JP3601627B2 - Electrophotographic photoreceptor - Google Patents

Description

【００１４】
（式中、Ａｒ_１、Ａｒ_２及びＡｒ_３は、 各々独立的に置換基を有していても良い芳香環基又は置換を有していても良い複素環基を表わし、又は−ＮＡｒ_２（Ａｒ_３）は環を形成していても良い。）
で表される化合物の少なくとも一種以上の化合物を含有することを特徴とする電子写真感光体を提供する。
【００１５】
本発明で使用するフタロシアニン反応生成物の製造方法は、特に限定されるものではないが、例えば、（１）オキシチタニウムフタロシアニン化合物と光学活性な（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール及び／又は（２Ｓ，３Ｓ）−（＋）−２，３−ブタンジオールとの反応による製造方法、（２）ジクロロチタニウムフタロシアニン等のジハロチタニウムフタロシアニン化合物と光学活性な（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール及び／又は（２Ｓ，３Ｓ）−（＋）−２，３−ブタンジオールとの反応による製造方法、（３）光学活性な（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール及び／又は（２Ｓ，３Ｓ）−（＋）−２，３−ブタンジオール存在下での四塩化チタン等のチタニウム塩とオルトフタロニトリル誘導体とのカップリング反応による製造方法、等が挙げられ、本発明では、いずれの製造方法によって得られた反応生成物をも用いることができる。
【００１６】
これらの製造方法のうち、オキシチタニウムフタロシアニン化合物と光学活性な（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール及び／又は（２Ｓ，３Ｓ）−（＋）−２，３−ブタンジオールとの反応は、操作が簡便であるので、好適である。
【００１７】
本発明で使用するフタロシアニン反応生成物は、上記製造方法により得られるものであるが、その構造は式（ＩＸ）
【００１８】
【化１０】

【００１９】
又は式（Ｘ）
【００２０】
【化１１】

【００２１】
で表わされる特定異性体構造のフタロシアニン反応生成物を含む結晶状態にあることが推定される。
【００２２】
本発明で使用するフタロシアニン反応生成物は、結晶状態にあることが好ましく、特にＣｕ−Ｋαに対するＸ線回折スペクトルにおいては、ブラッグ角（２θ±０．２゜）の９．５゜に主たるピークを有する結晶状態にあること、又は、８．３゜、２４．７゜、２５．１゜にピークを有する結晶状態にあることがより好ましい。
【００２３】
本発明の電子写真感光体においては、本発明で使用するフタロシアニン反応生成物の上記結晶状態を含有する電荷発生材料を用いて成る感光層を有するが、感光層のＣｕ−Ｋαに対するＸ線回折スペクトルにおいては、ブラッグ角（２θ±０．２゜）の９．５゜に主たるピークを有する感光層、８．３゜、２４．７゜、２５．１゜にピークを有する感光層、８．３゜に主たるピークを有する感光層が好ましく、特にブラッグ角（２θ±０．２゜）の８．３゜に主たるピークを有する感光層がより好ましい。
【００２４】
本発明で使用するフタロシアニン反応生成物を得るためのオキシチタニウムフタロシアニン化合物と光学活性な（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール及び／又は（２Ｓ，３Ｓ）−（＋）−２，３−ブタンジオールとの反応は、加熱条件で行うことが好ましく、反応温度は、３０〜３００℃の範囲が好ましく、５０〜２５０℃の範囲が特に好ましい。
【００２５】
本発明で使用するフタロシアニン反応生成物の合成原料となるオキシチタニウムフタロシアニン化合物は、本発明の効果を損なわない限りにおいて、置換基を有していても良いフタロシアニン骨格の中心にオキシチタニウムを有するものであれば良く、また本発明の効果を損なわない限りにおいて、α型、β型、α、β混合型、γ型、Ｙ型、非晶質型等の結晶型であっても良い。フタロシアニン骨格が置換基を有する場合、その置換基としては、メチル基、エチル基等の低級アルキル基、メトキシ基等のアルコキシ基；フッ素原子、塩素原子、臭素原子等のハロゲン原子、ニトロ基等が挙げられる。これらの置換基の数は１から１６が可能であり、２つ以上の置換基の組み合わせも可能である。
【００２６】
また、オキシチタニウムフタロシアニン化合物と光学活性な（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール及び／又は（２Ｓ，３Ｓ）−（＋）−２，３−ブタンジオールとの反応のモル比は、オキシチタニウムフタロシアニン化合物１モル当たり光学活性な（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール及び／又は（２Ｓ，３Ｓ）−（＋）−２，３−ブタンジオールが０．２５モル以上が好ましく、０．５〜１．５モルの範囲がより好ましい。
【００２７】
本発明で使用するフタロシアニン反応生成物の合成原料となる（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール及び／又は（２Ｓ，３Ｓ）−（＋）−２，３−ブタンジオールは、光学活性であり、（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール又は（２Ｓ，３Ｓ）−（＋）−２，３−ブタンジオールの一方のみの使用、あるいは両者の含有量の異なる光学活性なトレオ型２，３−ブタンジオールを使用することが好ましい。
【００２８】
本発明の電子写真感光体の電荷発生材料は、本発明で使用するフタロシアニン反応生成物の一つの光学異性体を単独で用いても良いし、それらの二種以上を混合して用いても良い。即ち、オキシチタニウムフタロシアニン化合物と（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオールとの反応生成物とオキシチタニウムフタロシアニン化合物と、（２Ｓ，３Ｓ）−（＋）−２，３−ブタンジオールとの反応生成物とを混合して用いても良い。
【００２９】
オキシチタニウムフタロシアニン化合物と（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール及び／又は（２Ｓ，３Ｓ）−（＋）−２，３−ブタンジオールとの反応等に際しては、必要に応じて公知慣用の各種の有機溶剤を併用することができる。そのような有機溶剤としては、例えば、ベンゼン、ニトロベンゼン、ジクロロベンゼン、トリクロロベンゼン、α−クロロナフタレン等の芳香族系有機溶剤；シクロヘキサノン、メチルエチルケトン、メチルイソブチルケトン等のケトン系有機溶剤；テトラヒドロフラン、ジメチルセロソルブ等のエーテル系有機溶剤；ブタン酸エチル、乳酸ブチル等のエステル系有機溶剤；ジメチルホルムアミド、ジメチルスルホキシド等の非プロトン系極性有機溶剤；トリクロロエタン等のハロゲン系有機溶剤；アミルアルコール、ドデカノール等の一価アルコール系有機溶剤等を挙げることができる。これらの溶剤は、単独でも二種以上の併用しても使用できる。
【００３０】
本発明で使用するフタロシアニン反応生成物を合成した後、必要に応じて昇華精製等の精製を行ってもよい。
【００３１】
上記のように、本発明で使用するフタロシアニン反応生成物の合成に際し、反応モル比、反応温度、反応時間、溶媒、触媒、精製方法、結晶化方法等の各製造条件は、適宜選択して採用することができる。
【００３２】
本発明の電子写真感光体において使用する電荷発生材料は、本発明で使用するフタロシアニン反応生成物を必須成分として含有するが、その特徴を損なわない限りにおいて、その他の電荷発生材料をそれに併用することも可能である。
【００３３】
併用可能な他の電荷発生材料としては、例えば、無金属フタロシアニン化合物、金属フタロシアニン化合物、或いは例えばα型、β型、α、β混合型、γ型、Ｙ型、等の結晶型あるいは非晶質型オキシチタニウムフタロシアニン化合物、アゾ系顔料、アントラキノン系顔料、ペリレン系顔料、多環キノン系顔料、スクエアリウム系顔料等を挙げることができるが、これらの例に限定されるものではない。
【００３４】
本発明の電子写真感光体に使用する電荷輸送材料は、前記一般式（Ｉ）で表わされる化合物を主成分として含有するが、一般式（Ｉ）で表わされる化合物の中でも、一般式（ＩＩ）
【００３５】
【化１２】

【００３６】
（式中、 Ａｒ_４は置換基を有していても良い芳香環基、置換を有していても良い複素環基を表わす。互いに異なる２つのベンゼン環はＹを介して環を形成していても良い。環を形成する場合、Ｙは互いに異なるベンゼン環と結合して環を形成するのに必要な残基を表わす。Ｒ_１及びＲ_２は、各々独立的に、水素原子、ハロゲン原子、アルコキシ基、置換基を有していても良いアルキル基又は置換基を有していても良いフェニル基を表わす。）
で表わされる化合物、一般式（ＩＩＩ）
【００３７】
【化１３】

【００３８】
（式中、Ａｒ_５及びＡｒ_６は置換基を有していても良い芳香環基、置換基を有していても良い複素環基を表わし、互いに異なる２つのベンゼン環はＷを介して環を形成していても良い。環を形成する場合、Ｗは互いに異なるベンゼン環と結合して環を形成するのに必要な残基を表わす。Ｒ_３、Ｒ_４、Ｒ_５及びＲ_６は、各々独立的に、水素原子、ハロゲン原子、アルコキシ基、置換基を有していても良いアルキル基又は置換を有していても良いフェニル基を表わす。）
で表わされる化合物及び一般式（ＩＶ）
【００３９】
【化１４】

【００４０】
（式中、ｍは０又は１を表わし、 Ａｒ_７、Ａｒ_８、Ａｒ_９及びＡｒ_１０は、各々独立的に、置換基を有していても良い芳香環基、置換を有していても良い複素環基を表わし、Ｚは、酸素原子、硫黄原子、置換基を有していても良いアミニレン基、置換基を有していても良い２価の芳香族残基又は置換基を有していても良い２価の複素環残基を表わし、互いに異なる２つのベンゼン環はＷを介して環を形成していても良い。環を形成する場合、Ｗは互いに異なるベンゼン環と結合して環を形成するのに必要な残基を表わす。 Ｒ_７、Ｒ_８、Ｒ_９及びＲ_１０は、各々独立的に、水素原子、ハロゲン原子、アルコキシ基、置換基を有していても良いアルキル基又は置換基を有していても良いフェニル基を表わす。）
で表わされる化合物から成る群から選ばれる少なくとも一種の化合物を含有するものがより好ましい。
【００４１】
次に、本発明の電子写真感光体に使用する電荷輸送材料の代表的な化合物の構造を下記に構造式で示すが、本発明は必ずしもこれらの例に限定されるものではない。なお、構造式の下に記載した数字は例示化合物の番号を表わす。
【００４２】
【化１５】

