JP4283052B2 - Aromatic polycarbonate resin and electrophotographic photoreceptor using the same - Google Patents

Description

【００１１】
一般式（１）において、Ａｒ¹、Ａｒ²、及びＡｒ³は水素原子、置換基を有していてもよいアルキル基、置換基を有してもよいアラルキル基、または置換基を有してもよいアリール基を示し、Ａｒ⁴は置換基を有してもよいアリール基を示し、Ａｒ⁵及びＡｒ⁶は置換基を有してもよいアリーレン基を示し、ｎは０〜２の整数を示す。
【００１２】
〔２〕下記一般式（２）で示される構成単位を含有する芳香族ポリカーボネート樹脂。
【００１３】
【化７】

【００１４】
一般式（２）において、Ａｒ¹、Ａｒ²、及びＡｒ³は水素原子、置換基を有していてもよいアルキル基、置換基を有してもよいアラルキル基、または置換基を有してもよいアリール基を示し、Ａｒ⁴は置換基を有してもよいアリール基を示し、Ａｒ⁵は置換基を有してもよいアリーレン基を示し、ｎは０〜２の整数を示す。
【００１５】
〔３〕下記一般式（３）で示される構成単位を含有する芳香族ポリカーボネート樹脂。
【００１６】
【化８】

【００１７】
一般式（３）において、Ａｒ¹及びＡｒ²は水素原子、置換基を有していてもよいアルキル基、置換基を有してもよいアラルキル基、または置換基を有してもよいアリール基を示し、Ａｒ⁴は置換基を有してもよいアリール基を示す。
【００１８】
〔４〕上記〔１〕における一般式（１）及び下記一般式（４）で示される構成単位からなる芳香族ポリカーボネート樹脂。
【００１９】
【化９】

【００２０】
一般式（４）において、Ｘは置換または無置換の鎖状脂肪族２価基、置換または無置換の環状脂肪族２価基、置換または無置換の芳香族２価基、置換または無置換の複素環２価基、またはこれらを連結して出来る２価基、またはこれらの２価基と酸素原子及び硫黄原子を含む群の中から任意のものを連結して出来る２価基を示す。
【００２１】
〔５〕上記〔４〕における一般式（１）で示される構成単位が、上記〔２〕における一般式（２）で示される構成単位であることを特徴とする芳香族ポリカーボネート樹脂。
【００２２】
〔６〕上記〔４〕における一般式（１）で示される構成単位が、上記〔３〕における一般式（３）で示される構成単位であることを特徴とする芳香族ポリカーボネート樹脂。
【００２３】
〔７〕上記〔４〕における一般式（４）中のＸが、下記一般式（５）で示される構成単位であることを特徴とする芳香族ポリカーボネート樹脂。
【００２４】
【化１０】

【００２５】
一般式（５）において、Ｒ¹及びＲ²は水素原子、Ｃ₁〜Ｃ₄の低級アルキル基、Ｃ₁〜Ｃ₄の低級アルコキシ基、またはハロゲン原子を示し、Ｙは単結合、酸素原子、硫黄原子、置換または無置換の鎖状脂肪族２価基、置換または無置換の環状脂肪族２価基、またはこれらを連結して出来る２価基を示し、ｊ及びｋはそれぞれ独立して１〜４の整数を示し、ｊ及びｋのそれぞれについて２以上の場合は、Ｒ¹及びＲ²のそれぞれについて、同じ置換基であってもよいし異なった置換基であってもよい。
【００２６】
〔８〕上記〔５〕における一般式（４）中のＸが、上記〔７〕における一般式（５）で示される構成単位であることを特徴とする芳香族ポリカーボネート樹脂。
【００２７】
〔９〕上記〔６〕における一般式（４）中のＸが、上記〔７〕における一般式（５）で示される構成単位であることを特徴とする芳香族ポリカーボネート樹脂。
【００２８】
また、本発明の芳香族ポリカーボネート樹脂を用いることにより得られる、優れた電子写真感光体としては、以下の〔１０〕〜〔１８〕で示される電子写真感光体が挙げられる。
【００２９】
〔１０〕導電性支持体上に、上記〔１〕における一般式（１）で示される構成単位を含有する芳香族ポリカーボネート樹脂を含む感光層を有することを特徴とする電子写真感光体。
【００３０】
〔１１〕導電性支持体上に、上記〔２〕における一般式（２）で示される構成単位を含有する芳香族ポリカーボネート樹脂を含む感光層を有することを特徴とする電子写真感光体。
【００３１】
〔１２〕導電性支持体上に、上記〔３〕における一般式（３）で示される構成単位を含有する芳香族ポリカーボネート樹脂を含む感光層を有することを特徴とする電子写真感光体。
【００３２】
〔１３〕導電性支持体上に、上記〔４〕に記載の芳香族ポリカーボネート樹脂を含む感光層を有することを特徴とする電子写真感光体。
【００３３】
〔１４〕導電性支持体上に、上記〔５〕に記載の芳香族ポリカーボネート樹脂を含む感光層を有することを特徴とする電子写真感光体。
【００３４】
〔１５〕導電性支持体上に、上記〔６〕に記載の芳香族ポリカーボネート樹脂を含む感光層を有することを特徴とする電子写真感光体。
【００３５】
〔１６〕導電性支持体上に、上記〔７〕に記載の芳香族ポリカーボネート樹脂を含む感光層を有することを特徴とする電子写真感光体。
【００３６】
〔１７〕導電性支持体上に、上記〔８〕に記載の芳香族ポリカーボネート樹脂を含む感光層を有することを特徴とする電子写真感光体。
【００３７】
〔１８〕導電性支持体上に、上記〔９〕に記載の芳香族ポリカーボネート樹脂を含む感光層を有することを特徴とする電子写真感光体。
【００３８】
【発明の実施の形態】
以下に本発明の芳香族ポリカーボネート樹脂について詳細に説明する。本発明のポリカーボネート樹脂は、従来よりポリカーボネート樹脂の製造法として公知である、ビスフェノールと炭酸誘導体との重合法で製造出来る。すなわち下記一般式（６）、（７）、または（８）で示される電荷輸送能を有するビスヒドロキシ置換化合物を少なくとも１種以上使用し、或いはこれらと下記一般式（９）で示されるビスヒドロキシ置換化合物とを併用し、ホスゲン、或いはトリホスゲン等のハロゲン化カルボニル化合物を用いた溶液重合、或いは界面重合により、またはビスアリールカーボネートとのエステル交換法により、またはビスヒドロキシ置換化合物から得られるビスクロロホルメートを用いる方法等により製造される。
【００３９】
【化１１】

【００４０】
一般式（６）におけるＡｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴、Ａｒ⁵、Ａｒ⁶、及びｎは、前記一般式（１）と同じ。
【００４１】
【化１２】

【００４２】
一般式（７）におけるＡｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴、Ａｒ⁵、及びｎは、前記一般式（２）と同じ。
【００４３】
【化１３】

