (I). )
[0020]
According to the present invention, the photosensitive layer can be incorporated in a large amount to improve the photosensitivity of the electrophotographic photosensitive member, and the characteristics during repeated use of the electrophotographic photosensitive member can be stabilized. Organic photoconductors that are non-toxic and resource-free compared to inorganic materials, have good transparency, are lightweight, have excellent film-forming properties, have both positive and negative chargeability, and are easy to manufacture. It is possible to provide an electrophotographic photosensitive member having the following advantages.
[0021]
The present invention is characterized in that the diamine compound is represented by the following general formula (III).
[0022]
Embedded image

[0023]
(In the formula, b is an alkyl group having 1 to 3 carbon atoms which may contain a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, and 1 to 5 carbon atoms which may contain a substituent. A perfluoroalkyl group, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and m represents an integer of 1 to 4, provided that m is 2 or more. , B may be the same or different and may form a ring with each other, l represents an integer of 1 to 5;¹, A, X, and n are as defined in general formula (I). )
[0024]
According to the present invention, the photosensitive layer can be incorporated in a large amount to improve the photosensitivity of the electrophotographic photosensitive member, and the characteristics during repeated use of the electrophotographic photosensitive member can be stabilized. Organic photoconductors that are non-toxic and resource-free compared to inorganic materials, have good transparency, are lightweight, have excellent film-forming properties, have both positive and negative chargeability, and are easy to manufacture. It is possible to provide an electrophotographic photosensitive member having the following advantages.
[0025]
The present invention is characterized in that the diamine compound is represented by the following general formula (IV).
[0026]
Embedded image

[0027]
(Wherein R¹, X, a, b, m and n have the same meanings as those shown in formula (III). )
According to the present invention, the photosensitive layer can be incorporated in a large amount to improve the photosensitivity of the electrophotographic photosensitive member, and the characteristics during repeated use of the electrophotographic photosensitive member can be stabilized. Organic photoconductors that are non-toxic and resource-free compared to inorganic materials, have good transparency, are lightweight, have excellent film-forming properties, have both positive and negative chargeability, and are easy to manufacture. It is possible to provide an electrophotographic photosensitive member having the following advantages.
[0028]
Moreover, this invention is characterized by the said diamine compound being shown by the following general formula (V).
[0029]
Embedded image

[0030]
(Wherein c and d are each an optionally substituted alkyl group having 1 to 3 carbon atoms, an optionally substituted fluoroalkyl group having 1 to 5 carbon atoms, and an optionally substituted carbon number. A 1-5 perfluoroalkyl group, a C1-C3 alkoxy group, a C1-C3 dialkylamino group, a halogen atom or a hydrogen atom is shown, and k and j each represent an integer of 1-4. When k and j are 2 or more, the corresponding c and d may be the same or different, and may form a ring with each other.¹, X, a and n have the same meanings as those shown in formula (I). )
[0031]
According to the present invention, the photosensitive layer can be incorporated in a large amount to improve the photosensitivity of the electrophotographic photosensitive member, and the characteristics during repeated use of the electrophotographic photosensitive member can be stabilized. Organic photoconductors that are non-toxic and resource-free compared to inorganic materials, have good transparency, are lightweight, have excellent film-forming properties, have both positive and negative chargeability, and are easy to manufacture. It is possible to provide an electrophotographic photosensitive member having the following advantages.
[0032]
The present invention is characterized in that the diamine compound is represented by the following general formula (VI).
[0033]
Embedded image