【００４３】
【化１６】

【００４４】
【化１７】

【００４５】
【化１８】

【００４６】
【化１９】

【００４７】
【化２０】

【００４８】
【化２１】

【００４９】
【化２２】

【００５０】
【化２３】

【００５１】
【化２４】

【００５２】
【化２５】

【００５３】
【化２６】

【００５４】
【化２７】

【００５５】
【化２８】

【００５６】
【化２９】

【００５７】
【化３０】

【００５８】
【化３１】

【００５９】
【化３２】

【００６０】
【化３３】

【００６１】
【化３４】

【００６２】
【化３５】

【００６３】
【化３６】

【００６４】
【化３７】

【００６５】
【化３８】

【００６６】
【化３９】

【００６７】
本発明の電子写真感光体の電荷輸送材料は、前記一般式（Ｉ）或いは一般式（ＩＩ）〜（ＩＶ）で表わされる化合物の少なくとも一種以上の化合物を含有するが、その特徴を損なわない限りにおいて、一般式（Ｉ）及び一般式（ＩＩ）〜（ＩＶ）で表わされる化合物以外の他の電荷輸送材料を併用することも可能である。
【００６８】
併用可能な他の電荷輸送材料としては、例えば、スチルベン系、ヒドラゾン系、ピラゾリン系、オキサゾール系、オキサジアゾール系、チアゾール系、カルバゾール系、ジフェノキノン系、アリールメタン系化合物、或いは、ポリ−Ｎ−ビニルカルバゾール、ポリシラン等の重合性化合物を挙げることができる。
【００６９】
これらの電荷輸送材料を併用して用いる場合は、全電荷輸送材料中の前記一般式（Ｉ）及び一般式（ＩＩ）〜（ＩＶ）で表わされる化合物の含有量は、重量比で２０％以上が好ましく、５０％以上であることが特に好ましい。
【００７０】
本発明の電子写真感光体の構成は、種々の構造を採ることができる。その例を図１から図３に示した。
【００７１】
図１及び図２の電子写真感光体は、導電性支持体１の上に電荷発生材料を主体とする電荷発生層２と、電荷輸送材料と結着樹脂からなる電荷輸送層３とから成る感光層４ａ又は４ｂをそれぞれ設けたものである。図３の電子写真感光体は導電性支持体１の上に電荷発生材料５を電荷移動媒体６の中に分散せしめた感光層４ｃを設けたものである。
【００７２】
図１及び図２の電子写真感光体の場合には、電荷発生層２に含まれる電荷発生材料が電荷を発生し、一方、電荷輸送層３は電荷の注入を受け、その輸送を行なう。即ち、光減衰に必要な電荷の生成が電荷発生材料で行なわれ、また、電荷の輸送が電荷輸送媒体で行なわれる。図３の電子写真感光体では電荷発生材料が光に対して電荷を発生し、電荷移動媒体により電荷の移動が行なわれる。
【００７３】
図１の電子写真感光体は、電荷発生材料の蒸着膜から成る電荷発生層上に、あるいは電荷発生材料の微粒子を必要に応じて結着樹脂を溶解した溶媒中に分散して得た分散液を塗布した後、乾燥させることによって得られる電荷発生層上に、電荷輸送材料を単独、あるいは必要に応じて結着樹脂を併用し溶解した溶液を塗布した後、乾燥させることによって得られる電荷輸送層を設けることによって製造することができる。
【００７４】
図２の電子写真感光体は、単独、あるいは必要に応じて結着樹脂を併用し溶解した溶液を導電性支持体上に塗布した後、乾燥させることによって得られる電荷輸送層上に、電荷発生材料の蒸着膜から成る電荷発生層、あるいは電荷発生材料の微粒子を溶剤又は結着樹脂溶液中に分散して得た分散液を塗布した後、乾燥させることによって得られる電荷発生層を設けることによって製造することができる。
【００７５】
図３の電子写真感光体は、電荷輸送材料を結着樹脂に溶解した溶液に電荷発生材料の微粒子を分散させて、これを導電性支持体上に塗布した後、乾燥させることによって製造することができる。
【００７６】
図１及び図２の電子写真感光体の場合、電荷発生層の厚さは５μｍ以下が好ましく、０．０１〜２μｍの範囲が特に好ましい。電荷輸送層の厚さは３〜５０μｍの範囲が好ましく、５〜３０μｍの範囲が特に好ましい。図３の電子写真感光体の場合、感光層の厚さは、３〜５０μｍの範囲が好ましく、５〜３０μｍの範囲が特に好ましい。
【００７７】
図１及び図２の電子写真感光体における電荷輸送層中の電荷輸送材料の割合は、５〜８０重量％の範囲が好ましく、３０〜７０重量％の範囲が特に好ましい。図１及び図２の電子写真感光体の電荷輸送層における結着樹脂の割合は、２０〜９５重量％の範囲が好ましく、３０〜７０重量％の範囲が特に好ましい。図１及び図２の電子写真感光体の電荷発生層中の電荷発生材料の割合は、５〜１００重量％の範囲が好ましく、４０〜８０重量％の範囲が特に好ましい。図３の電子写真感光体における感光層中の電荷輸送材料の割合は、５〜８０重量％の範囲が好ましく、結着樹脂は２０〜９４重量％の範囲が好ましく、また電荷発生材料の割合は、１〜５０重量％の範囲が好ましく、３〜２０重量％の範囲が特に好ましい。なお、図１〜図３のいずれの電子写真感光体の作製においても、結着樹脂と共に可塑剤、増感剤を用いることができる。
【００７８】
本発明の電子写真感光体に用いられる導電性基体としては、例えば、アルミニウム、銅、亜鉛、ステンレス、クロム、チタン、ニッケル、モリブデン、バナジウム、インジウム、金、白金等の金属又は合金、あるいは、導電性ポリマー、酸化インジウム等の導電性化合物；アルミニウム、パラジウム、金等の金属又は合金を塗布、蒸着、あるいはラミネートした紙、プラスチックフィルム、セラミックス等が挙げられ、必要に応じて導電性支持体表面は化学的又は物理的な処理を施してもよい。
【００７９】
本発明の電子写真感光体の形状は、用いる導電性基体によって異なるが、ドラム状、平板状、シート状、ベルト状等多種の形状が可能である。
【００８０】
本発明の電子写真感光体における電荷輸送材料を溶解してなる結着樹脂としては、疎水性で、電気絶縁性のフィルム形成可能な高分子重合体を用いるのが好ましい。このような高分子重合体としては、例えば、ポリカーボネート、ポリアリレート、ポリエステル、メタクリル樹脂、アクリル樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリスチレン、ポリビニルアセテート、スチレン−ブタジエン共重合体、塩化ビニル−酢酸ビニル−無水マレイン酸共重合体、シリコン樹脂、シリコン−アルキッド樹脂、フェノール−ホルムアルデヒド樹脂、スチレン−アルキッド樹脂、ポリ−Ｎ−ビニルカルバゾール、ポリビニルブチラール、ポリビニルフォルマール、ポリスルホン等が挙げられる。
【００８１】
これらの結着樹脂のうち、ポリカーボネート及びポリアリレートは、耐久性の高い感光層を形成することから好ましく、特に一般式（Ｖ）
【００８２】
【化４０】

【００８３】
（式中、芳香環上の水素原子はハロゲン原子、置換基を有していても良いアルキル基で置換されてもよく、Ｒ_１１及びＲ_１２は、水素原子、置換基を有していても良いアルキル基又は置換を有していても良い芳香族基を表わす。）
で表わされる繰り返し単位を有するポリカーボネート、一般式（ＶＩ）
【００８４】
【化４１】

【００８５】
（式中、芳香環上の水素原子はハロゲン原子、置換基を有していても良いアルキル基で置換されてもよく、Ｑは置換基を有していても良い炭素環又は置換基を有していても良い複素環を形成するのに必要な原子群を表わす。）
で表わされる繰り返し単位を有するポリカーボネート、上記一般式（Ｖ）で表わされる繰り返し単位と一般式（ＶＩＩ）
【００８６】
【化４２】

【００８７】
（式中、芳香環上の水素原子はハロゲン原子、置換基を有していても良いアルキル基で置換されてもよい。）
で表わされる繰り返し単位を有する共重合ポリカーボネート及び一般式（ＶＩＩＩ）
【００８８】
【化４３】

【００８９】
（式中、芳香環上の水素原子はハロゲン原子、置換基を有していても良いアルキル基で置換されてもよい。）
で表わされる繰り返し単位を有するポリアリレートは、本発明の電荷輸送材料を溶解する樹脂として、電気的安定性が高く、より好ましい。
【００９０】
これらの結着樹脂は、単独で、或いは、２種類以上の混合物として用いることもできる。
【００９１】
電荷発生材料の分散に必要に応じて使用することのできる結着樹脂は、疎水性で、電気絶縁性のフィルム形成可能な高分子化合物を用いるのが好ましく、前述の電荷輸送材料を溶解してなる結着樹脂と同様のものが好ましい。
【００９２】
また、電子写真感光体の成膜性、可撓性、機械的強度を向上するために、これらの結着樹脂と共に、周知の可塑剤、表面改質剤等の添加剤を使用することもできる。
【００９３】
可塑剤としては、例えば、ビフェニル、塩化ビフェニル、ｏ−ターフェニル、ｐ−ターフェニル、ジブチルフタレート、ジエチルグリコールフタレート、ジオクチルフタレート、トリフェニル燐酸、メチルナフタレン、ベンゾフェノン、塩素化パラフィン、ポリプロピレン、ポリスチレン、各種のフルオロ炭化水素等が挙げられる。
【００９４】
表面改質剤としては、例えば、シリコンオイル、フッソ樹脂等が挙げられる。
【００９５】
前記感光層に必要に応じて用いられる増感剤としては、いずれも周知のものが使用できる。
【００９６】
増感剤としては、例えば、クロラニル、テトラシアノエチレン、メチルバイオレット、ローダミンＢ、シアニン染料、メロシアニン染料、ピリリウム染料、チアピリリウム染料等が挙げられる。
【００９７】
また、本発明の電子写真感光体においては、保存性、耐久性、耐環境依存性を向上させるために、感光層中に酸化防止剤や光安定剤等の劣化防止剤を含有させることもできる。その例としては、フェノール化合物、ハイドロキノン化合物、アミン化合物等を挙げることができる。
【００９８】
更に、本発明においては、導電性支持体と感光層との接着性を向上させたり、導電性支持体から感光層への自由電荷の注入を阻止するため、導電性支持体と感光層との間に、必要に応じて接着層あるいはバリアー層を設けることもできる。
【００９９】
これらの層に用いられる材料としては、前記結着樹脂に用いられる高分子化合物のほか、カゼイン、ゼラチン、エチルセルロース、ニトロセルロース、カルボキシ−メチルセルロース、塩化ビニリデン系ポリマーラテックス、スチレン−ブタジエン系ポリマーラテックス、ポリビニルアルコール、ポリアミド、ポリウレタン、フェノール樹脂、酸化アルミニウム、酸化スズ、酸化チタン等が挙げられ、その膜厚は１μｍ以下が望ましい。
【０１００】
積層型電子写真感光体を塗工によって形成する場合、結着樹脂を溶解する溶剤は、結着樹脂の種類によって異なるが、下層を溶解しないものの中から選択することが望ましい。具体的な有機溶剤の例としては、例えば、メタノール、エタノール、ｎ−プロパノール等のアルコール類；アセトン、メチルエチルケトン、シクロヘキサノン等のケトン類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド類；テトラヒドロフラン、ジオキサン、メチルセロソルブ等のエーテル類；酢酸メチル、酢酸エチル等のエステル類；ジメチルスルホキシド、スルホラン等のスルホキシド及びスルホン類；ジクロロメタン、クロロホルム、四塩化炭素、トリクロロエタン等の脂肪族ハロゲン化炭化水素；ベンゼン、トルエン、キシレン、モノクロルベンゼン、ジクロルベンゼン等の芳香族類等が挙げられる。
【０１０１】
塗工法としては、例えば、浸漬コーティング法、スプレーコーティング法、スピンナーコーティング法、ビードコーティング法、ワイヤーバーコーティング法、ブレードコーティング法、ローラーコーティング法、カーテンコーティング法等のコーティング法を用いることができる。
【０１０２】
本発明の特定の電荷発生材料と特定の電荷輸送材料とを含有する感光層を設けて成る電子写真感光体は以上のような構成であって、以下の実施例からも明かなように、高感度であり、繰り返し使用時の電子写真特性の安定性と帯電性、環境安定性に優れたものである。
【０１０３】
【実施例】
以下、実施例を用いて本発明を更に詳細に説明するが、本発明はこれらの実施例の範囲に限定されるものではない。なお、以下の実施例において「部」はすべて「重量部」を表わす。
【０１０４】
（合成例１）
四塩化チタニウムとｏ−フタロニトリルより得られたオキシチタニウムフタロシアニン化合物であって、図４に示したＣｕＫα線による粉末Ｘ線回折スペクトルを示すオキシチタニウムフタロシアニン化合物２０部と、（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール４．４部とを、α−クロロナフタレン２４０部中で１９５〜２０５℃で攪絆しながら１．５時間反応させた。
【０１０５】
反応混合物を室温にまで冷却した後、濾別し、ベンゼン、メタノール、ジメチルホルムアミド（以下、ＤＭＦと省略する。）、水の順に洗浄した後、減圧乾燥させることにより、フタロシアニン反応生成物を得た。
【０１０６】
この反応生成物は、マススペクトルにおいてｍ／Ｚ＝６４８にピークを示した。この反応生成物のＣｕＫα線による粉末Ｘ線回折スペクトルを測定した結果を図５に示した。更に、この反応生成物の元素分析の結果を表１に示した。
【０１０７】
【表１】

【０１０８】
（実施例１）
合成例１で得たフタロシアニン反応生成物２部及びブチラール樹脂（積水化学工業社製の「エスレックＢＨ−３」）２部を、塩化メチレン６６部及び１，１，２−トリクロロエタン９９部から成る混合溶媒に添加し、ペイントコンディショナーで分散、混合して電荷発生材料の分散液を得た。
【０１０９】
このようにして得た電荷発生材料の分散液を金属薄板に浸漬塗布を行って得た膜厚５μｍの薄膜のＸ線回折スペクトルを図６に示した。
【０１１０】
次に、このようにして得た電荷発生材料の分散液を、アルミニウムを蒸着したポリエステルフィルム上にワイヤーバーを用いて乾燥後の膜厚が０．３μｍと成るように塗布した後、乾燥させて電荷発生層を形成した。
【０１１１】
この電荷発生層の上に、前記した例示化合物Ｎｏ． ８６の電荷輸送材料８部と構造式（ＸＩ）
【０１１２】
【化４４】