【００４４】
一般式（８）におけるＡｒ¹、Ａｒ²、及びＡｒ⁴は、前記一般式（３）と同じ。
【００４５】
【化１４】

【００４６】
一般式（９）におけるＸは、前記一般式（４）と同じ。
【００４７】
前記したように、一般式（６）、（７）、または（８）で示される電荷輸送能を有するビスヒドロキシ置換化合物１種以上と併用して、前記（９）で示されるビスヒドロキシ置換化合物を使用し、機械的特性や溶解性等の改良された共重合体を製造することが出来る。この場合、一般式（９）で示されるビスヒドロキシ置換化合物を１種或いは２種以上併用しても良い。一般式（６）、（７）、または（８）で示される電荷輸送能を有するビスヒドロキシ置換化合物と一般式（９）で示されるビスヒドロキシ置換化合物との割合は、所望の特性により広い範囲から選択することが出来る。
【００４８】
また、適当な重合操作を選択することにより、共重合体の中でもランダム共重合体、ブロック共重合体、交互共重合体、ランダムブロック共重合体等を得ることが出来る。例えば、一般式（６）、（７）、または（８）で示される電荷輸送能を有するビスヒドロキシ置換化合物１種以上と、一般式（９）で示されるビスヒドロキシ置換化合物を、最初から均一に混合してホスゲンとの縮合反応を行えば一般式（１）、（２）、または（３）で示される構成単位と一般式（４）で示される構成単位とからなるランダム共重合体が得られるし、また幾種類かのビスヒドロキシ置換化合物を反応の途中から加えれば、ランダムブロック共重合体が得られる。また、一般式（９）で示されるビスヒドロキシ置換化合物から誘導されるビスクロロフォルメートと、一般式（６）、（７）、または（８）で示される電荷輸送能を有するビスヒドロキシ置換化合物との縮合反応を行えば、交互共重合体が得られる。
【００４９】
ハロゲン化カルボニル化合物や、クロロフォルメートを用いる方法で、界面重合で行う場合には、ビスヒドロキシ置換化合物のアルカリ水溶液と、水に対し実質的に不溶性であり、かつポリカーボネート樹脂を溶解する有機溶媒との２相間で炭酸誘導体及び触媒の存在下に反応を行う。この際、高速撹拌や乳化剤の添加によって反応媒体を乳化させて行うことにより、短時間で分子量分布の狭いポリカーボネート樹脂を得ることが出来る。アルカリ水溶液に用いる塩基としては、水酸化ナトリウム、水酸化カリウム等の水酸化物、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム等の炭酸塩等が用いられる。これらの塩基は単独でも、あるいは混合して用いてもよいが、好ましくは水酸化ナトリウムまたは水酸化カリウムが用いられる。
【００５０】
有機溶剤としては、ジクロロメタン、クロロホルム、１，２−ジクロロエタン、１，２−ジクロロエチレン、クロロベンゼン、ジクロロベンゼン等のハロゲン化炭化水素や、テトラヒドロフラン、ジオキサン等の環状エーテル類が好ましく用いられるが、これらにトルエン、キシレン、ヘキサン、シクロヘキサン等の炭化水素を混合して用いてもよい。
【００５１】
ポリカーボネート製造時に使用されるポリカーボネート生成触媒としては、トリメチルアミン、トリエチルアミン、トリ−ｎ−プロピルアミン等の三級アミン、ベンジルトリメチルアンモニウムクロライド、テトラエチルアンモニウムブロマイド、テトラメチルアンモニウムクロライド等の四級アンモニウム塩、トリエチルホスフィン、トリフェニルホスフィン等の三級ホスフィン、ベンジルトリエチルホスホニウムクロライド、ベンジルトリフェニルホスホニウムクロライド等の四級ホスホニウム塩、Ｎ−エチルピリジン、Ｎ，Ｎ′−ジメチルピペラジン、４−メチルピリジン、１−メチルイミダゾール等の含窒素複素環化合物が用いられるが、好ましくは三級アミンが、さらにより好ましくはトリエチルアミンが用いられる。これらの触媒は、ホスゲンやトリホスゲン、ビスクロロホルメート化合物等の炭酸誘導体を反応系に加える際、あるいはその前後に添加することが出来る。
【００５２】
また、分子量調節剤として、フェノール、ｐ−ｔｅｒｔ−ブチルフェノール等のフェノール類を末端停止剤として用いることが望ましい。また、アルカリ水溶液中でのビスヒドロキシ置換化合物の酸化を防ぐためにハイドロサルファイトナトリウム等の酸化防止剤を加えてもよい。反応温度は、通常０〜４０℃、反応時間は数分〜６時間である。
【００５３】
上記の方法に従って製造される芳香族ポリカーボネート樹脂には、必要に応じ酸化防止剤、光安定剤、熱安定剤、滑剤、可塑剤等の添加剤を加えることが出来る。以下、本発明のポリカーボネート樹脂について、さらに詳細に説明する。
【００５４】
本発明の芳香族ポリカーボネート樹脂は、前記一般式（１）、（２）、または（３）で示される繰り返し単位からなる単独重合体、または前記一般式（１）と（４）で示される繰り返し単位からなる交互共重合体、または前記一般式（２）と（４）で示される繰り返し単位からなる交互共重合体、または（３）と（４）で示される繰り返し単位からなる交互共重合体、あるいは前記一般式（１）と（４）で示される繰り返し単位を構成単位とするランダムまたはブロック共重合体、または前記一般式（２）と（４）で示される繰り返し単位を構成単位とするランダムまたはブロック共重合体、または前記一般式（３）と（４）で示される繰り返し単位を構成単位とするランダムまたはブロック共重合体のいずれでもよい。また、本発明の芳香族ポリカーボネート樹脂の分子量は、ポリスチレン換算数平均分子量で１０００〜１００００００、好ましくは５０００〜１０００００である。
【００５５】
本発明の芳香族ポリカーボネート樹脂を構成する、前記（１）〜（５）で示される繰り返し単位を与える置換基の具体例を以下に示す。
【００５６】
（１）、（２）、または（３）におけるＡｒ¹、Ａｒ²、及びＡｒ³の具体例としては、水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｎ−ヘキシル基、ｎ−オクチル基、ｎ−オクタデシル基、２−メトキシエチル基、シクロヘキシル基などのアルキル基、ベンジル基、４−メチルベンジル基、３−メトキシベンジル基、２−（４−クロロフェニル）エチル基などのアラルキル基、またはフェニル基、４−メチルフェニル基、２メトキシフェニル基、４−クロロフェニル基、３−ジエチルアミノフェニル基、１−ナフチル基、１−ピレニル基などのアリール基を挙げることができる。
【００５７】
また、（１）、（２）、または（３）におけるＡｒ⁴の具体例としては、フェニル基、４−メチルフェニル基、２メトキシフェニル基、４−クロロフェニル基、３−ジエチルアミノフェニル基、１−ナフチル基、１−ピレニル基などのアリール基を挙げることができる。
【００５８】
また、（１）または（２）におけるＡｒ⁵及びＡｒ⁶の具体例としては、１，４−フェニレン基、１，２−フェニレン基、１，３−フェニレン基、２−メチル−１，４−フェニレン基、３−エチル−１，２−フェニレン基、２−クロロ−１，４−フェニレン基、４−メチル−１，３−フェニレン基、１，４−ナフチレン基、１，８−ナフチレン基、９，１０−アントリレン基、２，７−フェナントリレン基、４，４′−ビフェニレン基、３，４′−ビフェニレン基、などのアリーレン基を挙げることができる。
【００５９】
また、（１）または（２）におけるｎは、０〜２の整数を示す。
【００６０】
また、（４）におけるＸの具体例としては、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ヘキサメチレン基、２−メチルペンタメチレン基、２−クロロテトラメチレン基、３−メトキシペンタメチレン基などの鎖状脂肪族２価基、１，３−シクロペンチレン基、１，４−シクロヘキシレン基、シクロヘキサン−１，１−ジイル基、２，３−ジメトキシ−１，４−シクロヘキシレン基などの環状脂肪族２価基、フェニレン基、ナフチレン基、ビフェニリレン基、ターフェニリレン基、フルオレン−２，７−ジイル基、フェナントレン−２，７−ジイル基、ピレン−１，６−ジイル基、９，９−ジメチルフルオレン−２，７−ジイル基、スチルベン−４，４′−ジイル基などの芳香族２価基、１，４−ジメチルピペラジン−２，５−ジイル基、フラン−２，５−ジイル基、チオフェン−２，５−ジイル基、ピリジン−２，４−ジイル基、１−メチルインドール−４，６−ジイル基、Ｎ−エチルカルバゾール−３，６−ジイル基、３−メチルピラゾール−１，４−ジイル基、３−（４−メトキシフェニル）ピラゾール−１，４−ジイル基などの複素環２価基、またはこれらの基を連結して出来るシクロヘキシルベンゼン−４，４′−ジイル基、２−フェニルピリジン−３，４′−ジイル基、ジフェニルメタン−４，４′−ジイル基、２，２−ジフェニルプロパン−４′，４″−ジイル基、１，１−ジフェニルヘキサン−４′，４″−ジイル基、１，５−ジフェニルペンタン−４′，４″−ジイル基などの２価基、またはこれらの２価基と酸素原子及び硫黄原子を含む群の中から任意のものを連結して出来るジフェニルエーテル−４，４′−ジイル基、ジフェニルスルフィド−４，４′−ジイル基、３，６−ジオキサオクタン−１，８−ジイル基、３，６，９−トリオキサウンデカン−１，１１−ジイル基などの２価基を挙げることが出来る。
【００６１】
また、（５）におけるＲ¹及びＲ²の具体例としては、水素原子、またはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基などのＣ₁〜Ｃ₄の低級アルキル基、またはメトキシ基、エトキシ基、ｎ−プロピルオキシ基、イソプロピルオキシ基、ｎ−ブチルオキシ基などのＣ₁〜Ｃ₄の低級アルコキシ基、またはフッ素原子、塩素原子、臭素原子などのハロゲン原子を挙げることが出来る。また、Ｙの具体例としては、単結合、酸素原子、硫黄原子、またはメチレン基、エチレン基、トリメチレン基、テトラメチレン基、ヘキサメチレン基、４−メチルペンタメチレン基、２−クロロテトラメチレン基、３−メトキシペンタメチレン基などの鎖状脂肪族２価基、または１，３−シクロペンチレン基、１，４−シクロヘキシレン基、シクロヘキサン−１，１−ジイル基、２，３−ジメトキシ−１，４−シクロヘキシレン基などの環状脂肪族２価基、またはこれらを連結して出来るエチルシクロヘキサン−２，４′−ジイル基、３，６−ジオキサオクタン−１，８−ジイル基、などの２価基を挙げることが出来る。ｊ及びｋはそれぞれ独立して１〜４の整数を示し、ｊ及びｋのそれぞれについて２以上の場合は、Ｒ¹及びＲ²のそれぞれについて、同じ置換基であってもよいし、異なった置換基であってもよい。
【００６２】
本発明の芳香族ポリカーボネート樹脂の製造に用いられる、従来知られていなかった全く新しい電荷輸送能を有する一般式（６）、（７）、または（８）で示されるビスヒドロキシ置換化合物の好ましい例としては、Ａｒ¹及びＡｒ²の双方がメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基などのＣ₁〜Ｃ₄の低級アルキル基、またはフェニル基、４−メチルフェニル基、３−メチルフェニル基、４−フロロフェニル基、４−クロロフェニル基などの、無置換、またはＣ₁〜Ｃ₄の低級アルキル基、あるいはハロゲン原子で置換されたフェニル基、Ａｒ³が水素原子、Ａｒ⁴がフェニル基、４−メチルフェニル基、３−メチルフェニル基、４−エトキシフェニル基、４−フロロフェニル基、４−クロロフェニル基などの、無置換、またはＣ₁〜Ｃ₄の低級アルキル基、あるいはハロゲン原子で置換されたフェニル基、Ａｒ⁵が１，４−フェニレン基、Ａｒ⁵が１，４−フェニレン基、１，２−フェニレン基、等の無置換のフェニレン基で、ｎが０または１である化合物が挙げられる。
【００６３】
一般式（６）、（７）、または（８）で示されるビスヒドロキシ置換化合物の好ましい具体例としては、以下に示すＥＡ−１〜５５の化合物を挙げることが出来るが、これらに限定されるものではない。
【００６４】
【表１】