[0034]
(Wherein R¹, X, a, c, d, j, k, and n have the same meanings as those shown in the general formula (V). )
[0035]
According to the present invention, the photosensitive layer can be incorporated in a large amount to improve the photosensitivity of the electrophotographic photosensitive member, and the characteristics during repeated use of the electrophotographic photosensitive member can be stabilized. Organic photoconductors that are non-toxic and resource-free compared to inorganic materials, have good transparency, are lightweight, have excellent film-forming properties, have both positive and negative chargeability, and are easy to manufacture. It is possible to provide an electrophotographic photosensitive member having the following advantages.
[0036]
Further, the invention is characterized in that the photosensitive layer has a laminated structure of a charge generation layer containing a charge generation material and a charge transfer layer containing the charge transfer material.
[0037]
According to the present invention, a multilayer electrophotographic photosensitive member having high sensitivity and high durability can be provided by containing the diamine compound in the charge transfer layer.
[0038]
In the invention, it is preferable that the photosensitive layer is composed of a single layer containing a charge generation material and the charge transfer material.
[0039]
According to the present invention, a single layer type electrophotographic photosensitive member having high sensitivity and high durability can be provided by containing the diamine compound as a charge transfer material together with a charge generating material in a photosensitive layer.
[0040]
Further, the present invention is characterized in that an intermediate layer is provided between the conductive support and the photosensitive layer.
[0041]
According to the present invention, by providing an intermediate layer, the conductive support is protected, the adhesion between the conductive support and the photosensitive layer is increased, the coating property of the photosensitive layer is increased, and the conductive support is separated from the conductive support. The charge injection into the photosensitive layer can be improved.
[0042]
In the present invention, the charge transfer layer is laminated on the charge generation layer, and the charge transfer layer serves as a binder polymer, a polymer of a vinyl compound and a copolymer thereof, a polyester resin, a polycarbonate resin, a polyarylate resin, a polysulfone. It contains at least one selected from the group consisting of a resin, a polyvinyl butyral resin, a phenoxy resin, a cellulose resin, a urethane resin, and an epoxy resin.
[0043]
According to the present invention, an electrophotographic photoreceptor excellent in wear resistance can be provided by using the resin as a binder polymer for the photosensitive layer.
[0044]
DETAILED DESCRIPTION OF THE INVENTION
The diamine compound according to the present invention is represented by the following general formula (I).
[0045]
Embedded image

[0046]
  In general formula (I), Ar¹May contain substituentsIncluding 1 to 3 benzene ringsAn arylene group, a divalent heterocyclic group which may contain a substituent, and an alkylene group having 1 to 5 carbon atoms which may contain a substituent are shown.
[0047]
  Ar¹ Of the arylene group represented byAs a specific example,The followingIs mentioned.

Specific examples of the heterocyclic group include benzofuryl, benzothiophenyl, N-methylindolyl, benzothiazolyl, benzoxazolyl and N-ethylcarbazolyl. Specific examples of the alkyl group include n-propyl and isopropyl.
[0048]
In the general formula (I), Ar²May contain an aryl group that may contain a substituent, a heterocyclic group that may contain a substituent, an aralkyl group that may contain a substituent, an alkyl group having 1 to 5 carbon atoms that may contain a substituent, or a substituent. A C1-C5 fluoroalkyl group and a C1-C5 perfluoroalkyl group which may contain a substituent are shown.
[0049]
Ar²Specific examples of the aryl group include aryl groups such as phenyl, tolyl, anisyl, naphthyl, pyrenyl and biphenyl, and heterocycles such as benzofuryl, benzothiophenyl, N-methylindolyl, benzothiazolyl, benzoxazolyl and N-ethylcarbazolyl. Examples include cyclic groups, alkyl groups such as n-propyl and isopropyl.
[0050]
In the general formula (I), R¹Is an alkyl group having 1 to 3 carbon atoms which may contain a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, a perfluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, carbon A C1-C3 alkoxy group, a C1-C3 dialkylamino group, or a hydrogen atom is shown.
[0051]
R¹Specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl and isopropyl, alkoxy groups such as methoxy and ethoxy, and dialkylamino groups such as dimethylamino and diethylamino.
[0052]
In the general formula (I), a is an alkyl group having 1 to 3 carbon atoms which may contain a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, or 1 carbon atom which may contain a substituent. A -5 perfluoroalkyl group, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and n represents an integer of 1 to 4; However, when n is 2 or more, each of a may be the same or different and may form a ring with each other.
[0053]
Specific examples of a include alkyl groups such as methyl, ethyl, n-propyl and isopropyl, alkoxy groups such as methoxy, ethoxy, n-propoxy and isopropoxy, dialkylamino groups such as dimethylamino, diethylamino and isopropylamino, fluorine And halogen atoms such as chlorine and bromine. In general, an electron donating substituent is preferred.
[0054]
In the general formula (I), X is oxygen, a sulfur atom or N—R.²R²Represents an alkyl group having 1 to 3 carbon atoms which may contain a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, or a perfluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent. .
[0055]
Specific examples of X include oxygen, sulfur atom, N-methyl group and N-ethyl group.
[0056]
In particular, among the diamine compounds represented by the general formula (I), Ar is excellent from the viewpoints of electrophotographic characteristics, cost, production, and the like.¹Is a phenylene group, biphenylene group or naphthylene group, Ar²Is phenyl, p-tolyl, benzofuryl, benzothiophenyl or N-methylindolyl, R¹And a is a hydrogen atom, and X is an oxygen or sulfur atom.
[0057]
Specific examples of the diamine compound of the present invention represented by the general formula (I) include, for example, diamine compounds having the structures shown in Tables 1 to 3 below. It is not limited.
[0058]
[Table 1]