【０１１３】
の繰り返し単位を有するポリカーボネート（三菱瓦斯化学社製の「ユーピロンＺ２００」）１０部を、塩化メチレン５４部及びクロロベンゼン３６部から成る混合溶媒に溶解させた塗布液を、ワイヤーバーを用いて乾燥後の膜厚が２０μｍとなるように塗布した後、乾燥させて電荷輸送層を形成して、図１に示した層構成を有する電子写真感光体を得た。
【０１１４】
（合成例２）
合成例１において、（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオールに代えて（２Ｓ，３Ｓ）−（＋）−２，３−ブタンジオールを用いた以外は、合成例１と同様にしてフタロシアニン反応生成物を得た。
【０１１５】
この反応生成物は、マススペクトルにおいてｍ／Ｚ＝６４８にピークを示した。この反応生成物のＣｕＫα線による粉末Ｘ線回折スペクトルを測定した結果を図７に示した。
【０１１６】
（実施例２）
実施例１において、合成例１で得たフタロシアニン反応生成物に代えて、合成例２で得たフタロシアニン反応生成物を用いた以外は、実施例１と同様にして電子写真感光体を得た。
【０１１７】
（実施例３）
実施例１において、合成例１で得たフタロシアニン反応生成物２部に代えて、合成例１で得たフタロシアニン反応生成物１部及び合成例２で得たフタロシアニン反応生成物１部を用いた以外は、実施例１と同様にして、電子写真感光体を得た。
【０１１８】
（合成例３）
合成例１において、（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール４．４部に代えて、（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール２．２部を用いた以外は、合成例１と同様にしてフタロシアニンの反応生成物を得た。
【０１１９】
この反応生成物は、マススペクトルにおいてｍ／Ｚ＝５７６及び６４８にピークを示した。この反応生成物のＣｕＫα線による粉末Ｘ線回折スペクトルを測定した結果を図８に示した。
【０１２０】
（実施例４）
実施例１において、合成例１で得たフタロシアニン反応生成物に代えて、合成例３で得たフタロシアニン反応生成物を用いた以外は、実施例１と同様にして電子写真感光体を得た。
【０１２１】
また、実施例４で使用した電荷発生材料の分散液を金属薄板に乾燥後の膜厚が５μｍと成るように浸漬塗布した後、乾燥させて得た薄膜のＸ線回折スペクトルを図９に示した。
【０１２２】
（合成例４）
チタニウムテトライソプロポキシド及び１，３−ジイミノイソインドリンから得られたオキシチタニウムフタロシアニンを濃硫酸でアシッドペースト処理を行って得られるオキシチタニウムフタロシニン化合物であって、図１０に示したＣｕＫα線による粉末Ｘ線回折スペクトルを示すオキシチタニウムフタロシアニン化合物２０部と、（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール４．７部とを、α−クロロナフタレン２４０部中で１９５〜２０５℃で攪絆しながら１．５時間反応させた。
【０１２３】
反応混合物を室温まで冷却した後、濾別し、ベンゼン、メタノール、ＤＭＦ、水の順に洗浄した後、減圧乾燥させることにより、フタロシアニン反応生成物を得た。
【０１２４】
この反応生成物は、マススペクトルにおいてｍ／Ｚ＝５７６及び６４８にピークを示した。この反応生成物のＣｕＫα線による粉末Ｘ線回折スペクトルを測定した結果を図１１に示した。
【０１２５】
（実施例５）
実施例１において、合成例１で得たフタロシアニン反応生成物に代えて、合成例４で得たフタロシアニン反応生成物を用いた以外は、実施例１と同様にして電子写真感光体を得た。
【０１２６】
また、実施例５で使用した電荷発生材料の分散液を金属薄板に乾燥後の膜厚が５μｍと成るように浸漬塗布した後、乾燥させて得た薄膜のＸ線回折スペクトルを図１２に示した。
【０１２７】
（実施例６）
実施例１において、構造式（ＸＩ）で表わされる繰り返し単位を有するポリカーボネートに代えて、構造式（ＸＩＩ）
【０１２８】
【化４５】

【０１２９】
で表わされる繰り返し単位と構造式（ＸＩＩＩ）
【０１３０】
【化４６】

【０１３１】
で表わされる繰り返し単位を８６対１４の比率で有する共重合ポリカーボネートを用い、前記した例示化合物Ｎｏ． ８６の電荷輸送材料８部と共に２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．４部を用いた以外は、実施例１と同様にして電子写真感光体を得た。
【０１３２】
（実施例７）
実施例１において、電荷輸送層を、前記した例示化合物Ｎｏ． ８６の電荷輸送材料８部、２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．４部及び構造式（ＸＩＶ）
【０１３３】
【化４７】

【０１３４】
で表わされる繰り返し単位を有するポリカーボネート（帝人化成社製の「パンライトＣ１４００」）１０部を、塩化メチレン８０部及び１，１，２−トリクロロエタン２０部よりなる混合溶媒に溶解させた塗布液を、乾燥後の膜厚が２０μｍとなるように塗布した後、乾燥させて得られる電荷輸送層とした以外は、実施例１と同様にして、電子写真感光体を得た。
【０１３５】
（実施例８）
実施例１において、電荷輸送層を、前記した例示化合物Ｎｏ． ８６の電荷輸送材料８部、２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．４部及び構造式（ＸＶ）
【０１３６】
【化４８】

【０１３７】
で表わされる繰り返し単位を有するポリアリレート（イソノヴァ社製の「ＩＳＡＲＹＬ２５Ｓ」）１０部を、１，４−ジオキサン１００部に溶解させた塗布液を、乾燥後の膜厚が２０μｍと成るように塗布した後、乾燥させて得られる電荷輸送層とした以外は、実施例１と同様にして、電子写真感光体を得た。
【０１３８】
（合成例５）
合成例１において、（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール４．４部に代えて、（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオール３．１部を用いた以外は、合成例１と同様にして、フタロシアニン反応生成物を得た。
【０１３９】
この反応生成物は、マススペクトルにおいてｍ／Ｚ＝５７６及び６４８にピークを示した。この反応生成物のＣｕＫα線による粉末Ｘ線回折スペクトルを測定した結果を図１３に示した。
【０１４０】
（実施例９）
実施例１において、合成例１で得たフタロシアニン反応生成物に代えて、合成例５で得たフタロシアニン反応生成物を用いた以外は、実施例１と同様にして電子写真感光体を得た。
【０１４１】
また、実施例９で使用した電荷発生材料の分散液を金属薄板に乾燥後の膜厚が５μｍと成るように浸漬塗布した後、乾燥させて得た薄膜のＸ線回折スペクトルを図１４に示した。
【０１４２】
（実施例１０）
実施例１において、合成例１で得たフタロシアニン反応生成物に代えて、合成例３で得たフタロシアニン反応生成物２部を使用し、電荷輸送層を、例示化合物Ｎｏ． ８６の電荷輸荷輸送材料８部、２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．４部及び前記構造式（ＸＩＶ）で表わされる繰り返し単位を有するポリカーボネート（帝人化成社製の「パンライトＣ１４００」）１０部を、塩化メチレン４０部及び１，１，２−トリクロロエタン１０部から成る混合溶媒に溶解させた塗布液を、乾燥後の膜厚が２０μｍと成るように塗布した後、乾燥させて得られる電荷輸送層とした以外は、実施例１と同様にして、電子写真感光体を得た。
【０１４３】
（比較合成例１）
合成例１において、（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオールに代えて、メソ−２，３−ブタンジオールを用いた以外は、合成例１と同様にして、フタロシアニン反応生成物を得た。
【０１４４】
この反応生成物は、マススペクトルにおいてｍ／Ｚ＝６４８にピークを示した。この反応生成物のＣｕＫα線による粉末Ｘ線回折スペクトルを測定した結果を図１５に示した。
【０１４５】
（比較例１）
実施例１において、合成例１で得たフタロシアニン反応生成物に代えて、比較合成例１で得たフタロシアニン反応生成物を用いた以外は、実施例１と同様にして電子写真感光体を得た。
【０１４６】
また、比較例１で使用した電荷発生材料の分散液を金属薄板に乾燥後の膜厚が５μｍと成るように浸漬塗布した後、乾燥させて得た薄膜のＸ線回折スペクトルを図１６に示した。
【０１４７】
（比較合成例２）
合成例１において、（２Ｒ，３Ｒ）−（−）−２，３−ブタンジオールに代えて、エチレングリコールを用いた以外は、合成例１と同様にして、フタロシアニン反応生成物を得た。
【０１４８】
この反応生成物は、マススペクトルにおいてｍ／Ｚ＝６２０にピークを示した。この反応生成物のＣｕＫα線による粉末Ｘ線回折スペクトルを測定した結果を図１７に示した。
【０１４９】
（比較例２）
実施例１において、合成例１で得たフタロシアニン反応生成物に代えて、比較合成例２で得たフタロシアニン反応生成物を用いた以外は、実施例１と同様にして電子写真感光体を得た。
【０１５０】
また、比較例２で使用した電荷発生材料の分散液を金属薄板に乾燥後の膜厚が５μｍと成るように浸漬塗布した後、乾燥させて得た薄膜のＸ線回折スペクトルを図１８に示した。
【０１５１】
（比較例３）
実施例１において、前記した例示化合物Ｎｏ． ８６の電荷輸送材料に代えて、構造式（ＸＶＩ）
【０１５２】
【化４９】

【０１５３】
で表わされる電荷輸送材料を用いた以外は、実施例１と同様にして電子写真感光体を得た。
【０１５４】
（比較合成例３）
特開昭６１−１０９０５６号公報の製造例１記載の方法に準じて、即ち、フタロジニトリル４．６部をα−クロロナフタレン２５部中に仕込み、１２０℃で溶解させた後、四塩化チタン１．７ｇを滴下し、１５０℃で３０分間攪拌を続けた。その後、反応温度を徐々に昇温し、２２０℃で２時間加熱攪拌を続けた。
【０１５５】
反応終了後、反応混合物を１００℃まで放冷した時点で熱時濾過し、残渣をメタノール熱懸濁、熱水煮沸懸濁、Ｎ−メチルピロリドンにより１２０℃で１時間熱懸濁を行った後、熱時濾過し、メタノールで熱懸濁し、濾過した後、減圧乾燥させることにより青色粉末を得た。
【０１５６】
このようにして得た青色粉末を元素分析した結果、塩素の含有量は０．５１％であり、得られた青色粉末は、オキシチタニウムフタロシアニンに少量の塩化チタニウムフタロシアニンが混合した混合物であった。
【０１５７】
（比較例４）
実施例１において、合成例１で得たフタロシアニン反応生成物に代えて、比較合成例３で得たオキシチタニウムフタロシアニンに少量の塩化チタニウムフタロシアニンが混合した混合物を用いた以外は、実施例１と同様にして電子写真感光体を得た。
【０１５８】
（電子写真特性）
実施例１〜１０及び比較例１〜３で得た各電子写真感光体について、静電複写紙試験装置（川口電機製作所社製の「ＳＰ４２８」）を用いて、電子写真感光体を暗所で−６ＫＶのコロナ放電により帯電し、この時の電子写真感光体の表面電位Ｖ_０ （Ｖ）を測定した。次に、そのまま暗所で１０秒間放置したときの電子写真感光体の表面電位Ｖ_１０（Ｖ）を測定した。Ｖ_０ とＶ_１０より電子写真感光体の表面電位の電位保持率（％）：（Ｖ_１０／Ｖ_０ ）×１００を算出した。更に、表面電位Ｖ_１０に対して波長７８０ｎｍ、露光エネルギー１μＷ／ｃｍ^２ の光で露光を行ない、表面電位がＶ_１０の半分になるまでの時間より半減露光量Ｅ_１／２（μＪ／ｃｍ^２）を求めた。更にまた、露光開始１５秒後の表面電位、すなわち残留電位Ｖ_Ｒ （Ｖ）を測定した。測定結果を表２にまとめて示した。
【０１５９】
また、帯電、暗所放置１秒間、露光１秒間、３００ルクスの白色光による除電０．１秒間のプロセスを５００回繰り返した直後の測定結果も同様に表２及び表３にまとめて示した。
【０１６０】
【表２】