【００６５】
【表２】

【００６６】
また、一般式（９）で示されるビスヒドロキシ置換化合物の好ましい具体例としては、以下に示すＭＡ−１〜５０の化合物を挙げることが出来るが、これらに限定されるものではない。
【００６７】
【化１５】

【００６８】
【化１６】

【００６９】
【化１７】

【００７０】
【化１８】

【００７１】
【化１９】

【００７２】
本発明の芳香族ポリカーボネート樹脂の具体例としては、先に記述した置換基を有する、前記一般式（１）、（２）、または（３）で示される構成単位を含有する芳香族ポリカーボネート樹脂、あるいは、前記一般式（１）と（４）、または（２）と（４）、または（３）と（４）で示される構成単位を含有する芳香族ポリカーボネート樹脂、あるいは、前記一般式（１）と（５）、または（２）と（５）、または（３）と（５）で示される構成単位を含有する芳香族ポリカーボネート樹脂が挙げられるが、好ましい具体例としては、上記のＥＡ−１〜５５の化合物のいずれか１個または複数個を用いて、前述のごとく合成された芳香族ポリカーボネート樹脂、或いは上記のＥＡ−１〜５５の化合物のいずれか１個または複数個と、上記のＭＡ−１〜５０の化合物のいずれか１個または複数個を併用して合成された芳香族ポリカーボネート樹脂を挙げることが出来る。
【００７３】
以上のようにして得られる本発明の芳香族ポリカーボネート樹脂は、有機光導電性化合物として、センサー材料や有機ＥＬ素子等の電子デバイスや、また特に前述の有機電子写真感光体の、電荷輸送物質として好適に用いることが出来る。
【００７４】
次に本発明の有機電子写真感光体（以下、電子写真感光体と略す）について説明する。本発明の電子写真感光体は上記の請求項１〜９記載の芳香族ポリカーボネート樹脂を含む感光層を有するものである。
【００７５】
これらを含有する感光層を含む電子写真感光体の形態は、いずれのものでも用いることができる。例えば、導電性支持体上に電荷発生物質、電荷輸送物質、及びフィルム形成性結着剤樹脂からなる感光層を設けた、単層型の感光体や、導電性支持体上に、電荷発生物質と結着剤樹脂からなる電荷発生層と、電荷輸送物質と結着剤樹脂からなる電荷輸送層をこの順に設けた、機能分離型と呼ばれる積層型の感光体が知られているが、本発明の化合物はいずれの構成においても、これらの電荷輸送物質として極めて有用である。
【００７６】
本発明の化合物を用いて感光体を作製する支持体としては、金属製ドラム、金属板、導電性加工を施した紙やプラスチックフィルムのシート状、ドラム状あるいはベルト状の支持体などが使用される。
【００７７】
また、上記構成における電荷発生物質には無機系電荷発生物質と有機系電荷発生物質があり、前者の例としては例えばセレン、セレン−テルル合金、セレン−ヒ素合金、硫化カドミウム、酸化亜鉛、アモルファスシリコンなどが挙げられる。後者の例としては、例えばメチルバイオレット、ブリリアントグリーン、クリスタルバイオレットなどのトリフェニルメタン系染料、メチレンブルーなどのチアジン染料、キニザリンなどのキノン染料、シアニン染料、アクリジン染料、ピリリウム色素、チアピリリウム色素、スクエアリウム色素、フタロシアニン系顔料、アゾ系顔料、ペリノン系顔料、アントラキノン系顔料、ペリレン系顔料、等があるが、特に良く用いられるのは、金属含有あるいは無金属のフタロシアニン系顔料、またはビスアゾ顔料やトリスアゾ顔料等の、アゾ系顔料である。
【００７８】
フタロシアニン系顔料の例としては、無金属フタロシアニンは、特公昭４９−４３３８号公報、特開昭５８−１８２６３９号公報、或いはＪ．Ｐｈｙｓ．Ｃｈｅｍ．７２，３２３０（１９６８）に記載されているものを、チタニルオキシフタロシアニンは、特開昭６１−２１７０５０号公報、特開昭６２−６７０９４号公報、特開昭６３−３６５号公報、特開昭６３−１９８０６７号公報、特開昭６４−１７０６６号公報、或いは特開平１−１８９２００号公報に記載されているものを、銅フタロシアニンは、特公昭５２−１６６７号公報、或いは特開昭５１−１０８８４７号公報に記載されているものを、クロロアルミニウムフタロシアニンは、特開昭５８−１５８６４９号公報に記載されているものを、クロロインジウムフタロシアニンは特開平７−１３３７５号公報に記載されているものを、バナジルオキシフタロシアニンは、特開昭６３−１８３６１号公報、特開平１−２０４９６８号公報、特開平３−２６９０６３号公報、或いは特開平７−２４７４４２号公報に記載されているものを、ジフェノキシゲルマニウムフタロシアニンは、特開平４−３６０１５０号公報に記載されているものを、クロロガリウムフタロシアニンは、特開平５−１９４５２３号公報、或いは特開平７−１０２１８３号公報に記載されているものを、ヒドロキシガリウムフタロシアニンは、特開平５−２６３００７号公報、或いは特開平７−５３８９２号公報に記載されているものを、それぞれ挙げることができる。
【００７９】
アゾ系顔料の例としては、特開昭４７−３７５４３号公報に記載のベンジジン型ビスアゾ顔料、特開昭５６−１１６０３９号公報に記載のベンゾオキサゾール型ビスアゾ顔料、特開昭５７−１７６０５５号公報に記載のオキサジアゾール型ビスアゾ顔料、特公昭６０−４５６６４号公報に記載のフルオレノン型ビスアゾ顔料、或いは特開平１−２００２６７号公報や特開平１−２０２７５７号公報に記載のピラゾール型ビスアゾ顔料、などのようなビスアゾ顔料、または特開昭５７−１９５７６７号公報に記載のトリフェニルアミン型トリスアゾ顔料のようなトリスアゾ顔料を挙げることができる。
【００８０】
【実施例】
次に本発明を実施例により更に詳細に説明するが、本発明はこれらに何ら限定されるものではない。
【００８１】
実施例１
先の表１に記載の電荷輸送能を有するビスヒドロキシ置換化合物ＥＡ−１４：３．１２ｇ、先の一般式（９）で示されるビスヒドロキシ置換化合物ＭＡ−３１：１．５０ｇ、及び分子量調節剤として４−ｔ−ブチルフェノール：０．０５ｇを３００ｍｌ三つ口フラスコに入れ、ハイドロサルファイトナトリウム：０．０６ｇ、及び水酸化ナトリウム：２．６７ｇを蒸留水：４１ｍｌに溶かした溶液を加え、窒素気流下、室温でメカニカルスターラーで撹拌した。トリホスゲン：１．６０ｇをクロロホルム：５５ｍｌに溶かした溶液を加え、さらに３分後にトリエチルアミン：０．１ｍｌを加え、室温で２時間撹拌した。重合停止剤として、クロロギ酸フェニル：０．１３ｇをクロロホルム：２ｍｌに溶かした溶液を加え、さらに２時間室温下で撹拌した。クロロホルム：１５０ｍｌを追加し、２．５％水酸化ナトリウム溶液で洗浄、次いで１規定塩酸で洗浄、さらに蒸留水で洗浄した後、硫酸マグネシウムを加え、よく振りまぜて乾燥、減圧下約８０ｍｌに濃縮し、メタノール：３００ｍｌに注入して沈殿した結晶を濾取した。この結晶を再度７０ｍｌ：クロロホルムに溶かし、メタノール：３００ｍｌに注入する再沈殿処理を２回繰り返し、室温で減圧乾燥させて、目的とする下記のポリカーボネート樹脂（１０）：２．９２ｇ（７２．５％）を得た。
【００８２】
【化２０】

