JP3936576B2 - Full-color image forming apparatus and process cartridge - Google Patents

Description

【００８７】
式中、Ｒ_１，Ｒ_２，Ｒ_３はそれぞれ独立して置換もしくは無置換のアルキル基またはハロゲン原子、Ｒ_４は水素原子または置換もしくは無置換のアルキル基、Ｒ_５，Ｒ_６は置換もしくは無置換のアリール基、ｏ，ｐ，ｑはそれぞれ独立して０〜４の整数、ｋ，ｊは組成を表し、電荷輸送構造が３０重量％以上７０重量％以下になるように調節される。ｎは繰り返し単位数を表し５〜５０００の整数である。Ｘは脂肪族の２価基、環状脂肪族の２価基、または下記一般式（１−１）で表される２価基を表す。
【００８８】
【化２】

（式中、Ｒ_１０１，Ｒ_１０２は各々独立して置換もしくは無置換のアルキル基、アリール基またはハロゲン原子を表す。ｌ、ｍは０〜４の整数、Ｙは単結合、炭素原子数１〜１２の直鎖状、分岐状もしくは環状のアルキレン基、−Ｏ−，−Ｓ−，−ＳＯ−，−ＳＯ_２−，−ＣＯ−，−ＣＯ−Ｏ−Ｚ−Ｏ−ＣＯ−（式中Ｚは脂肪族の２価基を表す。）、
または、下記一般式（１−２）
【００８９】
【化３】

（式中、ａは１〜２０の整数、ｂは１〜２０００の整数、Ｒ_１０３，Ｒ_１０４は置換または無置換のアルキル基またはアリール基を表す。）を表す。ここで、Ｒ_１０１とＲ_１０２、Ｒ_１０３とＲ_１０４は、それぞれ同一でも異なってもよい。）
【００９０】
一般式（１）の具体例
Ｒ_１，Ｒ_２，Ｒ_３はそれぞれ独立して置換もしくは無置換のアルキル基またはハロゲン原子を表すが、その具体例としては以下のものを挙げることができ、同一であっても異なってもよい。
アルキル基として好ましくは、Ｃ_１〜Ｃ_１２ とりわけＣ_１〜Ｃ_８、さらに好ましくはＣ_１〜Ｃ_４の直鎖または分岐鎖のアルキル基であり、これらのアルキル基はさらにフッ素原子、水酸基、シアノ基、Ｃ_１〜Ｃ_４のアルコキシ基、フェニル基、またはハロゲン原子、Ｃ_１〜Ｃ_４のアルキル基もしくはＣ_１〜Ｃ_４のアルコキシ基で置換されたフェニル基を含有してもよい。具体的には、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、トリフルオロメチル基、２−ヒドロキシエチル基、２−シアノエチル基、２−エトキシエチル基、２−メトキシエチル基、ベンジル基、４−クロロベンジル基、４−メチルベンジル基、４−メトキシベンジル基、４−フェニルベンジル基等が挙げられる。
【００９１】
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
Ｒ_４は水素原子または置換もしくは無置換のアルキル基を表すがそのアルキル基の具体例としては上記のＲ_１，Ｒ_２，Ｒ_３と同様のものが挙げられる。
Ｒ_５，Ｒ_６は置換もしくは無置換のアリール基を表すが、その具体例としては以下のものを挙げることができ、同一であっても異なってもよい。
【００９２】
芳香族炭化水素基としては、フェニル基、縮合多環基としてナフチル基、ピレニル基、２−フルオレニル基、９，９−ジメチル−２−フルオレニル基、アズレニル基、アントリル基、トリフェニレニル基、クリセニル基、フルオレニリデンフェニル基、５Ｈ−ジベンゾ ［ａ，ｄ］シクロヘプテニリデンフェニル基、非縮合多環基としてビフェニリル基、ターフェニリル基などが挙げられる。
複素環基としては、チエニル基、ベンゾチエニル基、フリル基、ベンゾフラニル基、カルバゾリル基などが挙げられる。
【００９３】
上述のアリール基は以下に示す基を置換基として有してもよい。
（１）ハロゲン原子、トリフルオロメチル基、シアノ基、ニトロ基。
（２）アルキル基としては、上記のＲ_１，Ｒ_２，Ｒ_３と同様のものが挙げられる。
（３）アルコキシ基（−ＯＲ_１０５）、式中のＲ_１０５は（２）で定義したアルキル基を表す。具体的には、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｔ−ブトキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｉ−ブトキシ基、２−ヒドロキシエトキシ基、２−シアノエトキシ基、ベンジルオキシ基、４−メチルベンジルオキシ基、トリフルオロメトキシ基等が挙げられる。
（４）アリールオキシ基としては、アリール基としてフェニル基、ナフチル基が挙げられる。これは、Ｃ_１〜Ｃ_４ のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有してもよい。具体的には、フェノキシ基、１−ナフチルオキシ基、２−ナフチルオキシ基、４−メチルフェノキシ基、４−メトキシフェノキシ基、４−クロロフェノキシ基、６−メチル−２−ナフチルオキシ基等が挙げられる。
（５）置換メルカプト基またはアリールメルカプト基としては、具体的にはメチルチオ基、エチルチオ基、フェニルチオ基、ｐ−メチルフェニルチオ基等が挙げられる。
（６）アルキル置換アミノ基としては、アルキル基は（２）で定義したアルキル基を表す。具体的には、ジメチルアミノ基、ジエチルアミノ基、Ｎ−メチル−Ｎ−プロピルアミノ基、Ｎ，Ｎ−ジベンジルアミノ基等が挙げられる。
（７）アシル基としては、具体的にはアセチル基、プロピオニル基、ブチリル基、マロニル基、ベンゾイル基等が挙げられる。
【００９４】
Ｘは下記一般式（Ａ）のトリアリールアミノ基を有するジオール化合物をホスゲン法、エステル交換法等を用い重合するとき、下記一般式（Ｂ）のジオール化合物を併用することにより主鎖中に導入される。この場合、製造されるポリカーボネート樹脂はランダム共重合体、またはブロック共重合体となる。また、Ｘは下記一般式（Ａ）のトリアリールアミノ基を有するジオール化合物と下記一般式（Ｂ）から誘導されるビスクロロホーメートとの重合反応によっても繰り返し単位中に導入される。この場合、製造されるポリカーボネートは交互共重合体となる。
【００９５】
【化４】