[0059]
[Table 2]

[0060]
[Table 3]

[0061]
The electrophotographic photoreceptor according to the present invention contains one or more diamine compounds represented by the above general formula (I) as a charge transfer material for the photosensitive layer. The layer structure of the electrophotographic photosensitive member can take various forms as shown below.
[0062]
FIG. 1 is a cross-sectional view schematically showing an example of an electrophotographic photosensitive member having a function-separated type photosensitive layer having a charge transfer layer on a charge generation layer. A charge generation layer 5 in which a charge generation material 2 as a main component is dispersed in a binder polymer as a photosensitive layer 4 on a conductive support 1, and a charge transfer in which a charge transfer material 3 is dispersed in a binder polymer as a main component. This is a function-separated type photoconductor comprising a laminate with the layer 6. A charge transfer layer 6 is formed on the surface of the charge generation layer 5, and the charge transfer layer 6 contains the diamine compound according to the present invention as the charge transfer material 3.
[0063]
FIG. 2 shows a function-separated type photosensitive layer having a charge generation layer on a charge transfer layer. 1 is a function-separated type photoconductor composed of a stack of a charge generation layer 5 and a charge transfer layer 6 similar to FIG. 1, but the charge generation layer 5 is formed on the surface of the charge transfer layer 6 contrary to FIG. The charge transfer layer 6 contains the diamine compound according to the present invention as the charge transfer material 3.
[0064]
FIG. 3 is a cross-sectional view schematically showing an example of an electrophotographic photosensitive member having a dispersion type photosensitive layer. A structure of a single-layer type photoreceptor composed of a single layer in which a charge generating material 2 and a charge transfer material 3 are dispersed as a photosensitive layer 4 in a binder polymer on a conductive support 1 is shown.
[0065]
FIG. 4 is a cross-sectional view showing an example having the surface protective layer 7 in the electrophotographic photosensitive member of FIG. A structure of a single-layer type photoreceptor composed of a single layer by providing the surface protective layer 7 on the conductive support 1 and the same photosensitive layer 14 as in FIG. 3 is shown.
[0066]
FIG. 5 is a sectional view showing an example having the intermediate layer 8 in the electrophotographic photosensitive member of FIG. An intermediate layer 8 is provided between the conductive support 1 and a photosensitive layer 4 similar to that shown in FIG.
[0067]
FIG. 6 is a cross-sectional view showing an example having the intermediate layer 8 in the electrophotographic photosensitive member of FIG. An intermediate layer 8 is provided between the conductive support 1 and a photosensitive layer 14 similar to that shown in FIG. 3, and a configuration of a single-layer type photoreceptor composed of a single layer is shown.
[0068]
In order to use the above-mentioned diamine compound for an electrophotographic photoreceptor, various methods are conceivable. For example, as shown in FIG. 1, in the form of a laminated structure composed of a charge generation layer 5 and a charge transfer layer 6 having high carrier generation efficiency, a sensitizing dye, an azo pigment and a phthalocyanine pigment are represented on the conductive support 1. The charge generation layer 5 mainly composed of the pigment to be formed is provided. On the charge generation layer 5, a laminate type comprising a charge transfer layer in which the above-mentioned diamine compound is added with an antioxidant compound or an electron withdrawing compound as necessary and dissolved or dispersed in a binder polymer is provided. A function-separated photoreceptor is used. In addition, a coating solution in which the above-described diamine compound and sensitizing dye are added to a chemical sensitizer or an electron-withdrawing compound as necessary and dissolved or dispersed in a binder polymer is made conductive as shown in FIG. A single-layer type photoconductor coated on the support 1 is used. Thus, the diamine compound according to the present invention can be applied to any of these cases.
[0069]