【００８３】
このものは、¹Ｈ−ＮＭＲ（δ，ｐｐｍ，ＣＤＣｌ₃）において、７．３５〜７．１５（ｍ，面積比：１５．００Ｈ）、７．１４〜６．８０（ｍ，同：１４．０６Ｈ）、６．７７（ｂｒｓ，同：３．７７Ｈ）、６．６４（ｓ，同：１．００Ｈ）のピークを示している事、及びその面積比から、その構造及びＥＡ−１４由来の部分とＭＡ−３１由来の部分のモル組成比が確認された。
【００８４】
得られたポリカーボネート樹脂の分子量をゲルパーミュエーションクロマトグラフィーにより測定したところ、ポリスチレン換算の分子量は以下の通りであった。
【００８５】
数平均分子量：２６０００
重量平均分子量：５２０００
【００８６】
また、ＩＲ分析から、得られたポリカーボネート樹脂の、カーボネート部分のＣ＝Ｏ伸縮振動によるＩＲ吸収が、１７７５ｃｍ^-1に観測された。
【００８７】
同様にして以下の表３の実施例２〜２０に示すようなポリカーボネート樹脂を合成した。
【００８８】
【表３】

【００８９】
実施例２１
電荷発生物質として、下記構造式のビスアゾ顔料（Ｐ−１）１重量部及びポリエステル樹脂（東洋紡績製バイロン２００）１重量部をテトラヒドロフラン１００重量部と混合し、ペイントコンディショナー装置でガラスビーズと共に２時間分散した。こうして得た分散液を、アプリケーターにてアルミ蒸着ポリエステル上に塗布して乾燥し、膜厚約０．２μｍの電荷発生層を形成した。次に、電荷輸送物質として、本発明の化合物（１０）を、テトラヒドロフランを溶媒として１０重量％の溶液を作り、上記の電荷発生層の上にアプリケーターで塗布して膜厚約１８μｍの電荷輸送層を形成した。
【００９０】
【化２１】

【００９１】
この様にして作製した積層型感光体について、静電記録試験装置（川口電機製ＥＰＡ−８２００）を用いて電子写真特性の評価を行った。
測定条件：印加電圧−６ｋＶ、スタティックNo. ３（ターンテーブルの回転スピードモード：１０ｍ／ｍｉｎ ）。その結果、帯電電位（Ｖ₀）が−６５０Ｖ、半減露光量（Ｅ1/2）が０．７５ルックス・秒と高感度の値を示した。
【００９２】
更に同装置を用いて、帯電−除電（除電光：白色光で４００ルックス×１秒照射）を１サイクルとする繰返し使用に対する特性評価を行った。５０００回での繰返しによる帯電電位の変化を求めたところ、１回目の帯電電位（Ｖ₀）−６５０Ｖに対し、５０００回目の帯電電位（Ｖ₀）は−６４０Ｖであり、繰返しによる電位の低下がほとんどなく安定した特性を示した。また、１回目の半減露光量（Ｅ1/2）０．７５ルックス・秒に対して５０００回目の半減露光量（Ｅ1/2）は０．７５ルックス・秒と変化がなく優れた特性を示した。
【００９３】
実施例２２〜４８
実施例１のビスアゾ顔料（Ｐ−１）及び本発明の化合物（１０）の代わりに、それぞれ下記構造式（Ｐ−１）〜（Ｐ−５）のビスアゾ顔料、及び表３に示す本発明の化合物を用いた他は、実施例１と同様にして感光体を作製してその特性を評価した。結果を表４に示す。
【００９４】
【化２２】

【００９５】
【化２３】

【００９６】
【化２４】

【００９７】
【化２５】

【００９８】
【表４】

【００９９】
実施例４９
電荷発生物質として、ビスアゾ顔料（Ｐ−１）の代わりにＣｕＫα１．５４１ÅのＸ線に対するブラッグ角（２θ±０．２°）が、９．５°、９．７°、１１．７°、１５．０°、２３．５°、２４．１°、２７．３°に主要なピークを示すＸ線回折スペクトルを有するチタニルオキシフタロシアニン（Ｙ型チタニルオキシフタロシアニン）を用いた他は、実施例２１と同様にして感光体を作製し、その特性を実施例２１と同様に評価した。結果は、帯電電位（Ｖ₀）が−５２０Ｖ、半減露光量（Ｅ1/2）が０．２５ルックス・秒と高感度の値を示した。また、繰返し使用に対する特性評価でも、１回目の帯電電位（Ｖ₀）−５２０Ｖに対し、５０００回目の帯電電位（Ｖ₀）は−５１０Ｖであり、繰返しによる電位の低下がほとんどなく安定した特性を示した。また、１回目の半減露光量（Ｅ1/2）０．２５ルックス・秒に対して５０００回目の半減露光量（Ｅ1/2）は０．２５ルックス・秒と変化がなく優れた特性を示した。
【０１００】
実施例５０〜６８
実施例４９の本発明の化合物（１０）の代わりに表３に示す本発明の化合物を用いた他は、実施例４９と同様にして感光体を作製してその特性を評価した。結果を表５に示す。
【０１０１】
【表５】