【０１６１】
【表３】

【０１６２】
（実施例１１〜２４）
実施例１０において、例示化合物Ｎｏ． ８６の電荷輸荷輸送材料に代えて、下表４及び表５に示した電荷輸送材料を用いた以外は、実施例１０と同様にして電子写真感光体を得た。
【０１６３】
また、これらの電子写真感光体について、実施例１〜１０で得た電子写真感光体を評価した方法と同様の方法による電子写真特性も表４及び表５にまとめて示した。
【０１６４】
【表４】

【０１６５】
【表５】

【０１６６】
（実施例２５）
メタノール７部及びｎ−ブタノール７部から成る混合溶媒にポリアミド樹脂（東レ社製の「アミランＣＭ−８０００」）１部を溶解した樹脂溶液を得た。この樹脂溶液を、浸漬塗工法により、直径３０ｍｍ、肉厚１ｍｍのアルミニウム製ドラムの外周面に、乾燥後の膜厚が１μｍと成るように塗布した後、乾燥させてバリヤー層を設けた。
【０１６７】
次に、合成例３で得たフタロシアニン反応生成物２部及びブチラール樹脂（積水化学工業社製の「エスレックＢＨ−３」）２部を、塩化メチレン６６部及び１，１，２−トリクロロエタン９９部の混合溶媒に添加し、ペイントコンディショナーで分散、混合して電荷発生材料の分散液を得た。このようにして得た電荷発生材料の分散液を、浸漬塗工法により、上記バリヤー層の上に、乾燥後の膜厚が０．４μｍと成るように塗布した後、乾燥させて電荷発生層を設けた。
【０１６８】
次に、前記した例示化合物Ｎｏ． ８６の電荷輸荷輸送材料８部、２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．５部及び前記構造式（ＸＩ）の繰り返し単位を有するポリカーボネート（三菱瓦斯化学社製の「ユーピロンＺ２００」）１０部を、塩化メチレン５４部及びクロロベンゼン３６部よりなる混合溶媒に溶解させた電荷輸送材層形成用塗料を、上記電荷発生層上に、乾燥後の膜厚が２０μｍとなるように浸漬塗工した後、乾燥させて電荷輸送層を設けることにより、ドラム状電子写真感光体を得た。
【０１６９】
（実施例２６〜２８）
実施例２５において、例示化合物Ｎｏ． ８６の電荷輸送材料８部に代えて、下表６に示した電荷輸送材料１０部を用いた以外は、実施例２１と同様にして電子写真感光体を各々得た。
【０１７０】
（比較例５）
実施例２５において、例示化合物Ｎｏ． ８６の電荷輸荷輸送材料８部に代えて、前記構造式（ＸＶＩ）で表わされる電荷輸送材料１０部を用いた以外は、実施例２５と同様にして電子写真感光体を各々得た。
【０１７１】
（画像特性）
実施例２５〜２８及び比較例５で得たドラム状電子写真用感光体を、市販のレーザープリンタ（ヒューレットパッカード社製の「ＬａｓｅｒＪｅｔ ４」）に装着し、トナーを補給しながら連続印刷を行い、画像状態の評価を行った。
【０１７２】
表６に、初期及び１万枚の印字試験後の評価結果を一覧表にして示した。
【０１７３】
【表６】

【０１７４】
（実施例２９）
実施例２５で得たドラム状電子写真感光体をフォトレセプターアナライジングシステム ＣＹＮＴＨＩＡ３０（ジェンテック株式会社製）を使用し、印加電圧−５．５ＫＶで表面電位Ｖ_０ （Ｖ）にコロナ帯電させた直後に、７８０ｎｍの半導体レーザを用い、１．３ｅｒｇ／ｃｍ^２光照射した後の表面電位Ｖ_Ｌ（Ｖ）、及び帯電後暗所に１０秒間放置した時の表面電位Ｖ_１０を各環境下において求めた。Ｖ_０ とＶ_１０より電子写真感光体の表面電位の電位保持率Ｖ_Ｄ（％）：（Ｖ_１０／Ｖ_０）×１００を算出した。その結果を表７に示した。
【０１７５】
（比較合成例４）
特開平３−３５２４６号公報の合成例１記載の方法に準じて、即ち、フタロジニトリル６５ｇとｏ−クロルナフタレン５００ｍｌの混合物中に窒素気流下で１４．７ｍｌの四塩化チタンを滴下した後、徐々に２００℃まで昇温し、反応温度を２００〜２２０℃の間に保ちながら、３時間攪拌して反応を完結させた。反応終了後、反応混合物を１３０℃まで放冷した後、熱時濾過し、ｏ−クロルナフタレンで洗浄した後、メタノールで数回洗浄し、ジクロロチタニウムフタロシアニンを得た。更に８０℃の熱水で数回洗浄して得た結晶を乾燥させ、その５ｇを９６％硫酸１００ｇ中で３〜５℃に保ちながら攪拌した後、濾過して得られた硫酸溶液を水３．５リットル中に注いだ。析出した結晶を濾取し、洗浄液が中性となるまで水洗を繰り返した後、濾取し、ウェットケーキをジクロルエタンで処理し、メタノールで洗浄した後、乾燥させてチタニルフタロシアニンの結晶を得た。このようにして得たチタニルフタロシアニンは、ブラッグ角２θの９．６°±０．２゜のピークと２７．２°±０．２゜のピーク比が７８％であった。
【０１７６】
（比較例６）
実施例２５において、合成例３で得たフタロシアニン反応生成物２部に代えて、比較合成例４で得たチタニルフタロシアニンを用いた以外は、実施例２５と同様にしてドラム状電子写真感光体を作製し、実施例２９に準じて各環境下における電子写真特性を測定し、その結果を表７に示した。
【０１７７】
【表７】