Examples of the binder polymer include various types depending on the application field. That is, in the field of photoconductors for copying machines or printers, polystyrene resins, polyvinyl acetal resins, polysulfone resins, polycarbonate resins, polyphenylene oxide resins, polyester resins, alkyd resins, and polyarylate resins are desirable. These resins may be used alone or in combination of two or more. In particular, polystyrene resin, polycarbonate resin, polyarylate resin and polyphenylene oxide resin have a volume resistance of 10¹³Above Ω, it has excellent film properties and potential characteristics.
[0070]
The amount of these binder polymers added is preferably 0.2 to 20 times, more preferably 0.5 to 5 times the weight ratio of the diamine compound. When the ratio is less than 0.2 times, the diamine compound is precipitated from the surface of the photoreceptor, and when the ratio is more than 20 times, the sensitivity is significantly lowered.
[0071]
In particular, an alkaline binder is required for use in printing plates. The alkaline binder is a polymer substance having an acidic group that is soluble in water or an alcoholic alkaline solvent containing a mixed system with water. Examples of the soluble acidic group include an acid anhydride group, a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group, and a sulfonimide group. These alkaline binders usually preferably have a high acid value of 100 or more. A binder having a large acid value is readily soluble in an alkaline solvent or easily swelled. Such binders include, for example, styrene: maleic anhydride copolymer, vinyl acetate: maleic anhydride copolymer, vinyl acetate: crotonic acid copolymer, methacrylic acid: methacrylic acid ester copolymer, phenol resin and Methacrylic acid: styrene: methacrylic acid ester copolymer. These resins are added to the photoconductive organic substance at the same ratio as in the case of the photoconductor for copying machines.
[0072]
Examples of the sensitizing dye include triphenylmethane dyes represented by methyl violet, crystal violet, knight blue and victoria blue, acridine dyes represented by erythrosine, rhodamine B, rhodamine 3R, acridine orange and frappeosin And thiazine dyes typified by methylene blue and methylene green, oxazine dyes typified by capri blue and meldra blue, other cyanine dyes, styryl dyes, pyrylium salt dyes, and thiopyrylium salt dyes.
[0073]
Photoconductive pigments that generate carriers with extremely high efficiency by light absorption in the photosensitive layer include phthalocyanine pigments such as various metal phthalocyanines, metal-free phthalocyanines, and halogenated metal-free phthalocyanines, peryleneimides, and perylene acid anhydrides. Perylene acid pigments, azo pigments such as bisazo pigments and trisazo pigments, other quinacridone pigments, and anthraquinone pigments. Excellent electrophotography with high sensitivity, especially when the carrier-generating pigment is a metal-free phthalocyanine pigment, titanyl phthalocyanine pigment, a bisazo pigment containing a fullerene or a fluorenone ring, a bisazo pigment made of an aromatic amine, or a trisazo pigment Give the photoreceptor.
[0074]
The sensitizing dye may be used as a carrier generating substance. The above-mentioned dyes may be used alone, but in many cases, carriers are generated with higher efficiency by the coexistence of pigments.
[0075]
In addition to the sensitizers described above, it may be necessary to add various chemical substances for the purpose of preventing an increase in residual potential, a decrease in charging potential and a decrease in sensitivity due to repeated use. . Additives for these include 1-chloroanthraquinone, benzoquinone, 2,3-dichloronaphthoquinone, naphthoquinone, 4,4'-dinitrobenzophenone, 4,4'-dichlorobenzophenone, 4-nitrobenzophenone, 4-nitroben Zalmalondinitrile, ethyl α-cyano-β- (p-cyanophenyl) acrylate, 9-anthracenylmethylmalondinitrile, 1-cyano-1- (p-nitrophenyl) -2- (p-chloro) And electron withdrawing compounds such as phenyl) ethylene and 2,7-dinitrofluorenone. In addition, antioxidants, anti-curl agents, leveling agents, and the like can be added as necessary to the photoreceptor.
[0076]