【０１０２】
【発明の効果】
本発明の芳香族ポリカーボネート樹脂は、前述のように、それ自身が光導電性材料として有用であり、特に電子写真感光体の電荷輸送物質として優れた働きを示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel aromatic polycarbonate resin useful as an organic photoconductive material for use in electrophotographic photoreceptors and the like, and an electrophotographic photoreceptor using the same, in detail, which has not been known in the past. Highly sensitive and durable using a novel aromatic polycarbonate resin with charge transporting ability synthesized using a new bishydroxy-substituted compound, and a novel aromatic polycarbonate resin with charge transporting ability in the photosensitive layer The present invention relates to an electrophotographic photosensitive member.
[0002]
[Prior art]
As the aromatic polycarbonate resin, bisphenol A polycarbonate obtained by reacting phosgene or the like with 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A) is known as a typical one. For the purpose of improving heat resistance and flame resistance, polycarbonate, a compound in which a methyl group or a bromine atom is introduced into bisphenol A, and bisphenol A and various aromatic diols (for example, for the purpose of improving elasticity and solubility) 4,4'-dihydroxydiphenyl) and aliphatic diols (for example, hexanediol) have been reported. Such a polycarbonate resin generally has characteristics excellent in mechanical strength as compared with other thermoplastic resins, and particularly because of excellent weather resistance and mechanical properties at low temperature, etc. It is used in many fields.
[0003]
Polycarbonate resin is indispensable for organic electrophotographic photoconductors, which have been the mainstream photoconductor for terminal printers such as copiers and personal computers in recent years, because of their excellent wear resistance, dimensional stability, and durability. In most cases, it is used as a suitable constituent material. In a multilayer photoconductor, which is a typical example of an organic electrophotographic photoconductor, a charge generation layer containing a charge generation material is formed on a conductive support serving as a substrate, and a low molecular charge transport is formed thereon. It has a structure in which a charge transport layer (Charge Transport Layer, hereinafter abbreviated as CTL) containing a material (Charge Transport Material, abbreviated as CTL) is laminated. The outermost layer, CTL, is used as CTM and binder resin. Made of polycarbonate resin. In order to maintain the electrical characteristics as a photoconductor, an amount of CTM comparable to that of a binder resin is usually used in CTL, which reduces the mechanical strength inherent to the polycarbonate resin, and thus wear resistance of the photoconductor. It was a cause of impairing the durability and durability.
[0004]
An attempt to reduce the amount of CTM added to the CTL while maintaining the electrophotographic characteristics of the photoreceptor by improving the electrical characteristics of the CTM in order to improve the disadvantages of such an organic electrophotographic photoreceptor has been conventionally made. Various excellent CTMs having high sensitivity and high mobility characteristics have been developed so far, but in order to maintain the characteristics as a photoconductor, a certain amount or more of CTM is inevitably required. This has become a bottleneck in dramatically improving the durability of the photoreceptor.
[0005]
Furthermore, in recent years, as a means for solving this problem, and for the purpose of improving the physical and chemical durability of the photoreceptor and further improving the electrical characteristics, so-called organic polymer light that incorporates CTM into the binder. Conductive materials (polymer CTM) and organic low-molecular photoconductive materials (monomer CTM) as production intermediates have been proposed and studied. However, even with these low-molecular or high-molecular photoconductive materials that have been developed so far, in order to satisfy the demands for higher sensitivity and higher durability of the photoreceptor in the recent electrophotographic system. (For example, refer to Patent Documents 1 to 11).
[0006]
[Patent Document 1]
Japanese Patent Laid-Open No. 3-221522
[Patent Document 2]
JP-A-4-11627
[Patent Document 3]
JP-A-6-295077
[Patent Document 4]
JP-A-7-228557
[Patent Document 5]
JP 7-258399 A
[Patent Document 6]
JP-A-8-62864
[Patent Document 7]
JP-A-8-176293
[Patent Document 8]
Japanese Patent Laid-Open No. 9-194442
[Patent Document 9]
JP 2000-136169 A
[Patent Document 10]
JP 2001-72756 A
[Patent Document 11]
JP 2002-249472 A
[0007]
[Problems to be solved by the invention]
The object of the present invention is that when used as a material for an electrophotographic photosensitive member, all of the above-mentioned disadvantages of the conventional material are eliminated, the mechanical strength is excellent, the charging potential is high and the sensitivity is high, and it is used repeatedly. In addition to obtaining a photoconductor that can exhibit stable performance without changing various properties, it is widely used as a novel aromatic that exhibits excellent performance even when used in sensor materials, organic EL devices, electrostatic recording devices, etc. It is to provide a polycarbonate resin.
[0008]
[Means for Solving the Problems]
As a result of researches on organic photoconductive compounds to achieve the above object, the present inventors have synthesized a specific enamine in the molecule synthesized using a completely new bishydroxy-substituted compound as a raw material, which has not been known so far. A novel aromatic polycarbonate resin containing a unit as a structural unit has extremely excellent characteristics as an organic polymer photoconductive compound. By using this new aromatic polycarbonate resin, mechanical strength is improved. The inventors have found that an electrophotographic photosensitive member having excellent sensitivity and repetition characteristics can be obtained, and has led to the present invention. Examples of the aromatic polycarbonate resin containing the specific enamine unit as a constituent unit include the aromatic polycarbonate resins represented by the following [1] to [9].
[0009]
[1] An aromatic polycarbonate resin containing a structural unit represented by the following general formula (1).
[0010]
[Chemical 6]

[0011]
In the general formula (1), Ar ¹ , Ar ² And Ar ^Three Represents a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent; Ar ^Four Represents an aryl group which may have a substituent, Ar ^Five And Ar ⁶ Represents an arylene group which may have a substituent, and n represents an integer of 0 to 2.
[0012]
[2] An aromatic polycarbonate resin containing a structural unit represented by the following general formula (2).
[0013]
[Chemical 7]

[0014]
In the general formula (2), Ar ¹ , Ar ² And Ar ^Three Represents a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent; Ar ^Four Represents an aryl group which may have a substituent, Ar ^Five Represents an arylene group which may have a substituent, and n represents an integer of 0 to 2.
[0015]
[3] An aromatic polycarbonate resin containing a structural unit represented by the following general formula (3).
[0016]
[Chemical 8]

[0017]
In general formula (3), Ar ¹ And Ar ² Represents a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent; Ar ^Four Represents an aryl group which may have a substituent.
[0018]
[4] An aromatic polycarbonate resin comprising the structural units represented by the general formula (1) and the following general formula (4) in the above [1].
[0019]
[Chemical 9]

[0020]
In the general formula (4), X represents a substituted or unsubstituted chain aliphatic divalent group, a substituted or unsubstituted cyclic aliphatic divalent group, a substituted or unsubstituted aromatic divalent group, a substituted or unsubstituted A divalent heterocyclic group, a divalent group formed by linking these, or a divalent group formed by connecting any of these divalent groups and a group containing an oxygen atom and a sulfur atom are shown.
[0021]
[5] The aromatic polycarbonate resin, wherein the structural unit represented by the general formula (1) in [4] is the structural unit represented by the general formula (2) in [2].
[0022]
[6] The aromatic polycarbonate resin, wherein the structural unit represented by the general formula (1) in [4] is the structural unit represented by the general formula (3) in [3].
[0023]
[7] An aromatic polycarbonate resin, wherein X in the general formula (4) in the above [4] is a structural unit represented by the following general formula (5).
[0024]
[Chemical Formula 10]

[0025]
In the general formula (5), R ¹ And R ² Is a hydrogen atom, C ₁ ~ C _Four Lower alkyl group, C ₁ ~ C _Four Y represents a single bond, an oxygen atom, a sulfur atom, a substituted or unsubstituted chain aliphatic divalent group, a substituted or unsubstituted cyclic aliphatic divalent group, or these A divalent group formed by linking, j and k each independently represent an integer of 1 to 4, and in the case where each of j and k is 2 or more, R ¹ And R ² Each of these may be the same substituent or different substituents.
[0026]
[8] An aromatic polycarbonate resin, wherein X in the general formula (4) in the above [5] is a structural unit represented by the general formula (5) in the above [7].
[0027]
[9] An aromatic polycarbonate resin, wherein X in the general formula (4) in the above [6] is a structural unit represented by the general formula (5) in the above [7].
[0028]
Further, examples of the excellent electrophotographic photosensitive member obtained by using the aromatic polycarbonate resin of the present invention include electrophotographic photosensitive members represented by the following [10] to [18].
[0029]
[10] An electrophotographic photoreceptor comprising a photosensitive layer containing an aromatic polycarbonate resin containing the structural unit represented by the general formula (1) in [1] above on a conductive support.
[0030]
[11] An electrophotographic photosensitive member having a photosensitive layer containing an aromatic polycarbonate resin containing the structural unit represented by the general formula (2) in [2] above on a conductive support.
[0031]
[12] An electrophotographic photosensitive member comprising a photosensitive layer containing an aromatic polycarbonate resin containing the structural unit represented by the general formula (3) in [3] above on a conductive support.
[0032]
[13] An electrophotographic photoreceptor comprising a photosensitive layer containing the aromatic polycarbonate resin according to [4] above on a conductive support.
[0033]
[14] An electrophotographic photosensitive member having a photosensitive layer containing the aromatic polycarbonate resin according to [5] above on a conductive support.
[0034]
[15] An electrophotographic photoreceptor comprising a photosensitive layer containing the aromatic polycarbonate resin described in [6] above on a conductive support.
[0035]
[16] An electrophotographic photoreceptor comprising a photosensitive layer containing the aromatic polycarbonate resin according to [7] above on a conductive support.
[0036]
[17] An electrophotographic photoreceptor comprising a photosensitive layer containing the aromatic polycarbonate resin according to [8] above on a conductive support.
[0037]
[18] An electrophotographic photosensitive member having a photosensitive layer containing the aromatic polycarbonate resin described in [9] above on a conductive support.
[0038]
DETAILED DESCRIPTION OF THE INVENTION
The aromatic polycarbonate resin of the present invention is described in detail below. The polycarbonate resin of the present invention can be produced by a polymerization method of bisphenol and a carbonic acid derivative, which is conventionally known as a method for producing a polycarbonate resin. That is, at least one bishydroxy-substituted compound having a charge transport ability represented by the following general formula (6), (7), or (8) is used, or these and a bishydroxyl represented by the following general formula (9). A bischloroform obtained from a bishydroxy substituted compound by solution polymerization using a carbonyl compound such as phosgene or triphosgene, or by interfacial polymerization, or by transesterification with bisaryl carbonate It is manufactured by a method using a mate.
[0039]
Embedded image