【０１７８】
表７に示した結果から、実施例２９で得たドラム状電子写真感光体は、比較例６で得たドラム状電子写真感光体と比較して、帯電性及び電位保持率において優れており、各環境下における露光後電位の最大値と最小値の差が小さく、環境の変化に強いことが明らかである。
【０１７９】
【発明の効果】
本発明の電子写真感光体は、７５０ｎｍ付近の長波長光源に高い感度を有し、繰り返し使用時での高い安定性と帯電性、環境の変動における高い安定性を保っており、実用上極めて有用である。
【図面の簡単な説明】
【図１】本発明に係わる電子写真感光体の層構成の一例を示す模式断面図である。
【図２】本発明に係わる電子写真感光体の層構成の一例を示す模式断面図である。
【図３】本発明に係わる電子写真感光体の層構成の一例を示す模式断面図である。
【図４】合成例１で製造原料として使用したオキシチタニウムフタロシアニン化合物のＣｕＫα線による粉末Ｘ線回折スペクトル図である。
【図５】合成例１で得たフタロシアニン反応生成物のＣｕＫα線による粉末Ｘ線回折スペクトル図である。
【図６】実施例１で作製したフタロシアニン反応生成物の樹脂分散液を金属薄板に浸漬塗布して得られた薄膜のＸ線回折スペクトル図である。
【図７】合成例２で得たフタロシアニン反応生成物のＣｕＫα線による粉末Ｘ線回折スペクトル図である。
【図８】合成例３で得たフタロシアニン反応生成物のＣｕＫα線による粉末Ｘ線回折スペクトル図である。
【図９】実施例４で作製したフタロシアニン反応生成物の樹脂分散液を金属薄板に浸漬塗布して得られた薄膜のＸ線回折スペクトル図である。
【図１０】合成例４で製造原料として使用したオキシチタニウムフタロシアニン化合物のＣｕＫα線による粉末Ｘ線回折スペクトル図である。
【図１１】合成例４で得たフタロシアニン反応生成物のＣｕＫα線による粉末Ｘ線回折スペクトル図である。
【図１２】実施例５で作製したフタロシアニン反応生成物の樹脂分散液を金属薄板に浸漬塗布して得られた薄膜のＸ線回折スペクトル図である。
【図１３】合成例５で得たフタロシアニン反応生成物のＣｕＫα線による粉末Ｘ線回折スペクトル図である。
【図１４】実施例９で作製したフタロシアニン反応生成物の樹脂分散液を金属薄板に浸漬塗布して得られた薄膜のＸ線回折スペクトル図である。
【図１５】比較合成例１で得たフタロシアニン反応生成物のＣｕＫα線による粉末Ｘ線回折スペクトル図である。
【図１６】比較例１で作製したフタロシアニン反応生成物の樹脂分散液を金属薄板に浸漬塗布して得られた薄膜のＸ線回折スペクトル図である。
【図１７】比較合成例２で得たフタロシアニン反応生成物のＣｕＫα線による粉末Ｘ線回折スペクトル図である。
【図１８】比較例２で作製したフタロシアニン反応生成物の樹脂分散液を金属薄板に浸漬塗布して得られた薄膜のＸ線回折スペクトル図である。
【符号の説明】
１ 導電性支持体
２ 電荷担体発生層
３ 電荷輸送層
４ａ 感光層
４ｂ 感光層
４ｃ 感光層
５ 電荷担体発生材料
６ 電荷移動媒体
７ 電子写真感光体[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member used in, for example, a copying machine, an LD printer, an LED printer, and the like.
[0002]
[Prior art]
In recent years, with increasing demands for higher sensitivity and higher durability of electrophotographic photoconductors, a function-separated electrophotographic photoconductor in which the charge generation function and the charge transport function of the electrophotographic photoconductor are shared by different materials. Has been actively developed.
[0003]
It is also used in electrophotographic photoreceptors such as copiers, LD printers, and LED printers that use long-wavelength light sources near 750 nm represented by semiconductor lasers (LDs) and light-emitting diodes (LEDs) with the development of the electronics industry. As such materials, phthalocyanine compounds sensitive to these light sources have attracted attention.
[0004]
As an electrophotographic photoreceptor using a phthalocyanine compound, for example, JP-A-63-210941 discloses that at least one selected from τ, τ ′, η and η ′ type metal-free phthalocyanine is used for a conductive support. An electrophotographic photosensitive member comprising a charge generation layer containing a metal-free phthalocyanine and a charge transfer layer containing a butadiene derivative or a hexatriene derivative is described.
[0005]
Further, JP-A-63-210942 discloses an electrophotographic method comprising using a conductive support with a charge generator containing a titanium phthalocyanine compound and a charge transfer agent containing a butadiene derivative or a hexatriene derivative. JP-A-61-109056 discloses an electrophotographic photosensitive member comprising a charge generation layer containing a titanium phthalocyanine compound and a binder polymer, and a charge transport layer containing a hydrazone compound and a binder polymer laminated on the charge generation layer. Is described.
[0006]
Further, JP-A-3-35246 discloses that in an X-ray diffraction spectrum with respect to Cu-Kα ray, peaks are at least at Bragg angles 2θ of 9.6 ° ± 0.2 ° and 27.2 ° ± 0.2 °. A titanyl phthalocyanine in a crystalline state having a peak intensity at 9.6 ° ± 0.2 ° of 40% or more of a peak intensity at 27.2 ° ± 0.2 °, a hydrazone compound, an arylamine compound, and a polysilane compound Japanese Patent Application Laid-Open No. 5-27463 discloses an electrophotographic photosensitive member containing at least one of the following: a Bragg angle 2θ ± 0.2 ° in X-ray diffraction spectrum with respect to Cu-Kα ray of 9.0 ° and 14.2 °. An electrophotographic photoreceptor containing oxytitanium phthalocyanine having strong peaks at °, 23.9 ° and 27.1 ° and a fluorenone compound having a diarylamino substituent is described. There.
[0007]
JP-A-5-273775 discloses an electrophotographic photoreceptor containing an adduct of titanyl phthalocyanine and 2,3-butanediol and a stilbene compound.
[0008]
However, even with these electrophotographic photoreceptors, high sensitivity and stability upon repeated use, or chargeability, stability of electrophotographic characteristics under each environment is not necessarily sufficient, and further improvement is required. I have.
[0009]
In addition, in a function-separated type electrophotographic photoreceptor, it is generally known that a combination of a specific charge transporting material with respect to a specific charge generating material is effective in sensitivity, stability, durability, and the like. The charge transport material that has been effective in combination with the charge generation material is not necessarily applicable to all electrophotographic photosensitive members. An improper combination of the charge generation material and the charge transport material not only does not allow the functions of the charge generation material and the charge transport material to be sufficiently exhibited, but also degrades the performance as an electrophotographic photosensitive member. However, the universal rule in selecting a combination of a charge generation material and a charge transport material is not always clear, and it has been difficult to find a specific charge transport material combination that is effective for a specific charge generation material.
[0010]
[Problems to be solved by the invention]
The problem to be solved by the present invention is that it has high sensitivity to a long-wavelength light source near 750 nm and can be used in an electrophotographic printer or copier using a semiconductor laser (LD) or a light emitting diode (LED) as a light source. Another object of the present invention is to provide an electrophotographic photoreceptor having high sensitivity, high stability when used repeatedly, and having stable chargeability and electrophotographic characteristics under various environments.
[0011]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in view of the above circumstances, and as a result, an electrophotographic photosensitive member including a photosensitive layer containing a specific charge generating material and a specific charge transport material has excellent sensitivity and excellent repetition time. The present inventors have found that they exhibit potential stability, chargeability, and environmental stability, and have completed the present invention.
[0012]
That is, the present invention, in order to solve the above problems,
In an electrophotographic photoreceptor having a photosensitive layer formed by using a charge generation material and a charge transport material on a conductive substrate, the charge generation material comprises an oxytitanium phthalocyanine compound and a (2R, 3R)-(-)-2,3- It contains a reaction product with butanediol and / or (2S, 3S)-(+)-2,3-butanediol (hereinafter referred to as a phthalocyanine reaction product used in the ED of the present invention). Formula (I)
[0013]
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[0014]
(Wherein, Ar ₁ , Ar ₂ And Ar ₃ Represents an aromatic ring group which may have a substituent or a heterocyclic group which may have a substituent, or -NAr ₂ (Ar ₃ ) May form a ring. )
An electrophotographic photosensitive member comprising at least one compound represented by the formula:
[0015]
The method for producing the phthalocyanine reaction product used in the present invention is not particularly limited. For example, (1) an oxytitanium phthalocyanine compound and an optically active (2R, 3R)-(-)-2,3- Production method by reaction with butanediol and / or (2S, 3S)-(+)-2,3-butanediol, (2) dihalo titanium phthalocyanine compound such as dichloro titanium phthalocyanine and optically active (2R, 3R) -(-)-2,3-butanediol and / or (2S, 3S)-(+)-2,3-butanediol, a production method by reaction, (3) optically active (2R, 3R)-( Titanium salts such as titanium tetrachloride and orthophthalonitrile in the presence of-)-2,3-butanediol and / or (2S, 3S)-(+)-2,3-butanediol Method of manufacturing due to the coupling reaction with the conductor, etc., and the present invention can also be used a reaction product obtained by any production method.
[0016]
Among these production methods, an oxytitanium phthalocyanine compound and an optically active (2R, 3R)-(-)-2,3-butanediol and / or (2S, 3S)-(+)-2,3-butanediol Is preferred because the operation is simple.
[0017]
The phthalocyanine reaction product used in the present invention is obtained by the above production method, and its structure is represented by the formula (IX)
[0018]
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[0019]
Or formula (X)
[0020]
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[0021]
Is presumed to be in a crystalline state containing a phthalocyanine reaction product of a specific isomer structure represented by
[0022]
The phthalocyanine reaction product used in the present invention is preferably in a crystalline state, and particularly, in the X-ray diffraction spectrum of Cu-Kα, a main peak at 9.5 ° of Bragg angle (2θ ± 0.2 °). More preferably, it is in a crystalline state, or in a crystalline state having peaks at 8.3, 24.7, and 25.1.
[0023]
The electrophotographic photoreceptor of the present invention has a photosensitive layer using a charge generation material containing the above crystalline state of the phthalocyanine reaction product used in the present invention. The X-ray diffraction spectrum of the photosensitive layer with respect to Cu-Kα , A photosensitive layer having a main peak at 9.5 ° of the Bragg angle (2θ ± 0.2 °), a photosensitive layer having peaks at 8.3 °, 24.7 ° and 25.1 °, and 8.3. A photosensitive layer having a main peak at ゜ is preferable, and a photosensitive layer having a main peak at 8.3 ° at Bragg angle (2θ ± 0.2 °) is more preferable.
[0024]
An oxytitanium phthalocyanine compound for obtaining a phthalocyanine reaction product used in the present invention is combined with an optically active (2R, 3R)-(-)-2,3-butanediol and / or (2S, 3S)-(+)-. The reaction with 2,3-butanediol is preferably performed under heating conditions, and the reaction temperature is preferably in the range of 30 to 300 ° C, particularly preferably in the range of 50 to 250 ° C.
[0025]
The oxytitanium phthalocyanine compound serving as a raw material for synthesizing the phthalocyanine reaction product used in the present invention has an oxytitanium at the center of the phthalocyanine skeleton which may have a substituent, as long as the effect of the present invention is not impaired. Any type may be used as long as the effects of the present invention are not impaired, and crystalline forms such as α-type, β-type, α-β mixed-type, γ-type, Y-type, and amorphous-type may be used. When the phthalocyanine skeleton has a substituent, examples of the substituent include a lower alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group; a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, and a nitro group. No. The number of these substituents can be from 1 to 16, and a combination of two or more substituents is also possible.
[0026]
Also, the moles of the reaction between the oxytitanium phthalocyanine compound and the optically active (2R, 3R)-(-)-2,3-butanediol and / or (2S, 3S)-(+)-2,3-butanediol. The ratio is such that optically active (2R, 3R)-(-)-2,3-butanediol and / or (2S, 3S)-(+)-2,3-butanediol are present in an amount of 0 mol per mol of the oxytitanium phthalocyanine compound. .25 mol or more is preferable, and the range of 0.5 to 1.5 mol is more preferable.
[0027]
(2R, 3R)-(-)-2,3-butanediol and / or (2S, 3S)-(+)-2,3-butanediol used as a raw material for the synthesis of the phthalocyanine reaction product used in the present invention are , Optically active, using only one of (2R, 3R)-(-)-2,3-butanediol or (2S, 3S)-(+)-2,3-butanediol, or the content of both It is preferable to use an optically active threo type 2,3-butanediol different from the above.
[0028]
The charge generating material of the electrophotographic photoreceptor of the present invention may use one optical isomer of the phthalocyanine reaction product used in the present invention alone, or may use a mixture of two or more thereof. . That is, a reaction product of an oxytitanium phthalocyanine compound and (2R, 3R)-(-)-2,3-butanediol, an oxytitanium phthalocyanine compound, and (2S, 3S)-(+)-2,3-butane A reaction product with a diol may be used as a mixture.
[0029]
In the reaction of the oxytitanium phthalocyanine compound with (2R, 3R)-(-)-2,3-butanediol and / or (2S, 3S)-(+)-2,3-butanediol, if necessary, Various known organic solvents can be used in combination. Examples of such an organic solvent include aromatic organic solvents such as benzene, nitrobenzene, dichlorobenzene, trichlorobenzene, and α-chloronaphthalene; ketone organic solvents such as cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone; tetrahydrofuran and dimethyl cellosolve Ether organic solvents such as ethyl butanoate and butyl lactate; aprotic polar organic solvents such as dimethylformamide and dimethyl sulfoxide; halogen organic solvents such as trichloroethane; monovalent such as amyl alcohol and dodecanol. Alcohol organic solvents and the like can be mentioned. These solvents can be used alone or in combination of two or more.
[0030]
After synthesizing the phthalocyanine reaction product used in the present invention, purification such as sublimation purification may be performed as necessary.
[0031]
As described above, in synthesizing the phthalocyanine reaction product used in the present invention, each production condition such as a reaction molar ratio, a reaction temperature, a reaction time, a solvent, a catalyst, a purification method, and a crystallization method is appropriately selected and adopted. can do.
[0032]
The charge generating material used in the electrophotographic photoreceptor of the present invention contains the phthalocyanine reaction product used in the present invention as an essential component, and other charge generating materials may be used in combination with the charge generating material as long as its characteristics are not impaired. Is also possible.
[0033]
As other charge generating materials that can be used in combination, for example, a metal-free phthalocyanine compound, a metal phthalocyanine compound, or a crystal type or amorphous type such as α-type, β-type, α-β mixed type, γ-type, Y-type, etc. Oxytitanium phthalocyanine compounds, azo-based pigments, anthraquinone-based pigments, perylene-based pigments, polycyclic quinone-based pigments, squarium-based pigments, and the like can be used, but are not limited thereto.
[0034]
The charge transporting material used in the electrophotographic photoreceptor of the present invention contains the compound represented by the general formula (I) as a main component, and among the compounds represented by the general formula (I),
[0035]
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[0036]
(Wherein, Ar ₄ Represents an aromatic ring group which may have a substituent, or a heterocyclic group which may have a substituent. Two different benzene rings may form a ring via Y. When forming a ring, Y represents a residue necessary for bonding to different benzene rings to form a ring. R ₁ And R ₂ Each independently represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. )
A compound represented by the general formula (III)
[0037]
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[0038]
(Wherein, Ar ₅ And Ar ₆ Represents an aromatic ring group which may have a substituent, or a heterocyclic group which may have a substituent, and two different benzene rings may form a ring via W. When forming a ring, W represents a residue necessary for bonding to different benzene rings to form a ring. R ₃ , R ₄ , R ₅ And R ₆ Each independently represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. )
And a compound represented by the general formula (IV)
[0039]
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[0040]