The diamine compound according to the present invention prepares a coating solution by dissolving or dispersing it in an appropriate solvent together with the above-mentioned various additives according to the form of the photoreceptor as described above, and the coating solution is used as a conductive support. The photosensitive member is manufactured by coating on 1 and drying. Solvents for the coating solution include aromatic solvents such as benzene, toluene, xylene and monochlorobenzene, halogenated hydrocarbons such as dichloromethane and dichloroethane, single solvents such as tetrahydrofuran, dioxane, dimethoxymethyl ether, and dimethylformamide, or two kinds. The above mixed solvent is mentioned. These solvents can be used by further adding a solvent such as alcohols, acetonitrile, and methyl ethyl ketone as necessary.
[0077]
As an intermediate layer provided between the conductive support 1 and the photosensitive layer 4 or 14, an inorganic layer such as an aluminum anodic oxide film, aluminum oxide, aluminum hydroxide and titanium oxide is employed. Polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, polyacrylic acid, celluloses, gelatin, starch, polyurethane, polyimide, polyamide, casein, N-methoxymethylated nylon and the like are used. In these, particles such as titanium oxide, tin oxide and aluminum oxide may be dispersed.
[0078]
The intermediate layer 8 provided between the conductive support 1 and the photosensitive layer 4 or 14 provides a protective function and an adhesive function, enhances coating properties, and further improves charge injection from the support to the photosensitive layer. It is an object. Examples of such materials include casein, polyvinyl butyral, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide (nylon 6, nylon 66, nylon 610, copolymer nylon, alkoxymethylated nylon, etc.), polyurethane, gelatin, Aluminum oxide, titanium oxide, etc. are suitable.
[0079]
EXAMPLES Hereinafter, the manufacture example of the diamine compound by this invention and the electrophotographic photoreceptor by this invention are demonstrated concretely based on an Example.
[0080]
(Production Example 1)
To 33.0 g (3.3 equivalents) of 5-methylbenzofuran, 21.0 g (1.0 equivalents) of iodine was added, and a solution of 14.0 ml (3.0 equivalents) nitric acid / 14.0 ml water was added to the well-stirred solution. The mixture was added dropwise with vigorous stirring under ice cooling. After the dropwise addition, the reaction was completed by refluxing for 30 minutes, and 100 ml of chloroform was added to the cooled reaction mixture to extract the organic layer. The organic layer was washed thoroughly with a dilute aqueous NaOH solution and dried over calcium chloride. After distilling off the solvent, the residue was distilled under reduced pressure to obtain 2-iodo-5-methylbenzofuran as an intermediate. The yield was 60%.
[0081]
Next, 22.4 g (4.1 equivalent) of synthesized 2-iodo-5-methylbenzofuran, 3.68 g (1.0 equivalent) of benzidine, 1.06 g (0.2 equivalent) of 18-crown-6-ether Then, 5.1 g (4.0 equivalents) of copper powder and 22.1 g (8.0 equivalents) of anhydrous potassium carbonate were mixed with 150 ml of o-dichlorobenzene, and the mixture was vigorously heated, stirred and refluxed for 30 hours. After completion of the reaction, the mixture was filtered through Celite while hot, the filtrate was concentrated, and the residue was purified by silica gel column chromatography (eluted with n-hexane / methylene chloride = 3/7 to methylene chloride alone) to give the desired diamine compound (example) Compound No. 3) 9.2 g was obtained. The yield was 65%. Of the obtained diamine compound (Exemplary Compound No. 3)¹The 1 H-NMR spectrum showed 2.30 ppm (s, 12H, Me), 6.8-7.7 ppm (m, 24H, benzene and benzofuran). The elemental analysis values were C, 81.0%; H, 5.1%; N, 4.0% (calculated value C, 81.80%; H, 5.15%; N, 3.97%) It was confirmed that it was the target compound.
[0082]
(Production Examples 2 to 7)
Diamine compounds of Exemplary Compounds 1, 5, 8, 9, 10 and 23 were synthesized.
[0083]
First, benzofuran and N-methylindole were synthesized in the same manner as in Production Example 1 to obtain 2-iodobenzofuran and N-methyl-2-iodoindole. The yields of 2-iodobenzofuran and N-methyl-2-iodoindole were 70% and 62%.
[0084]
Next, the Uromann reaction of the iodo compound and diamino compound shown in Table 4 was carried out under the same reaction conditions as in Production Example 1 to obtain the target diamine compound. The results of the synthesis are shown in Table 4.¹From the results of H-NMR spectrum and elemental analysis, it was confirmed that the target compound was obtained in high yield.
[0085]
[Table 4]