[0040]
Ar in the general formula (6) ¹ , Ar ² , Ar ^Three , Ar ^Four , Ar ^Five , Ar ⁶ And n are the same as those in the general formula (1).
[0041]
Embedded image

[0042]
Ar in the general formula (7) ¹ , Ar ² , Ar ^Three , Ar ^Four , Ar ^Five And n are the same as those in the general formula (2).
[0043]
Embedded image

[0044]
Ar in the general formula (8) ¹ , Ar ² And Ar ^Four Is the same as in the general formula (3).
[0045]
Embedded image

[0046]
X in the general formula (9) is the same as that in the general formula (4).
[0047]
As described above, the bishydroxy-substituted compound represented by the above (9) is used in combination with one or more bishydroxy-substituted compounds having a charge transporting ability represented by the general formula (6), (7), or (8). Can be used to produce a copolymer with improved mechanical properties and solubility. In this case, one or more bishydroxy-substituted compounds represented by the general formula (9) may be used in combination. The ratio of the bishydroxy-substituted compound having the charge transporting ability represented by the general formula (6), (7) or (8) and the bishydroxy-substituted compound represented by the general formula (9) is in a wide range depending on the desired properties. You can choose from.
[0048]
Further, by selecting an appropriate polymerization operation, among the copolymers, a random copolymer, a block copolymer, an alternating copolymer, a random block copolymer and the like can be obtained. For example, at least one bishydroxy-substituted compound having the charge transporting ability represented by the general formula (6), (7), or (8) and the bishydroxy-substituted compound represented by the general formula (9) are uniformly mixed from the beginning. And a random copolymer comprising a structural unit represented by the general formula (1), (2) or (3) and a structural unit represented by the general formula (4) In addition, a random block copolymer can be obtained by adding several kinds of bishydroxy-substituted compounds from the middle of the reaction. Further, a bischloroformate derived from a bishydroxy-substituted compound represented by the general formula (9) and a bishydroxy-substituted compound having a charge transporting ability represented by the general formula (6), (7), or (8) When the condensation reaction with is carried out, an alternating copolymer is obtained.
[0049]
When interfacial polymerization is performed by a method using a carbonyl halide compound or chloroformate, an alkaline aqueous solution of a bishydroxy-substituted compound and an organic solvent that is substantially insoluble in water and dissolves the polycarbonate resin In the presence of a carbonic acid derivative and a catalyst. At this time, a polycarbonate resin having a narrow molecular weight distribution can be obtained in a short time by emulsifying the reaction medium by high-speed stirring or addition of an emulsifier. Examples of the base used in the alkaline aqueous solution include hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate, potassium carbonate and sodium hydrogen carbonate. These bases may be used alone or in combination, but sodium hydroxide or potassium hydroxide is preferably used.
[0050]
As the organic solvent, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, 1,2-dichloroethylene, chlorobenzene and dichlorobenzene, and cyclic ethers such as tetrahydrofuran and dioxane are preferably used. A mixture of hydrocarbons such as xylene, hexane, and cyclohexane may be used.
[0051]
Polycarbonate production catalysts used in the production of polycarbonate include tertiary amines such as trimethylamine, triethylamine and tri-n-propylamine, quaternary ammonium salts such as benzyltrimethylammonium chloride, tetraethylammonium bromide and tetramethylammonium chloride, triethylphosphine , Tertiary phosphines such as triphenylphosphine, quaternary phosphonium salts such as benzyltriethylphosphonium chloride, benzyltriphenylphosphonium chloride, N-ethylpyridine, N, N'-dimethylpiperazine, 4-methylpyridine, 1-methylimidazole, etc. The nitrogen-containing heterocyclic compound is preferably a tertiary amine, more preferably triethylamine. These catalysts can be added when a carbonic acid derivative such as phosgene, triphosgene, or a bischloroformate compound is added to the reaction system, or before or after that.
[0052]
Moreover, it is desirable to use phenols, such as phenol and p-tert-butylphenol, as a molecular weight regulator as a terminal terminator. In addition, an antioxidant such as sodium hydrosulfite may be added to prevent oxidation of the bishydroxy-substituted compound in an aqueous alkali solution. The reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 6 hours.
[0053]
If necessary, additives such as antioxidants, light stabilizers, heat stabilizers, lubricants, plasticizers, and the like can be added to the aromatic polycarbonate resin produced according to the above method. Hereinafter, the polycarbonate resin of the present invention will be described in more detail.
[0054]
The aromatic polycarbonate resin of the present invention is a homopolymer composed of a repeating unit represented by the general formula (1), (2), or (3), or a repeating represented by the general formulas (1) and (4). An alternating copolymer comprising units, an alternating copolymer comprising repeating units represented by the general formulas (2) and (4), or an alternating copolymer comprising repeating units represented by (3) and (4) Or a random or block copolymer having the repeating units represented by the general formulas (1) and (4) as structural units, or the repeating units represented by the general formulas (2) and (4) as structural units. Either a random or block copolymer, or a random or block copolymer having the repeating unit represented by the general formulas (3) and (4) as a constituent unit may be used. The molecular weight of the aromatic polycarbonate resin of the present invention is 1000 to 1000000, preferably 5000 to 100000 in terms of polystyrene-equivalent number average molecular weight.
[0055]
Specific examples of the substituent that gives the repeating unit represented by the above (1) to (5) and constitutes the aromatic polycarbonate resin of the present invention are shown below.
[0056]
Ar in (1), (2), or (3) ¹ , Ar ² And Ar ^Three Specific examples of the hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group, n-octadecyl group, 2-methoxyethyl group, cyclohexyl Alkyl groups such as benzyl groups, benzyl groups, 4-methylbenzyl groups, 3-methoxybenzyl groups, aralkyl groups such as 2- (4-chlorophenyl) ethyl groups, or phenyl groups, 4-methylphenyl groups, 2methoxyphenyl groups, Examples include aryl groups such as 4-chlorophenyl group, 3-diethylaminophenyl group, 1-naphthyl group, and 1-pyrenyl group.
[0057]
In addition, Ar in (1), (2), or (3) ^Four Specific examples of the aryl group include aryl groups such as a phenyl group, a 4-methylphenyl group, a 2-methoxyphenyl group, a 4-chlorophenyl group, a 3-diethylaminophenyl group, a 1-naphthyl group, and a 1-pyrenyl group.
[0058]
Ar in (1) or (2) ^Five And Ar ⁶ Specific examples of these include 1,4-phenylene group, 1,2-phenylene group, 1,3-phenylene group, 2-methyl-1,4-phenylene group, 3-ethyl-1,2-phenylene group, 2 -Chloro-1,4-phenylene group, 4-methyl-1,3-phenylene group, 1,4-naphthylene group, 1,8-naphthylene group, 9,10-anthrylene group, 2,7-phenanthrylene group, 4 , 4'-biphenylene group, 3,4'-biphenylene group, and the like.
[0059]
Moreover, n in (1) or (2) shows the integer of 0-2.
[0060]
Specific examples of X in (4) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a 2-methylpentamethylene group, a 2-chlorotetramethylene group, and a 3-methoxypentamethylene group. Chain aliphatic divalent groups such as 1,3-cyclopentylene group, 1,4-cyclohexylene group, cyclohexane-1,1-diyl group, 2,3-dimethoxy-1,4-cyclohexylene group, etc. Cycloaliphatic divalent groups, phenylene groups, naphthylene groups, biphenylylene groups, terphenylylene groups, fluorene-2,7-diyl groups, phenanthrene-2,7-diyl groups, pyrene-1,6-diyl groups, 9,9 -Aromatic divalent groups such as dimethylfluorene-2,7-diyl group, stilbene-4,4'-diyl group, 1,4-dimethylpiperazine-2 5-diyl group, furan-2,5-diyl group, thiophene-2,5-diyl group, pyridine-2,4-diyl group, 1-methylindole-4,6-diyl group, N-ethylcarbazole-3 , 6-diyl group, 3-methylpyrazole-1,4-diyl group, 3- (4-methoxyphenyl) pyrazole-1,4-diyl group and the like, or these groups are linked. Cyclohexylbenzene-4,4'-diyl group, 2-phenylpyridine-3,4'-diyl group, diphenylmethane-4,4'-diyl group, 2,2-diphenylpropane-4 ', 4 "-diyl group , 1,1-diphenylhexane-4 ′, 4 ″ -diyl group, 1,5-diphenylpentane-4 ′, 4 ″ -diyl group or the like, or these divalent groups, oxygen atom and sulfur atom Group containing Diphenyl ether-4,4'-diyl group, diphenyl sulfide-4,4'-diyl group, 3,6-dioxaoctane-1,8-diyl group, 3,6, Bivalent groups such as 9-trioxaundecane-1,11-diyl group can be exemplified.
[0061]
R in (5) ¹ And R ² Specific examples of C include hydrogen atom or C such as methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group. ₁ ~ C _Four Lower alkyl group or C such as methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, etc. ₁ ~ C _Four Or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom. Specific examples of Y include a single bond, oxygen atom, sulfur atom, or methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, 4-methylpentamethylene group, 2-chlorotetramethylene group, Chain aliphatic divalent groups such as 3-methoxypentamethylene group, 1,3-cyclopentylene group, 1,4-cyclohexylene group, cyclohexane-1,1-diyl group, 2,3-dimethoxy-1 Cyclic aliphatic divalent groups such as 1,4-cyclohexylene group, or ethylcyclohexane-2,4'-diyl group, 3,6-dioxaoctane-1,8-diyl group formed by linking them A divalent group can be mentioned. j and k each independently represent an integer of 1 to 4, and when each of j and k is 2 or more, R ¹ And R ² The same substituent may be sufficient about each of these, and a different substituent may be sufficient.
[0062]
Preferred examples of the bishydroxy-substituted compound represented by the general formula (6), (7), or (8) having a completely new charge transport ability, which has not been conventionally used, for the production of the aromatic polycarbonate resin of the present invention. As Ar ¹ And Ar ² Both are C such as methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group. ₁ ~ C _Four A lower alkyl group, or a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 4-fluorophenyl group, a 4-chlorophenyl group, or the like, or C ₁ ~ C _Four Or a phenyl group substituted with a halogen atom, Ar ^Three Is a hydrogen atom, Ar ^Four Is unsubstituted, such as phenyl group, 4-methylphenyl group, 3-methylphenyl group, 4-ethoxyphenyl group, 4-fluorophenyl group, 4-chlorophenyl group, or C ₁ ~ C _Four Or a phenyl group substituted with a halogen atom, Ar ^Five Is a 1,4-phenylene group, Ar ^Five Is a unsubstituted phenylene group such as 1,4-phenylene group, 1,2-phenylene group, etc., and n is 0 or 1.
[0063]
Preferable specific examples of the bishydroxy-substituted compound represented by the general formula (6), (7), or (8) include, but are not limited to, the following compounds EA-1 to 55. It is not a thing.
[0064]
[Table 1]