(Wherein m represents 0 or 1, Ar ₇ , Ar ₈ , Ar ₉ And Ar ₁₀ Each independently represents an aromatic ring group which may have a substituent, a heterocyclic group which may have a substituent, and Z has an oxygen atom, a sulfur atom, and a substituent. Represents a good aminylene group, a divalent aromatic residue which may have a substituent or a divalent heterocyclic residue which may have a substituent, and two different benzene rings represent W And a ring may be formed through the ring. When forming a ring, W represents a residue necessary for bonding to different benzene rings to form a ring. R ₇ , R ₈ , R ₉ And R ₁₀ Each independently represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. )
Those containing at least one compound selected from the group consisting of compounds represented by
[0041]
Next, the structures of typical compounds of the charge transporting material used in the electrophotographic photoreceptor of the present invention are shown by the following structural formulas, but the present invention is not necessarily limited to these examples. The numbers described below the structural formulas represent the numbers of the exemplified compounds.
[0042]
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[0043]
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[0044]
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[0045]
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[0046]
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[0047]
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[0048]
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[0049]
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[0050]
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[0051]
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[0052]
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[0053]
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[0054]
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[0055]
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[0056]
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[0057]
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[0058]
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[0059]
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[0060]
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[0061]
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[0062]
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[0063]
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[0064]
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[0065]
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[0066]
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[0067]
The charge transporting material of the electrophotographic photoreceptor of the present invention contains at least one compound selected from the compounds represented by Formula (I) or Formulas (II) to (IV), provided that the characteristics are not impaired. In the above, other charge transport materials other than the compounds represented by the general formulas (I) and (II) to (IV) can be used in combination.
[0068]
Other charge transporting materials that can be used in combination include, for example, stilbene-based, hydrazone-based, pyrazoline-based, oxazole-based, oxadiazole-based, thiazole-based, carbazole-based, diphenoquinone-based, arylmethane-based compounds, or poly-N- Examples thereof include polymerizable compounds such as vinyl carbazole and polysilane.
[0069]
When these charge transport materials are used in combination, the content of the compounds represented by the general formulas (I) and (II) to (IV) in all the charge transport materials is 20% or more by weight. Is particularly preferable, and it is particularly preferable that it is 50% or more.
[0070]
The configuration of the electrophotographic photoreceptor of the present invention can take various structures. Examples are shown in FIGS.
[0071]
The electrophotographic photoreceptor shown in FIGS. 1 and 2 has a photosensitive structure comprising a charge generation layer 2 mainly composed of a charge generation material on a conductive support 1 and a charge transport layer 3 made of a charge transport material and a binder resin. It is provided with a layer 4a or 4b, respectively. The electrophotographic photoreceptor shown in FIG. 3 includes a conductive support 1 and a photosensitive layer 4c in which a charge generation material 5 is dispersed in a charge transfer medium 6.
[0072]
In the case of the electrophotographic photoreceptor shown in FIGS. 1 and 2, the charge generating material contained in the charge generating layer 2 generates charges, while the charge transporting layer 3 receives the charges and transports them. That is, the charge required for light attenuation is generated by the charge generating material, and the charge is transported by the charge transport medium. In the electrophotographic photoreceptor of FIG. 3, the charge generating material generates a charge with respect to light, and the charge is transferred by a charge transfer medium.
[0073]
The electrophotographic photoreceptor of FIG. 1 is a dispersion obtained by dispersing fine particles of the charge generating material in a solvent in which a binder resin is dissolved, if necessary, on a charge generating layer composed of a deposited film of the charge generating material. Is applied, and a charge transporting material obtained by drying is applied on the charge generating layer obtained by drying, or a solution prepared by dissolving the charge transporting material in combination with a binder resin as necessary is dried, and then the charge transporting obtained by drying is performed. It can be manufactured by providing a layer.
[0074]
The electrophotographic photoreceptor shown in FIG. 2 has a charge generation layer formed on a charge transport layer obtained by applying a solution alone or in combination with a binder resin as necessary and then drying the solution on a conductive support. By providing a charge generation layer composed of a vapor-deposited film of the material, or a dispersion obtained by dispersing fine particles of the charge generation material in a solvent or a binder resin solution, and then drying the charge generation layer to provide the charge generation layer. Can be manufactured.
[0075]
The electrophotographic photoreceptor in FIG. 3 is manufactured by dispersing fine particles of a charge generating material in a solution in which a charge transporting material is dissolved in a binder resin, applying the fine particles on a conductive support, and then drying. Can be.
[0076]
In the case of the electrophotographic photosensitive members shown in FIGS. 1 and 2, the thickness of the charge generation layer is preferably 5 μm or less, and particularly preferably in the range of 0.01 to 2 μm. The thickness of the charge transport layer is preferably in the range of 3 to 50 μm, particularly preferably in the range of 5 to 30 μm. In the case of the electrophotographic photoreceptor of FIG. 3, the thickness of the photosensitive layer is preferably in the range of 3 to 50 μm, and particularly preferably in the range of 5 to 30 μm.
[0077]
The ratio of the charge transporting material in the charge transporting layer in the electrophotographic photosensitive member of FIGS. 1 and 2 is preferably in the range of 5 to 80% by weight, and particularly preferably in the range of 30 to 70% by weight. The ratio of the binder resin in the charge transport layer of the electrophotographic photosensitive member of FIGS. 1 and 2 is preferably in the range of 20 to 95% by weight, and particularly preferably in the range of 30 to 70% by weight. The ratio of the charge generation material in the charge generation layer of the electrophotographic photoreceptor of FIGS. 1 and 2 is preferably in the range of 5 to 100% by weight, particularly preferably in the range of 40 to 80% by weight. In the electrophotographic photoreceptor of FIG. 3, the proportion of the charge transporting material in the photosensitive layer is preferably in the range of 5 to 80% by weight, the binder resin is preferably in the range of 20 to 94% by weight, and the proportion of the charge generating material is , 1 to 50% by weight, and particularly preferably 3 to 20% by weight. In the production of any of the electrophotographic photosensitive members shown in FIGS. 1 to 3, a plasticizer and a sensitizer can be used together with the binder resin.
[0078]
As the conductive substrate used in the electrophotographic photoreceptor of the present invention, for example, metals or alloys such as aluminum, copper, zinc, stainless steel, chromium, titanium, nickel, molybdenum, vanadium, indium, gold, platinum, or conductive Conductive polymers such as conductive polymers and indium oxide; paper, plastic films, ceramics, etc. coated, vapor-deposited or laminated with metals or alloys such as aluminum, palladium, and gold, and the like. Chemical or physical treatment may be performed.
[0079]
Although the shape of the electrophotographic photoreceptor of the present invention varies depending on the conductive substrate used, various shapes such as a drum shape, a flat plate shape, a sheet shape, and a belt shape are possible.
[0080]
As the binder resin obtained by dissolving the charge transport material in the electrophotographic photoreceptor of the present invention, it is preferable to use a high molecular polymer which is hydrophobic and capable of forming an electrically insulating film. Examples of such high-molecular polymers include polycarbonate, polyarylate, polyester, methacrylic resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, and vinyl chloride-vinyl acetate. -Maleic anhydride copolymer, silicone resin, silicon-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole, polyvinyl butyral, polyvinyl formal, polysulfone and the like.
[0081]
Among these binder resins, polycarbonate and polyarylate are preferable because they form a highly durable photosensitive layer.
[0082]
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[0083]
(Wherein, a hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group which may have a substituent; ₁₁ And R ₁₂ Represents a hydrogen atom, an alkyl group which may have a substituent or an aromatic group which may have a substituent. )
A polycarbonate having a repeating unit represented by the general formula (VI):
[0084]
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[0085]
(In the formula, a hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group which may have a substituent, and Q has a carbon ring or a substituent which may have a substituent. Represents the atoms necessary to form a heterocyclic ring which may be substituted.)
A polycarbonate having a repeating unit represented by the formula (V) and a repeating unit represented by the formula (V) and a formula (VII)
[0086]
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[0087]
(In the formula, a hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group which may have a substituent.)
A copolymerized polycarbonate having a repeating unit represented by the general formula (VIII):
[0088]
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[0089]
(In the formula, a hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group which may have a substituent.)
A polyarylate having a repeating unit represented by the formula (1) is more preferable as a resin for dissolving the charge transporting material of the present invention because of its high electrical stability.
[0090]
These binder resins can be used alone or as a mixture of two or more.
[0091]
The binder resin that can be used as necessary for dispersing the charge generating material is preferably a hydrophobic, electrically insulating film-forming polymer compound, and is preferably prepared by dissolving the above-described charge transport material. The same binder resin is preferable.
[0092]
Further, in order to improve the film formability, flexibility, and mechanical strength of the electrophotographic photoreceptor, well-known additives such as a plasticizer and a surface modifier can be used together with these binder resins. .
[0093]
Examples of the plasticizer include biphenyl, biphenyl chloride, o-terphenyl, p-terphenyl, dibutyl phthalate, diethyl glycol phthalate, dioctyl phthalate, triphenylphosphoric acid, methylnaphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, various types And the like.
[0094]
Examples of the surface modifier include silicone oil, fluorine resin and the like.
[0095]
Well-known sensitizers can be used for the photosensitive layer as needed.
[0096]
Examples of the sensitizer include chloranil, tetracyanoethylene, methyl violet, rhodamine B, cyanine dye, merocyanine dye, pyrylium dye, and thiapyrylium dye.
[0097]
Further, in the electrophotographic photoreceptor of the present invention, in order to improve storability, durability and environmental resistance, the photosensitive layer may contain a deterioration inhibitor such as an antioxidant or a light stabilizer. . Examples thereof include phenol compounds, hydroquinone compounds, and amine compounds.
[0098]
Further, in the present invention, in order to improve the adhesion between the conductive support and the photosensitive layer, or to prevent the injection of free charge from the conductive support to the photosensitive layer, the conductive support and the photosensitive layer In between, an adhesive layer or a barrier layer can be provided as necessary.
[0099]
Materials used for these layers include, in addition to the high molecular compounds used for the binder resin, casein, gelatin, ethyl cellulose, nitrocellulose, carboxy-methyl cellulose, vinylidene chloride-based polymer latex, styrene-butadiene-based polymer latex, polyvinyl Examples thereof include alcohol, polyamide, polyurethane, phenolic resin, aluminum oxide, tin oxide, and titanium oxide, and the thickness is preferably 1 μm or less.
[0100]
When the laminated electrophotographic photosensitive member is formed by coating, the solvent for dissolving the binder resin varies depending on the type of the binder resin, but it is preferable to select a solvent that does not dissolve the lower layer. Specific examples of organic solvents include, for example, alcohols such as methanol, ethanol and n-propanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; amides such as N, N-dimethylformamide and N, N-dimethylacetamide Ethers such as tetrahydrofuran, dioxane, and methyl cellosolve; esters such as methyl acetate and ethyl acetate; sulfoxides and sulfones such as dimethyl sulfoxide and sulfolane; aliphatic halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, and trichloroethane. Hydrogen; aromatics such as benzene, toluene, xylene, monochlorobenzene, and dichlorobenzene;
[0101]
As the coating method, for example, a coating method such as a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method, and a curtain coating method can be used.
[0102]
The electrophotographic photoreceptor provided with the photosensitive layer containing the specific charge generation material and the specific charge transport material of the present invention has the above-described structure, and as is apparent from the following examples, It has excellent sensitivity, excellent electrophotographic stability, chargeability and environmental stability when used repeatedly.
[0103]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the scope of these Examples. In the following examples, "parts" all mean "parts by weight".
[0104]
(Synthesis example 1)
An oxytitanium phthalocyanine compound obtained from titanium tetrachloride and o-phthalonitrile, which is 20 parts of an oxytitanium phthalocyanine compound showing a powder X-ray diffraction spectrum by CuKα ray shown in FIG. 4, and (2R, 3R)-( -) 4.4 parts of 2,3-butanediol was reacted in 240 parts of α-chloronaphthalene at 195 to 205 ° C for 1.5 hours while stirring.
[0105]
The reaction mixture was cooled to room temperature, filtered, washed with benzene, methanol, dimethylformamide (hereinafter abbreviated as DMF) and water in that order, and dried under reduced pressure to obtain a phthalocyanine reaction product. .
[0106]
This reaction product showed a peak at m / Z = 648 in the mass spectrum. The result of measuring the powder X-ray diffraction spectrum of this reaction product by CuKα radiation is shown in FIG. Further, the results of elemental analysis of this reaction product are shown in Table 1.
[0107]
[Table 1]