[0086]
(Examples 1-4 and comparative examples)
As the charge transfer material 3 contained in the charge transfer layer 6 shown in FIG. 1, No. 1 5, no. 13 or No. Using the diamine compound shown in No. 21 or the conventionally known charge transfer substance 4- (diethylamino) -benzaldehyde-N, N-diphenylhydrazone as a comparative example, a photosensitive layer 4 having a laminated structure containing each of them was formed. Thus, five types of electrophotographic photoreceptors of Examples 1 to 4 and Comparative Example were produced.
[0087]
A 1% tetrahydrofuran (THF) solution of a phenazo resin (manufactured by Union Carbide: PKHH) with a bisazo pigment represented by the following structural formula (VII) as a conductive support 1 is a polyester film (a film thickness of 80 μm) deposited on aluminum. The same amount as the resin was added by weight. Subsequently, it was dispersed in a paint conditioner (manufactured by Red Devil) together with glass beads having a diameter of 1.5 mm for about 2 hours, applied by a doctor blade method and dried to form a charge generation layer 5 as a pigment layer. The film thickness after drying was 0.2 μm.
[0088]
Embedded image

[0089]
On the formed charge generation layer 5, the exemplified compound No. 1 of the diamine compound according to the present invention is used. 1, No. 1 5, no. 13, no. A solution (15%) of 21 or 4- (diethylamino) -benzaldehyde-N, N-diphenylhydrazone and 1.2 g of polyarylate resin (Unitika: U-100) dissolved in tetrahydrofuran was applied by a squeezing doctor. did. Thus, the charge transfer layer 6 which is a resin-diamine compound solid solution phase having a dry film thickness of 25 μm was formed, and five types of laminated electrophotographic photoreceptors of Examples 1 to 4 and Comparative Example were produced.
[0090]
The electrophotographic characteristics of the produced laminated electrophotographic photosensitive member were evaluated by an electrostatic recording paper test apparatus (SP-428: manufactured by Kawaguchi Electric Co., Ltd.). Applied voltage: -6 kV and static: No. Exposure amount E required to attenuate from −700 V to −1000 V by white light irradiation (irradiation light: 5 lux) under the measurement condition 3₁₀₀(Looks-seconds) and initial potential V₀(-Volt) was measured and the value is shown in Table 5. Further, using the same apparatus, exposure amount E after performing the same operation 10,000 times with one cycle of charge-charge removal (charge removal light: irradiation of 40 lux white light for 1 second).₁₀₀(Looks-seconds) and initial potential V₀Measure (-volt) and E₁₀₀And V₀I examined the changes.
[0091]
[Table 5]

[0092]
From Table 5, it was found that the diamine compound according to the present invention has better sensitivity repeatability than the conventional compounds.
[0093]
(Example 5)
As the charge transfer material 3 contained in the charge transfer layer 6 shown in FIG. A photosensitive layer 4 having a laminated structure containing the diamine compound shown in FIG. 8 was formed to produce an electrophotographic photosensitive member.
[0094]
An aluminum vapor-deposited polyester film is used as the conductive support 1, and 2.1 g of titanium oxide and 3.9 g of copolymerized nylon (CM8000, manufactured by Toray Industries, Inc.), 32.9 g of methyl alcohol, and 61. A solution dissolved in 1 g of a mixed solvent was applied and dried to form an intermediate layer 8 having a thickness of 1 μm. On this intermediate layer 8, 0.4 g of an X-type metal-free phthalocyanine represented by the following structural formula (VIII) (Fastgen Blue 8120: manufactured by Dainippon Ink Co., Ltd.) was added to a vinyl chloride: vinyl acetate copolymer resin (ESREX M (Manufactured by Sekisui Chemical Co., Ltd.) In 30 ml of ethyl acetate solution in which 0.3 g was dissolved, it was dispersed in a paint conditioner for about 20 minutes. The dispersion was applied by a doctor blade method, and the charge generation layer 5 was formed so that the film thickness after drying was 0.4 μm.
[0095]
Embedded image

[0096]
On the formed charge generation layer 5, Exemplified Compound No. 1 which is a diamine compound according to the present invention is used. 8, a charge transfer layer 6 which is a polyarylate layer containing 50% by weight was laminated to prepare a photoreceptor composed of three layers of an intermediate layer 8, a charge generation layer 5 and a charge transfer layer 6.
[0097]
The energy required to reduce the potential by half using the light of 780 nm of the produced photoreceptor (E₅₀) And initial potential (−V₀)₀= -720 (volt) and E₅₀= 0.20 (μJ), the photoconductor was very sensitive and highly chargeable.
[0098]
In addition, the laser printer (WD-580P: manufactured by Sharp) was remodeled, the photoconductor produced on the drum part was attached, and after continuous non-copying (Non Copy Aging) 10,000 times, the initial potential and sensitivity were reduced. The degree was also examined. As a result, V₀= -710 (volt) and E₅₀= 0.21 (μJ), almost no change was observed compared to the first time.
[0099]
(Examples 6 to 9)
As the charge transfer material 3 shown in FIG. 3, No. 9, no. 19 and no. Four types of electrophotographic photoreceptors of Examples 6 to 9 were produced by forming a single photosensitive layer 4 containing each of the diamine compounds shown in No. 23.
[0100]
Exemplified compound No. 1 of the diamine compound according to the present invention is formed on the conductive support 1 whose surface is anodized (alumite layer: 7 μm). 3, No. 9, no. 19 or No. 1 g of 23, 1.1 g of a polycarbonate resin represented by the following structural formula (IX), 0.15 g of N, N-3,5-xylyl-3,4,9,10-perylenetetracarboxylimide and 0. A solution of 05 g in methylene chloride was prepared. At this time, the imide compound was partially dispersed. The prepared solution was applied by an applicator to obtain a single layer type photoreceptor having a dry film thickness of 20 μm.
[0101]
Embedded image