[0065]
[Table 2]

[0066]
Specific examples of the bishydroxy-substituted compound represented by the general formula (9) include the following compounds MA-1 to 50, but are not limited thereto.
[0067]
Embedded image

[0068]
Embedded image

[0069]
Embedded image

[0070]
Embedded image

[0071]
Embedded image

[0072]
Specific examples of the aromatic polycarbonate resin of the present invention include an aromatic polycarbonate resin having the substituent described above and containing the structural unit represented by the general formula (1), (2), or (3), Alternatively, the aromatic polycarbonate resin containing the structural unit represented by the general formulas (1) and (4), (2) and (4), or (3) and (4), or the general formula (1) ) And (5), or (2) and (5), or (3) and aromatic polycarbonate resin containing the structural unit represented by (5) is mentioned. Preferred examples include EA- Any one or more of the compounds 1 to 55, the aromatic polycarbonate resin synthesized as described above, or one or more of the compounds EA-1 to 55 described above, and the above M Any one or combination to synthesize a plurality aromatic polycarbonate resin can be cited the compounds of -1～50.
[0073]
The aromatic polycarbonate resin of the present invention obtained as described above is used as an organic photoconductive compound, an electronic device such as a sensor material or an organic EL element, and particularly as a charge transport material of the aforementioned organic electrophotographic photoreceptor. It can be suitably used.
[0074]
Next, the organic electrophotographic photoreceptor of the present invention (hereinafter abbreviated as electrophotographic photoreceptor) will be described. The electrophotographic photoreceptor of the present invention has a photosensitive layer containing the aromatic polycarbonate resin according to any one of claims 1 to 9.
[0075]
Any type of electrophotographic photoreceptor including a photosensitive layer containing these can be used. For example, a single-layer type photoreceptor in which a photosensitive layer made of a charge generating substance, a charge transporting substance, and a film-forming binder resin is provided on a conductive support, or a charge generating substance on a conductive support. There is known a laminated type photoconductor called a function separation type in which a charge generation layer made of a binder resin and a charge transport layer made of a charge transport material and a binder resin are provided in this order. These compounds are extremely useful as these charge transport materials in any configuration.
[0076]
As a support for producing a photoreceptor using the compound of the present invention, a metal drum, a metal plate, a sheet of paper or plastic film subjected to conductive processing, a drum-like or belt-like support, and the like are used. The
[0077]
In addition, the charge generating material in the above configuration includes an inorganic charge generating material and an organic charge generating material. Examples of the former include selenium, selenium-tellurium alloy, selenium-arsenic alloy, cadmium sulfide, zinc oxide, amorphous silicon. Etc. Examples of the latter include, for example, triphenylmethane dyes such as methyl violet, brilliant green, and crystal violet, thiazine dyes such as methylene blue, quinone dyes such as quinizarin, cyanine dyes, acridine dyes, pyrylium dyes, thiapyrylium dyes, squalium dyes Phthalocyanine pigments, azo pigments, perinone pigments, anthraquinone pigments, perylene pigments, etc., but metal-containing or metal-free phthalocyanine pigments, bisazo pigments, trisazo pigments, etc. This is an azo pigment.
[0078]
As examples of phthalocyanine pigments, metal-free phthalocyanines are disclosed in JP-B-49-4338, JP-A-58-182639, or J.P. Phys. Chem. 72 3230 (1968), titanyloxyphthalocyanine is disclosed in JP-A-61-217050, JP-A-62-267094, JP-A-63-365, JP-A-63-3. Copper phthalocyanine described in Japanese Patent Publication No. 198067, Japanese Patent Application Laid-Open No. 64-17066, or Japanese Patent Application Laid-Open No. 1-189200 is Japanese Patent Publication No. 52-1667 or Japanese Patent Application Laid-Open No. 51-108847. The chloroaluminum phthalocyanine described in JP-A-58-158649, the chloroindium phthalocyanine described in JP-A-7-13375, the vanadyloxy Phthalocyanines are disclosed in JP-A-63-18361, JP-A-1-204968, and JP-A-3. No. 269063 or JP-A-7-247442, diphenoxygermanium phthalocyanine is described in JP-A-4-360150, and chlorogallium phthalocyanine is described in JP-A-5- No. 194523 or JP-A-7-102183, and hydroxygallium phthalocyanine described in JP-A-5-263007 or JP-A-7-53892, respectively. Can be mentioned.
[0079]
Examples of azo pigments include benzidine type bisazo pigments described in JP-A-47-37543, benzoxazole-type bisazo pigments described in JP-A-56-116039, and JP-A-57-176055. Oxadiazole type bisazo pigments described in Japanese Patent Publication No. 60-45664, or pyrazole type bisazo pigments described in Japanese Patent Application Laid-Open Nos. 1-220027 and 1-202757. And a trisazo pigment such as the triphenylamine type trisazo pigment described in JP-A-57-195767.
[0080]
【Example】
EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to these at all.
[0081]
Example 1
Bishydroxy-substituted compound EA-14 having charge transport ability described in Table 1 above: 3.12 g, bishydroxy-substituted compound MA-31: 1.50 g represented by the general formula (9), and molecular weight regulator 4-t-butylphenol: 0.05 g in a 300 ml three-necked flask, a solution prepared by dissolving hydrosulfite sodium: 0.06 g and sodium hydroxide: 2.67 g in distilled water: 41 ml was added, and a nitrogen stream Under stirring at room temperature with a mechanical stirrer. A solution prepared by dissolving 1.60 g of triphosgene in 55 ml of chloroform was added, and further after 3 minutes, 0.1 ml of triethylamine was added, followed by stirring at room temperature for 2 hours. As a polymerization terminator, a solution prepared by dissolving 0.13 g of phenyl chloroformate in 2 ml of chloroform was added, and the mixture was further stirred at room temperature for 2 hours. Chloroform: 150 ml was added, washed with 2.5% sodium hydroxide solution, then with 1N hydrochloric acid, further washed with distilled water, added with magnesium sulfate, shaken well, dried and concentrated to about 80 ml under reduced pressure. Then, the solution was poured into 300 ml of methanol and the precipitated crystals were collected by filtration. This crystal was dissolved again in 70 ml: chloroform and re-precipitation treatment poured into methanol: 300 ml was repeated twice and dried under reduced pressure at room temperature to obtain the target polycarbonate resin (10): 2.92 g (72.5% )
[0082]
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[0083]
This thing is ¹ H-NMR (δ, ppm, CDCl _Three ) 7.35 to 7.15 (m, area ratio: 15.00H), 7.14 to 6.80 (m, same: 14.06H), 6.77 (brs, same: 3.77H) , 6.64 (s, same: 1.00H), and the area ratio, the structure and the molar composition ratio of the EA-14-derived part and the MA-31-derived part were confirmed. It was.
[0084]
When the molecular weight of the obtained polycarbonate resin was measured by gel permeation chromatography, the molecular weight in terms of polystyrene was as follows.
[0085]
Number average molecular weight: 26000
Weight average molecular weight: 52,000
[0086]
Further, from the IR analysis, IR absorption due to C═O stretching vibration of the carbonate portion of the obtained polycarbonate resin was 1775 cm. ^-1 Observed.
[0087]
Similarly, polycarbonate resins as shown in Examples 2 to 20 in Table 3 below were synthesized.
[0088]
[Table 3]