[0108]
(Example 1)
A mixture consisting of 2 parts of the phthalocyanine reaction product obtained in Synthesis Example 1 and 2 parts of butyral resin (“ESLEC BH-3” manufactured by Sekisui Chemical Co., Ltd.) is composed of 66 parts of methylene chloride and 99 parts of 1,1,2-trichloroethane. The mixture was added to a solvent, dispersed and mixed with a paint conditioner to obtain a dispersion of the charge generation material.
[0109]
FIG. 6 shows an X-ray diffraction spectrum of a thin film having a thickness of 5 μm obtained by dip coating the thus obtained dispersion of the charge generating material on a thin metal plate.
[0110]
Next, the thus obtained dispersion of the charge generation material was applied on a polyester film on which aluminum was deposited using a wire bar so that the thickness after drying was 0.3 μm, and then dried. A charge generation layer was formed.
[0111]
On the charge generation layer, the above-described Compound No. 86 of the charge transporting material and the structural formula (XI)
[0112]
Embedded image

[0113]
A coating solution obtained by dissolving 10 parts of a polycarbonate having a repeating unit of (Iupilon Z200 manufactured by Mitsubishi Gas Chemical Company) in a mixed solvent consisting of 54 parts of methylene chloride and 36 parts of chlorobenzene was dried using a wire bar. After coating so as to have a film thickness of 20 μm, it was dried to form a charge transporting layer, and an electrophotographic photoreceptor having the layer configuration shown in FIG. 1 was obtained.
[0114]
(Synthesis example 2)
Synthesis Example 1 was the same as Synthesis Example 1 except that (2S, 3S)-(+)-2,3-butanediol was used instead of (2R, 3R)-(−)-2,3-butanediol. A phthalocyanine reaction product was obtained in the same manner.
[0115]
This reaction product showed a peak at m / Z = 648 in the mass spectrum. FIG. 7 shows the result of measuring the powder X-ray diffraction spectrum of the reaction product by CuKα radiation.
[0116]
(Example 2)
An electrophotographic photosensitive member was obtained in the same manner as in Example 1, except that the phthalocyanine reaction product obtained in Synthesis Example 2 was used instead of the phthalocyanine reaction product obtained in Synthesis Example 1.
[0117]
(Example 3)
In Example 1, except that 1 part of the phthalocyanine reaction product obtained in Synthesis Example 1 and 1 part of the phthalocyanine reaction product obtained in Synthesis Example 2 were used instead of 2 parts of the phthalocyanine reaction product obtained in Synthesis Example 1 In the same manner as in Example 1, an electrophotographic photosensitive member was obtained.
[0118]
(Synthesis example 3)
In Synthesis Example 1, 2.2 parts of (2R, 3R)-(-)-2,3-butanediol was replaced with 4.4 parts of (2R, 3R)-(-)-2,3-butanediol. Except for using, a reaction product of phthalocyanine was obtained in the same manner as in Synthesis Example 1.
[0119]
This reaction product showed peaks at m / Z = 576 and 648 in the mass spectrum. The result of measuring the powder X-ray diffraction spectrum of this reaction product by CuKα radiation is shown in FIG.
[0120]
(Example 4)
An electrophotographic photosensitive member was obtained in the same manner as in Example 1, except that the phthalocyanine reaction product obtained in Synthesis Example 3 was used instead of the phthalocyanine reaction product obtained in Synthesis Example 1.
[0121]
FIG. 9 shows an X-ray diffraction spectrum of a thin film obtained by dip coating the dispersion of the charge generation material used in Example 4 on a thin metal plate so that the film thickness after drying was 5 μm, and then drying. Was.
[0122]
(Synthesis example 4)
An oxytitanium phthalosinine compound obtained by subjecting oxytitanium phthalocyanine obtained from titanium tetraisopropoxide and 1,3-diiminoisoindoline to an acid paste treatment with concentrated sulfuric acid, using a CuKα ray shown in FIG. 20 parts of an oxytitanium phthalocyanine compound exhibiting a powder X-ray diffraction spectrum and 4.7 parts of (2R, 3R)-(-)-2,3-butanediol were subjected to 195 to 205 ° C in 240 parts of α-chloronaphthalene. The mixture was reacted for 1.5 hours while shaking.
[0123]
After the reaction mixture was cooled to room temperature, it was separated by filtration, washed with benzene, methanol, DMF, and water in that order, and dried under reduced pressure to obtain a phthalocyanine reaction product.
[0124]
This reaction product showed peaks at m / Z = 576 and 648 in the mass spectrum. FIG. 11 shows the result of measuring the powder X-ray diffraction spectrum of this reaction product by CuKα radiation.
[0125]
(Example 5)
An electrophotographic photosensitive member was obtained in the same manner as in Example 1, except that the phthalocyanine reaction product obtained in Synthesis Example 4 was used instead of the phthalocyanine reaction product obtained in Synthesis Example 1.
[0126]
FIG. 12 shows an X-ray diffraction spectrum of a thin film obtained by dip coating the dispersion of the charge generation material used in Example 5 on a thin metal plate so that the film thickness after drying was 5 μm, and then drying. Was.
[0127]
(Example 6)
In Example 1, the structural formula (XII) was used instead of the polycarbonate having the repeating unit represented by the structural formula (XI).
[0128]
Embedded image

[0129]
And a repeating unit represented by the formula (XIII)
[0130]
Embedded image

[0131]
Using a copolymerized polycarbonate having a repeating unit represented by the following formula at a ratio of 86:14, An electrophotographic photoreceptor was obtained in the same manner as in Example 1, except that 0.4 parts of 2,6-di-t-butyl-p-cresol was used together with 8 parts of the charge transport material of 86.
[0132]
(Example 7)
In Example 1, the charge transporting layer was formed using the above-described Compound No. 86 parts of the charge transporting material, 0.4 parts of 2,6-di-t-butyl-p-cresol and the structural formula (XIV)
[0133]
Embedded image

[0134]
A coating solution obtained by dissolving 10 parts of a polycarbonate having a repeating unit represented by the following formula (“PANLITE C1400” manufactured by Teijin Chemicals Limited) in a mixed solvent consisting of 80 parts of methylene chloride and 20 parts of 1,1,2-trichloroethane: An electrophotographic photoreceptor was obtained in the same manner as in Example 1, except that the film was applied so that the film thickness after drying became 20 μm, and then dried to form a charge transporting layer.
[0135]
(Example 8)
In Example 1, the charge transporting layer was formed using the above-described Compound No. 86 parts of a charge transport material, 0.4 parts of 2,6-di-t-butyl-p-cresol and a structural formula (XV)
[0136]
Embedded image

[0137]
A coating solution prepared by dissolving 10 parts of polyarylate having a repeating unit represented by the following formula ("ISARYL25S" manufactured by Isonova) in 100 parts of 1,4-dioxane was applied so that the film thickness after drying was 20 μm. Thereafter, an electrophotographic photosensitive member was obtained in the same manner as in Example 1, except that the charge transport layer was obtained by drying.
[0138]
(Synthesis example 5)
In Synthesis Example 1, 3.1 parts of (2R, 3R)-(-)-2,3-butanediol was replaced with 4.4 parts of (2R, 3R)-(-)-2,3-butanediol. Except for using, a phthalocyanine reaction product was obtained in the same manner as in Synthesis Example 1.
[0139]
This reaction product showed peaks at m / Z = 576 and 648 in the mass spectrum. The result of measuring the powder X-ray diffraction spectrum of this reaction product by CuKα radiation is shown in FIG.
[0140]
(Example 9)
An electrophotographic photoreceptor was obtained in the same manner as in Example 1, except that the phthalocyanine reaction product obtained in Synthesis Example 5 was used instead of the phthalocyanine reaction product obtained in Synthesis Example 1.
[0141]
FIG. 14 shows an X-ray diffraction spectrum of a thin film obtained by dip coating the dispersion of the charge generation material used in Example 9 on a thin metal plate so that the film thickness after drying was 5 μm, and then drying. Was.
[0142]
(Example 10)
In Example 1, in place of the phthalocyanine reaction product obtained in Synthesis Example 1, 2 parts of the phthalocyanine reaction product obtained in Synthesis Example 3 was used. Polycarbonate having 8 parts of a charge transport material, 86 parts of 2,6-di-t-butyl-p-cresol and 0.4 part of a repeating unit represented by the above structural formula (XIV) ("Pan" manufactured by Teijin Chemicals Limited) Light C1400 ”) was coated with a coating solution prepared by dissolving 10 parts of a mixed solvent consisting of 40 parts of methylene chloride and 10 parts of 1,1,2-trichloroethane so that the film thickness after drying was 20 μm, and then dried. An electrophotographic photoreceptor was obtained in the same manner as in Example 1 except that the charge transport layer was obtained.
[0143]
(Comparative Synthesis Example 1)
In Synthesis Example 1, a phthalocyanine reaction was produced in the same manner as in Synthesis Example 1 except that meso-2,3-butanediol was used instead of (2R, 3R)-(-)-2,3-butanediol. I got something.
[0144]
This reaction product showed a peak at m / Z = 648 in the mass spectrum. The result of measuring the powder X-ray diffraction spectrum of this reaction product by CuKα radiation is shown in FIG.
[0145]
(Comparative Example 1)
An electrophotographic photosensitive member was obtained in the same manner as in Example 1, except that the phthalocyanine reaction product obtained in Comparative Synthesis Example 1 was used instead of the phthalocyanine reaction product obtained in Synthesis Example 1. .
[0146]
FIG. 16 shows an X-ray diffraction spectrum of a thin film obtained by dip coating the dispersion of the charge generation material used in Comparative Example 1 on a thin metal plate so that the film thickness after drying was 5 μm, and then drying. Was.
[0147]
(Comparative Synthesis Example 2)
In Synthesis Example 1, a phthalocyanine reaction product was obtained in the same manner as in Synthesis Example 1 except that ethylene glycol was used instead of (2R, 3R)-(-)-2,3-butanediol.
[0148]
This reaction product showed a peak at m / Z = 620 in the mass spectrum. The result of measuring the powder X-ray diffraction spectrum of this reaction product by CuKα radiation is shown in FIG.
[0149]
(Comparative Example 2)
An electrophotographic photoreceptor was obtained in the same manner as in Example 1, except that the phthalocyanine reaction product obtained in Comparative Synthesis Example 2 was used instead of the phthalocyanine reaction product obtained in Synthesis Example 1. .
[0150]
FIG. 18 shows an X-ray diffraction spectrum of a thin film obtained by dip coating the dispersion of the charge generation material used in Comparative Example 2 on a thin metal plate so that the film thickness after drying was 5 μm, and then drying. Was.
[0151]
(Comparative Example 3)
In Example 1, Example Compound No. 86, in place of the charge transport material of formula (XVI)
[0152]
Embedded image

[0153]
An electrophotographic photosensitive member was obtained in the same manner as in Example 1, except that the charge transporting material represented by the following formula was used.
[0154]
(Comparative Synthesis Example 3)
According to the method described in Production Example 1 of JP-A-61-109056, that is, 4.6 parts of phthalodinitrile was charged into 25 parts of α-chloronaphthalene, dissolved at 120 ° C., and titanium tetrachloride was added. 1.7 g was added dropwise, and stirring was continued at 150 ° C. for 30 minutes. Thereafter, the reaction temperature was gradually raised, and heating and stirring were continued at 220 ° C. for 2 hours.
[0155]
After completion of the reaction, the reaction mixture was allowed to cool to 100 ° C., filtered while hot, and the residue was subjected to methanol hot suspension, hot water boiling suspension, and N-methylpyrrolidone for 1 hour at 120 ° C. for 1 hour. The mixture was filtered while hot, suspended hot with methanol, filtered, and dried under reduced pressure to obtain a blue powder.
[0156]
As a result of elemental analysis of the blue powder thus obtained, the chlorine content was 0.51%. The obtained blue powder was a mixture of oxytitanium phthalocyanine and a small amount of titanium chloride phthalocyanine.
[0157]
(Comparative Example 4)
In the same manner as in Example 1 except that the mixture of oxytitanium phthalocyanine obtained in Comparative Synthesis Example 3 and a small amount of titanium phthalocyanine was used in place of the phthalocyanine reaction product obtained in Synthesis Example 1 in Example 1, Thus, an electrophotographic photosensitive member was obtained.
[0158]
(Electrophotographic characteristics)
For each of the electrophotographic photosensitive members obtained in Examples 1 to 10 and Comparative Examples 1 to 3, the electrophotographic photosensitive members were placed in a dark place using an electrostatic copying paper test apparatus ("SP428" manufactured by Kawaguchi Electric Works, Ltd.). Charged by a −6 KV corona discharge, and the surface potential V of the electrophotographic photosensitive member at this time is ₀ (V) was measured. Next, the surface potential V of the electrophotographic photosensitive member when left as it is in a dark place for 10 seconds. ₁₀ (V) was measured. V ₀ And V ₁₀ The potential holding ratio (%) of the surface potential of the electrophotographic photoreceptor: (V ₁₀ / V ₀ ) × 100 was calculated. Further, the surface potential V ₁₀ Wavelength 780 nm, exposure energy 1 μW / cm ² Exposure with light of ₁₀ Exposure E _1/2 (ΜJ / cm ² ). Furthermore, the surface potential 15 seconds after the start of exposure, that is, the residual potential V _R (V) was measured. Table 2 summarizes the measurement results.
[0159]
Tables 2 and 3 also show the measurement results immediately after the process of charging, leaving in a dark place for 1 second, exposing for 1 second, and removing static electricity with 300 lux white light for 0.1 second was repeated 500 times.
[0160]
[Table 2]

[0161]
[Table 3]

[0162]
(Examples 11 to 24)
In Example 10, Exemplified Compound No. An electrophotographic photoreceptor was obtained in the same manner as in Example 10, except that the charge transport materials shown in Tables 4 and 5 were used instead of the charge transport material 86.
[0163]
Tables 4 and 5 also show the electrophotographic characteristics of these electrophotographic photosensitive members according to the same method as the method for evaluating the electrophotographic photosensitive members obtained in Examples 1 to 10.
[0164]
[Table 4]

[0165]
[Table 5]