【００９６】
一般式（Ｂ）のジオール化合物の具体例としては以下のものが挙げられる。
１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，８−オクタンジオール、１，１０−デカンジオール、２−メチル−１，３−プロパンジオール、２，２−ジメチル−１，３−プロパンジオール、２−エチル−１，３−プロパンジオール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ポリテトラメチレンエーテルグリコール等の脂肪族ジオールや１，４−シクロヘキサンジオール、１，３−シクロヘキサンジオール、シクロヘキサン−１，４−ジメタノール等の環状脂肪族ジオールが挙げられる。
また、芳香環を有するジオールとしては、４，４’−ジヒドロキシジフェニル、ビス（４−ヒドロキシフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、２，２−ビス（４−ヒドロキシフェニル）プロパン、２，２−ビス（３−メチル−４−ヒドロキシフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、１，１−ビス（４−ヒドロキシフェニル）シクロペンタン、２，２−ビス（３−フェニル−４−ヒドロキシフェニル）プロパン、２，２−ビス（３−イソプロピル−４−ヒドロキシフェニル）プロパン、２，２−ビス（４−ヒドロキシフェニル）ブタン、２，２−ビス（３，５−ジメチル−４−ヒドロキシフェニル）プロパン、２，２−ビス（３，５−ジブロモ−４−ヒドロキシフェニル）プロパン、４，４’−ジヒドロキシジフェニルスルホン、４，４’−ジヒドロキシジフェニルスルホキシド、４，４’−ジヒドロキシジフェニルスルフィド、３，３’−ジメチル−４，４’−ジヒドロキシジフェニルスルフィド、４，４’−ジヒドロキシジフェニルオキシド、２，２−ビス（４−ヒドロキシフェニル）ヘキサフルオロプロパン、９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（４−ヒドロキシフェニル）キサンテン、エチレングリコール−ビス（４−ヒドロキシベンゾエート）、ジエチレングリコール−ビス（４−ヒドロキシベンゾエート）、トリエチレングリコール−ビス（４−ヒドロキシベンゾエート）、１，３−ビス（４−ヒドロキシフェニル）−テトラメチルジシロキサン、フェノール変性シリコーンオイル等が挙げられる。
【００９７】
高分子電荷輸送物質の第２の例としては下記一般式（２）で表されるトリアリールアミン構造有するポリカーボネートがある。
【００９８】
【化５】