[0089]
Example 21
As a charge generation material, 1 part by weight of a bisazo pigment (P-1) having the following structural formula and 1 part by weight of a polyester resin (Toyobo's Byron 200) are mixed with 100 parts by weight of tetrahydrofuran and mixed with glass beads for 2 hours in a paint conditioner device. Distributed. The dispersion thus obtained was applied onto an aluminum vapor-deposited polyester with an applicator and dried to form a charge generation layer having a thickness of about 0.2 μm. Next, as a charge transport material, a 10% by weight solution of the compound (10) of the present invention is prepared using tetrahydrofuran as a solvent, and the charge transport layer is coated on the charge generation layer with an applicator and has a thickness of about 18 μm. Formed.
[0090]
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[0091]
The multilayer photoconductor produced in this manner was evaluated for electrophotographic characteristics using an electrostatic recording test apparatus (EPA-8200 manufactured by Kawaguchi Electric).
Measurement conditions: applied voltage -6 kV, static No. 3 (turn table rotation speed mode: 10 m / min). As a result, the charging potential (V ₀ ) Was -650 V, and the half-exposure amount (E1 / 2) was 0.75 lux.sec.
[0092]
Further, using the same apparatus, the characteristics were evaluated for repeated use with one cycle of charge-static elimination (static elimination light: 400 lux × 1 second irradiation with white light). When the change in charging potential due to repetition at 5000 times was determined, the first charging potential (V ₀ ) -650V vs. 5000th charging potential (V ₀ ) Was -640 V, and showed a stable characteristic with almost no decrease in potential due to repetition. In addition, the first half exposure (E1 / 2) was 0.75 lux · second, and the 5000 half exposure (E1 / 2) was 0.75 lux · second, showing no change. .
[0093]
Examples 22-48
Instead of the bisazo pigment (P-1) of Example 1 and the compound (10) of the present invention, the bisazo pigments of the following structural formulas (P-1) to (P-5) and the present invention shown in Table 3, respectively. Except for using the compound, a photoconductor was prepared in the same manner as in Example 1, and its characteristics were evaluated. The results are shown in Table 4.
[0094]
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[0095]
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[0096]
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[0097]
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[0098]
[Table 4]

[0099]
Example 49
As a charge generation material, the Bragg angle (2θ ± 0.2 °) of CuKα1.541Å with respect to the X-ray instead of the bisazo pigment (P-1) is 9.5 °, 9.7 °, 11.7 °, 15 Example 21 was used except that titanyloxyphthalocyanine (Y-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing main peaks at 0.0 °, 23.5 °, 24.1 °, and 27.3 ° was used. Photoconductors were produced in the same manner, and the characteristics were evaluated in the same manner as in Example 21. The result is charged potential (V ₀ ) Was -520 V, and the half-exposure amount (E1 / 2) was 0.25 lux.sec. Also, in the characteristic evaluation for repeated use, the first charging potential (V ₀ ) -520V vs. 5000th charging potential (V ₀ ) Was −510 V, and showed stable characteristics with almost no decrease in potential due to repetition. The first half exposure (E1 / 2) was 0.25 lux · sec, and the 5000th half exposure (E1 / 2) was 0.25 lux · sec. .
[0100]
Examples 50-68
A photoconductor was prepared and evaluated in the same manner as in Example 49 except that the compound of the present invention shown in Table 3 was used instead of the compound (10) of Example 49 of the present invention. The results are shown in Table 5.
[0101]
[Table 5]

[0102]
【The invention's effect】
As described above, the aromatic polycarbonate resin of the present invention itself is useful as a photoconductive material, and particularly exhibits an excellent function as a charge transport material of an electrophotographic photoreceptor.

Claims (18)

An aromatic polycarbonate resin containing a structural unit represented by the following general formula (1).

(In General Formula (1), Ar ¹ , Ar ² , and Ar ³ have a hydrogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or a substituent. Ar ⁴ represents an aryl group which may have a substituent, Ar ⁵ and Ar ⁶ represent an arylene group which may have a substituent, and n is an integer of 0 to 2 Is shown.) An aromatic polycarbonate resin containing a structural unit represented by the following general formula (2).

(In General Formula (2), Ar ¹ , Ar ² , and Ar ³ have a hydrogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or a substituent. Ar ⁴ represents an aryl group which may have a substituent, Ar ⁵ represents an arylene group which may have a substituent, and n represents an integer of 0 to 2. ) An aromatic polycarbonate resin containing a structural unit represented by the following general formula (3).

(In General Formula (3), Ar ¹ and Ar ² are a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl which may have a substituent. And Ar ⁴ represents an aryl group which may have a substituent. The aromatic polycarbonate resin which consists of a structural unit shown by General formula (1) in Claim 1, and following General formula (4).

(In the general formula (4), X represents a substituted or unsubstituted chain aliphatic divalent group, a substituted or unsubstituted cyclic aliphatic divalent group, a substituted or unsubstituted aromatic divalent group, a substituted or unsubstituted group. Or a divalent group formed by linking these, or a divalent group formed by linking any of these divalent groups and a group containing an oxygen atom and a sulfur atom. ) The aromatic polycarbonate resin according to claim 4, wherein the structural unit represented by the general formula (1) in claim 4 is a structural unit represented by the general formula (2). The aromatic polycarbonate resin according to claim 4, wherein the structural unit represented by the general formula (1) in claim 4 is a structural unit represented by the general formula (3). The aromatic polycarbonate resin according to claim 4, wherein X in the general formula (4) in claim 4 is a structural unit represented by the following general formula (5).

(In General Formula (5), R ¹ and R ² represent a hydrogen atom, a C ₁ -C ₄ lower alkyl group, a C ₁ -C ₄ lower alkoxy group, or a halogen atom, Y represents a single bond, an oxygen atom , A sulfur atom, a substituted or unsubstituted chain aliphatic divalent group, a substituted or unsubstituted cyclic aliphatic divalent group, or a divalent group formed by linking them, j and k are each independently And represents an integer of 1 to 4, and when each of j and k is 2 or more, each of R ¹ and R ² may be the same or different substituent. The aromatic polycarbonate resin according to claim 5, wherein X in the general formula (4) in claim 5 is a structural unit represented by the general formula (5) in claim 7. The aromatic polycarbonate resin according to claim 6, wherein the structural unit represented by the general formula (4) in claim 6 is a structural unit represented by the general formula (5) in claim 7. An electrophotographic photosensitive member comprising a photosensitive layer containing an aromatic polycarbonate resin containing a structural unit represented by the general formula (1) in claim 1 on a conductive support. An electrophotographic photosensitive member comprising a photosensitive layer containing an aromatic polycarbonate resin containing a structural unit represented by the general formula (2) in claim 2 on a conductive support. An electrophotographic photoreceptor comprising a photosensitive layer containing an aromatic polycarbonate resin containing a structural unit represented by formula (3) in claim 3 on a conductive support. An electrophotographic photoreceptor comprising a photosensitive layer containing the aromatic polycarbonate resin according to claim 4 on a conductive support. An electrophotographic photoreceptor comprising a photosensitive layer containing the aromatic polycarbonate resin according to claim 5 on a conductive support. An electrophotographic photoreceptor comprising a photosensitive layer containing the aromatic polycarbonate resin according to claim 6 on a conductive support. An electrophotographic photoreceptor comprising a photosensitive layer containing the aromatic polycarbonate resin according to claim 7 on a conductive support. An electrophotographic photoreceptor comprising a photosensitive layer containing the aromatic polycarbonate resin according to claim 8 on a conductive support. An electrophotographic photoreceptor comprising a photosensitive layer containing the aromatic polycarbonate resin according to claim 9 on a conductive support.