[0102]
The electrophotographic characteristics of the obtained photoreceptor were evaluated by an electrostatic recording paper testing apparatus. Measurement conditions were applied voltage: 5.5 kV and static: No. 3. Exposure amount E required to attenuate from + 700V to + 100V by white light irradiation₁₀₀(Looks · second) was measured, and the value is shown in Table 6. In addition, 10,000 blank copy tests were performed and sensitivity (E₁₀₀Table 6 also shows the degree of decrease in).
[0103]
[Table 6]

[0104]
From Table 6, it was found that the photoconductor using the diamine compound according to the present invention has excellent sensitivity and repeatability even in positive charging.
[0105]
【The invention's effect】
As described above, according to the present invention, an unprecedented novel diamine compound can be provided. Since the diamine compound has a wide conjugated system, it can be used as a charge transfer material for an electrophotographic photoreceptor. For example, the charge mobility can be increased to improve the residual potential characteristics of the electrophotographic photosensitive member.
[0106]
In addition, according to the present invention, by containing the diamine compound, an organic electrophotographic photosensitive member having high sensitivity and high durability, which is nontoxic and resource-free as compared with an inorganic one, It has the advantages of an organic photoreceptor that is transparent, lightweight, excellent in film formability, has both positive and negative chargeability, and is easy to manufacture, and has almost no decrease in photosensitivity even after repeated use. It is possible to provide an electrophotographic photosensitive member having an excellent characteristic that it does not occur.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view schematically showing an example of an electrophotographic photoreceptor having a function-separated photosensitive layer having a charge transfer layer on a charge generation layer.
FIG. 2 is a function separation type photosensitive layer having a charge generation layer on a charge transfer layer.
FIG. 3 is a cross-sectional view schematically showing an example of an electrophotographic photosensitive member having a dispersion type photosensitive layer.
4 is a cross-sectional view showing an example having a surface protective layer 7 in the electrophotographic photosensitive member of FIG. 3. FIG.
5 is a cross-sectional view showing an example having an intermediate layer 8 in the electrophotographic photosensitive member of FIG.
6 is a cross-sectional view showing an example having an intermediate layer 8 in the electrophotographic photosensitive member of FIG. 3. FIG.
[Explanation of symbols]
1 Conductive support
2 Charge generation materials
3 Charge transfer materials
4,14 Photosensitive layer
5 Charge generation layer
6 Charge transfer layer
7 Surface protective layer
8 Middle class

Claims (11)

A diamine compound represented by the following general formula (I):

(Wherein, Ar ¹ is an arylene group containing also good KuKatsu 1-3 benzene rings contain a substituent group, also be divalent include optionally substituted heterocyclic group, which may the number of carbon atoms 1 to include a substituent 5 represents an alkylene group, and Ar ² represents an aryl group that may contain a substituent, a heterocyclic group that may contain a substituent, an aralkyl group that may contain a substituent, or a C 1-5 that may contain a substituent. An alkyl group, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, and a perfluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, R ¹ represents ¹ carbon atom which may contain a substituent. 1 to 3 alkyl groups, a C 1-5 fluoroalkyl group that may contain a substituent, a C 1-5 perfluoroalkyl group that may contain a substituent, an alkoxy group having 1 to 3 carbon atoms, a carbon number 1 to 3 dialkylamino groups or A represents a hydrogen atom, a represents an alkyl group having 1 to 3 carbon atoms which may contain a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, and 1 to 5 carbon atoms which may contain a substituent; A perfluoroalkyl group, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and n represents an integer of 1 to 4, provided that when n is 2 or more, each of a may be the same or different, and may form a ring with each other, X represents an oxygen atom, a sulfur atom or N—R ² , and R ² may have a substituent, and may have a substituent. Group, a C1-C5 fluoroalkyl group which may contain a substituent, and a C1-C5 perfluoroalkyl group which may contain a substituent.) The photosensitive layer provided on the conductive support contains a diamine compound having a benzofuran, benzothiophene or indole ring represented by the following general formula (I) as a charge transfer material. .