[0166]
(Example 25)
A resin solution was prepared by dissolving 1 part of a polyamide resin (“Amilan CM-8000” manufactured by Toray Industries, Inc.) in a mixed solvent consisting of 7 parts of methanol and 7 parts of n-butanol. This resin solution was applied to the outer peripheral surface of an aluminum drum having a diameter of 30 mm and a thickness of 1 mm by a dip coating method so that the film thickness after drying was 1 μm, and then dried to form a barrier layer.
[0167]
Next, 2 parts of the phthalocyanine reaction product obtained in Synthesis Example 3 and 2 parts of a butyral resin (“ESLEC BH-3” manufactured by Sekisui Chemical Co., Ltd.) were added to 66 parts of methylene chloride and 99 parts of 1,1,2-trichloroethane. And mixed with a paint conditioner to obtain a dispersion of the charge generation material. The thus obtained dispersion of the charge generating material is applied on the barrier layer by a dip coating method so that the film thickness after drying is 0.4 μm, and then dried to form a charge generating layer. Provided.
[0168]
Next, the above-mentioned exemplified compound No. Polycarbonate having 8 parts of a charge transporting material of 86, 0.5 part of 2,6-di-t-butyl-p-cresol and a repeating unit of the structural formula (XI) ("Iupilon Z200" manufactured by Mitsubishi Gas Chemical Company, Inc.). ") Dip 10 parts of a coating material for forming a charge transporting material layer in a mixed solvent consisting of 54 parts of methylene chloride and 36 parts of chlorobenzene on the charge generating layer so that the film thickness after drying is 20 μm. After coating, the resultant was dried to provide a charge transport layer, thereby obtaining a drum-shaped electrophotographic photosensitive member.
[0169]
(Examples 26 to 28)
In Example 25, Exemplified Compound No. Electrophotographic photoreceptors were obtained in the same manner as in Example 21, except that 10 parts of the charge transporting material shown in Table 6 below were used instead of 8 parts of the charge transporting material of 86.
[0170]
(Comparative Example 5)
In Example 25, Exemplified Compound No. Electrophotographic photoreceptors were obtained in the same manner as in Example 25 except that 10 parts of the charge transporting material represented by the structural formula (XVI) was used instead of 8 parts of the charge transporting and transporting material of 86.
[0171]
(Image characteristics)
The drum-shaped electrophotographic photosensitive members obtained in Examples 25 to 28 and Comparative Example 5 were mounted on a commercially available laser printer (“LaserJet 4” manufactured by Hewlett-Packard Company), and continuous printing was performed while toner was being supplied. Evaluation of the image state was performed.
[0172]
Table 6 shows a list of the evaluation results at the initial stage and after the printing test of 10,000 sheets.
[0173]
[Table 6]

[0174]
(Example 29)
The drum-shaped electrophotographic photosensitive member obtained in Example 25 was subjected to a surface potential V at an applied voltage of -5.5 KV using a photoreceptor analyzing system CYNTHIA30 (manufactured by Gentec Corporation). ₀ Immediately after corona charging to (V), a semiconductor laser of 780 nm was used and 1.3 erg / cm ² Surface potential V after light irradiation _L (V) and surface potential V when left for 10 seconds in a dark place after charging ₁₀ Was determined under each environment. V ₀ And V ₁₀ More potential holding ratio V of surface potential of electrophotographic photosensitive member _D (%): (V ₁₀ / V ₀ ) × 100 was calculated. Table 7 shows the results.
[0175]
(Comparative Synthesis Example 4)
According to the method described in Synthesis Example 1 of JP-A-3-35246, 14.7 ml of titanium tetrachloride was dropped into a mixture of 65 g of phthalodinitrile and 500 ml of o-chloronaphthalene under a nitrogen stream, The temperature was gradually raised to 200 ° C., and the reaction was completed by stirring for 3 hours while maintaining the reaction temperature at 200 to 220 ° C. After the completion of the reaction, the reaction mixture was allowed to cool to 130 ° C., filtered while hot, washed with o-chloronaphthalene, and washed several times with methanol to obtain dichlorotitanium phthalocyanine. Further, the crystals obtained by washing several times with hot water at 80 ° C. are dried, and 5 g of the crystals are stirred in 100 g of 96% sulfuric acid while keeping the temperature at 3 to 5 ° C., and the sulfuric acid solution obtained by filtration is washed with water 3 Pour into 5 liters. The precipitated crystals were collected by filtration, washed repeatedly with water until the washing liquid became neutral, filtered, and the wet cake was treated with dichloroethane, washed with methanol, and dried to obtain titanyl phthalocyanine crystals. In the titanyl phthalocyanine thus obtained, the ratio of the peak at a Bragg angle 2θ of 9.6 ° ± 0.2 ° to the peak at 27.2 ° ± 0.2 ° was 78%.
[0176]
(Comparative Example 6)
In Example 25, a drum-shaped electrophotographic photosensitive member was prepared in the same manner as in Example 25 except that the titanyl phthalocyanine obtained in Comparative Synthesis Example 4 was used instead of 2 parts of the phthalocyanine reaction product obtained in Synthesis Example 3. It was manufactured, and the electrophotographic characteristics under each environment were measured according to Example 29. The results are shown in Table 7.
[0177]
[Table 7]

[0178]
From the results shown in Table 7, the drum-shaped electrophotographic photosensitive member obtained in Example 29 was superior in the chargeability and the potential holding ratio as compared with the drum-shaped electrophotographic photosensitive member obtained in Comparative Example 6, It is clear that the difference between the maximum value and the minimum value of the post-exposure potential under each environment is small, and it is strong against environmental changes.
[0179]
【The invention's effect】
The electrophotographic photoreceptor of the present invention has high sensitivity to a long-wavelength light source near 750 nm, maintains high stability and chargeability upon repeated use, and high stability in environmental fluctuations, and is extremely useful in practical use. It is.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view illustrating an example of a layer configuration of an electrophotographic photosensitive member according to the present invention.
FIG. 2 is a schematic cross-sectional view illustrating an example of a layer configuration of an electrophotographic photosensitive member according to the present invention.
FIG. 3 is a schematic cross-sectional view illustrating an example of a layer configuration of the electrophotographic photosensitive member according to the present invention.
FIG. 4 is a powder X-ray diffraction spectrum diagram of CuO using the oxytitanium phthalocyanine compound used as a raw material in Synthesis Example 1.
FIG. 5 is an X-ray powder diffraction spectrum of the phthalocyanine reaction product obtained in Synthesis Example 1 by CuKα radiation.
FIG. 6 is an X-ray diffraction spectrum of a thin film obtained by dip-coating a resin dispersion of the phthalocyanine reaction product prepared in Example 1 on a thin metal plate.
FIG. 7 is a powder X-ray diffraction spectrum of the phthalocyanine reaction product obtained in Synthesis Example 2 by CuKα radiation.
FIG. 8 is an X-ray powder diffraction spectrum of the phthalocyanine reaction product obtained in Synthesis Example 3 by CuKα radiation.
FIG. 9 is an X-ray diffraction spectrum of a thin film obtained by dip-coating a resin dispersion of a phthalocyanine reaction product prepared in Example 4 on a thin metal plate.
FIG. 10 is a powder X-ray diffraction spectrum diagram of CuOα ray of the oxytitanium phthalocyanine compound used as a raw material in Synthesis Example 4.
FIG. 11 is an X-ray powder diffraction spectrum of the phthalocyanine reaction product obtained in Synthesis Example 4 by CuKα radiation.
FIG. 12 is an X-ray diffraction spectrum of a thin film obtained by dip-coating a resin dispersion of a phthalocyanine reaction product prepared in Example 5 on a thin metal plate.
FIG. 13 is a powder X-ray diffraction spectrum of the phthalocyanine reaction product obtained in Synthesis Example 5 by CuKα radiation.
FIG. 14 is an X-ray diffraction spectrum of a thin film obtained by dip-coating a resin dispersion of the phthalocyanine reaction product prepared in Example 9 on a thin metal plate.
FIG. 15 is an X-ray powder diffraction spectrum of the phthalocyanine reaction product obtained in Comparative Synthesis Example 1 by CuKα radiation.
FIG. 16 is an X-ray diffraction spectrum of a thin film obtained by dip-coating a resin dispersion of a phthalocyanine reaction product prepared in Comparative Example 1 onto a thin metal plate.
17 is an X-ray powder diffraction spectrum of the phthalocyanine reaction product obtained in Comparative Synthesis Example 2 using CuKα radiation. FIG.
FIG. 18 is an X-ray diffraction spectrum of a thin film obtained by dip-coating a resin dispersion of a phthalocyanine reaction product prepared in Comparative Example 2 on a thin metal plate.
[Explanation of symbols]
1 conductive support
2 Charge carrier generation layer
3 charge transport layer
4a Photosensitive layer
4b Photosensitive layer
4c Photosensitive layer
5 Charge carrier generation material
6 Charge transfer media
7 Electrophotographic photoreceptor

Claims (5)

In an electrophotographic photoreceptor having a photosensitive layer formed by using a charge generation material and a charge transport material on a conductive substrate, the charge generation material comprises an oxytitanium phthalocyanine compound, (2R, 3R) -2,3-butanediol and And / or contains a reaction product with (2S, 3S) -2,3-butanediol, and the reaction product has a Bragg angle (2θ ± 0.2 °) of 8 in the X-ray diffraction spectrum of Cu-Kα. 0.3, 24.7 and 25.1, and the charge transporting material has the general formula (I)

(Wherein, Ar ₁ , Ar ₂ and Ar ₃ each independently represent an aromatic ring group which may have a substituent or a heterocyclic group which may have a substituent, or —NAr ₂ ( Ar ₃ ) may form a ring.) An electrophotographic photoreceptor comprising at least one compound represented by the formula: In an electrophotographic photoreceptor having a photosensitive layer formed by using a charge generation material and a charge transport material on a conductive substrate, the charge generation material comprises an oxytitanium phthalocyanine compound, (2R, 3R) -2,3-butanediol and 7. The photosensitive layer contains a reaction product with (2S, 3S) -2,3-butanediol, and the photosensitive layer has a Bragg angle (2θ ± 0.2 °) in an X-ray diffraction spectrum of Cu-Kα. Having a main peak at 3 ° and a charge transporting material represented by general formula (I)

(Wherein, Ar ₁ , Ar ₂ and Ar ₃ each independently represent an aromatic ring group which may have a substituent or a heterocyclic group which may have a substituent, or —NAr ₂ ( Ar ₃ ) may form a ring.) An electrophotographic photoreceptor comprising at least one compound represented by the formula: 2. The electrophotographic photoconductor according to claim 1, wherein the photosensitive layer has a charge generation layer composed of a charge generation material and a charge transport layer formed by dispersing a charge transport material in a binder resin. The charge transport material has the general formula (II)

(Wherein, Ar ₄ represents an aromatic ring group which may have a substituent or a heterocyclic group which may have a substituent. Two different benzene rings form a ring via Y. When forming a ring, Y represents a residue necessary for bonding to different benzene rings to form a ring, and R ₁ and R ₂ each independently represent a hydrogen atom or a halogen atom. , An alkoxy group, an alkyl group which may have a substituent or a phenyl group which may have a substituent.), A compound represented by the general formula (III)

(In the formula, Ar ₅ and Ar ₆ represent an aromatic ring group which may have a substituent or a heterocyclic group which may have a substituent, and two different benzene rings are linked via W When forming a ring, W represents a residue necessary for bonding to different benzene rings to form a ring, and R ₃ , R ₄ , R ₅ and R ₆ represent Each independently represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group which may have a substituent or a phenyl group which may have a substituent.) And a compound represented by the general formula (IV)

(In the formula, m represents 0 or 1, and Ar ₇ , Ar ₈ , Ar _9, and Ar ₁₀ each independently represent an aromatic ring group which may have a substituent, And Z represents an oxygen atom, a sulfur atom, an optionally substituted aminylene group, an optionally substituted divalent aromatic residue or a substituent. May represent a divalent heterocyclic residue which may be different from each other, and two different benzene rings may form a ring via W. In the case of forming a ring, W is bonded to different benzene rings to form a ring. R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent a hydrogen atom, a halogen atom, an alkoxy group, or an alkyl which may have a substituent; Represents a phenyl group which may have a group or a substituent.) Claim 1 or 2 electrophotographic photosensitive member according to characterized in that it contains at least one compound that The binder resin used for the charge transport material is represented by the general formula (V)

(In the formula, a hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group, and R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, or an aromatic group. May have a substituent.) Polycarbonate having a repeating unit represented by the general formula (VI)

(In the formula, a hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group, and W represents a group of atoms necessary for forming a carbocyclic ring and a heterocyclic ring. And a repeating unit represented by formula (V) and a repeating unit represented by formula (VII):

Wherein a hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group, and these groups may have a substituent. General formula (VIII)

(Where the hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group, and these groups may have a substituent). The electrophotographic photoconductor according to claim 1, wherein the electrophotographic photoconductor contains at least one or more kinds of polycarbonates or polyarylates selected from the group.

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