(Wherein, Ar ¹ is an arylene group containing also good KuKatsu 1-3 benzene rings contain a substituent group, also be divalent include optionally substituted heterocyclic group, which may the number of carbon atoms 1 to include a substituent 5 represents an alkylene group, and Ar ² represents an aryl group that may contain a substituent, a heterocyclic group that may contain a substituent, an aralkyl group that may contain a substituent, or a C 1-5 that may contain a substituent. An alkyl group, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, and a perfluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, R ¹ represents ¹ carbon atom which may contain a substituent. 1 to 3 alkyl groups, a C 1-5 fluoroalkyl group that may contain a substituent, a C 1-5 perfluoroalkyl group that may contain a substituent, an alkoxy group having 1 to 3 carbon atoms, a carbon number 1 to 3 dialkylamino groups or A represents a hydrogen atom, a represents an alkyl group having 1 to 3 carbon atoms which may contain a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, and 1 to 5 carbon atoms which may contain a substituent; A perfluoroalkyl group, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and n represents an integer of 1 to 4, provided that when n is 2 or more, each of a may be the same or different, and may form a ring with each other, X represents an oxygen atom, a sulfur atom or N—R ² , and R ² may have a substituent, and may have a substituent. Group, a C1-C5 fluoroalkyl group which may contain a substituent, and a C1-C5 perfluoroalkyl group which may contain a substituent.) The electrophotographic photosensitive member according to claim 2, wherein the diamine compound is represented by the following general formula (II).

(In the formula, Ar ¹ , R ¹ , X, a and n have the same meanings as those shown in the general formula (I).) The electrophotographic photosensitive member according to claim 2, wherein the diamine compound is represented by the following general formula (III).

(In the formula, b is an alkyl group having 1 to 3 carbon atoms which may contain a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, and 1 to 5 carbon atoms which may contain a substituent. A perfluoroalkyl group, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and m represents an integer of 1 to 4, provided that m is 2 or more. , B may be the same or different and may form a ring with each other, l represents an integer of 1 to 5. R ¹ , a, X, and n are the same as those shown in the general formula (I). Synonymous.) The electrophotographic photosensitive member according to claim 2, wherein the diamine compound is represented by the following general formula (IV).

(In the formula, R ¹ , X, a, b, m and n have the same meanings as those shown in formula (III).) The electrophotographic photosensitive member according to claim 2, wherein the diamine compound is represented by the following general formula (V).

(Wherein c and d are each an alkyl group having 1 to 3 carbon atoms which may contain a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, or a carbon number which may contain a substituent) A 1-5 perfluoroalkyl group, a C1-C3 alkoxy group, a C1-C3 dialkylamino group, a halogen atom or a hydrogen atom is shown, and k and j each represent an integer of 1-4. When k and j are 2 or more, the corresponding c and d may be the same or different and may form a ring with each other, and R ¹ , X, a and n are as shown in the general formula (I) Is synonymous with.) The electrophotographic photosensitive member according to claim 2 , wherein the diamine compound is represented by the following general formula (VI).

(In the formula, R ¹ , X, a, c, d, j, k and n have the same meanings as those shown in the general formula (V).)   8. The photosensitive layer according to claim 2, wherein the photosensitive layer has a stacked structure of a charge generation layer containing a charge generation material and a charge transfer layer containing the charge transfer material. Electrophotographic photoreceptor.   8. The electrophotographic photosensitive member according to claim 2, wherein the photosensitive layer comprises a single layer containing a charge generating substance and the charge transfer substance.   8. The electrophotographic photosensitive member according to claim 2, wherein an intermediate layer is provided between the conductive support and the photosensitive layer.   The charge transfer layer is laminated on the charge generation layer, the charge transfer layer serving as a binder polymer, a polymer of a vinyl compound and a copolymer thereof, a polyester resin, a polycarbonate resin, a polyarylate resin, a polysulfone resin, a polyvinyl butyral resin. 9. The electrophotographic photoreceptor according to claim 8, comprising at least one selected from the group consisting of phenoxy resin, cellulose resin, urethane resin, and epoxy resin.

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