【００９９】
式中、Ｒ_７，Ｒ_８は置換もしくは無置換のアリール基、Ａｒ_１，Ａｒ_２，Ａｒ_３は同一または異なるアリレン基を表す。 Ｘ、ｋ、ｊおよびｎは、一般式（１）の場合と同じである。
【０１００】
一般式（２）の具体例
Ｒ_７，Ｒ_８は置換もしくは無置換のアリール基を表すが、その具体例としては以下のものを挙げることができ、同一であっても異なってもよい。
芳香族炭化水素基としては、フェニル基、縮合多環基としてナフチル基、ピレニル基、２−フルオレニル基、９，９−ジメチル−２−フルオレニル基、アズレニル基、アントリル基、トリフェニレニル基、クリセニル基、フルオレニリデンフェニル基、５Ｈ−ジベンゾ［ａ，ｄ］シクロヘプテニリデンフェニル基、非縮合多環基としてビフェニリル基、ターフェニリル基、または下記一般式（２−１）
【０１０１】
【化６】

【０１０２】
（ここで、Ｗは−Ｏ−，−Ｓ−，−ＳＯ−，−ＳＯ_２−，−ＣＯ−および下記一般式（２−２）、（２−３）、（２−４）、（２−５）；
【０１０３】
【化７】

【０１０４】
【化８】

【０１０５】
【化９】

【０１０６】
【化１０】

で表される２価基を表す。）
で表される基を示す。
【０１０７】
複素環基としては、チエニル基、ベンゾチエニル基、フリル基、ベンゾフラニル基、カルバゾリル基などが挙げられる。
【０１０８】
また、Ａｒ_１，Ａｒ_２およびＡｒ_３で示されるアリレン基としてはＲ_７および Ｒ_８で示したアリール基の２価基が挙げられ、同一であっても異なってもよい。
上述のアリール基およびアリレン基は以下に示す基を置換基として有してもよい。また、これら置換基は上記一般式中のＲ_１０６，Ｒ_１０７，Ｒ_１０８の具体例として表される。
（１）ハロゲン原子、トリフルオロメチル基、シアノ基、ニトロ基。
（２）アルキル基としては、好ましくは、Ｃ_１〜Ｃ_１２ とりわけＣ_１〜Ｃ_１８、さらに好ましくはＣ_１〜Ｃ_４の直鎖または分岐鎖のアルキル基であり、これらのアルキル基はさらにフッ素原子、水酸基、シアノ基、Ｃ_１〜Ｃ_４のアルコキシ基、フェニル基、またはハロゲン原子、Ｃ_１〜Ｃ_４のアルキル基もしくはＣ_１〜Ｃ_４のアルコキシ基で置換されたフェニル基を含有してもよい。具体的には、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、トリフルオロメチル基、２−ヒドロキシエチル基、２−シアノエチル基、２−エトキシエチル基、２−メトキシエチル基、ベンジル基、４−クロロベンジル基、４−メチルベンジル基、４−メトキシベンジル基、４−フェニルベンジル基等が挙げられる。
（３）アルコキシ基（−ＯＲ_１０９）、式中のＲ_１０９は（２）で定義したアルキル基を表わす。具体的には、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｔ−ブトキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｉ−ブトキシ基、２−ヒドロキシエトキシ基、２−シアノエトキシ基、ベンジルオキシ基、４−メチルベンジルオキシ基、トリフルオロメトキシ基等が挙げられる。
（４）アリールオキシ基としては、アリール基としてフェニル基、ナフチル基が挙げられる。これは、Ｃ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有してもよい。具体的には、フェノキシ基、１−ナフチルオキシ基、２−ナフチルオキシ基、４−メチルフェノキシ基、４−メトキシフェノキシ基、４−クロロフェノキシ基、６−メチル−２−ナフチルオキシ基等が挙げられる。
（５）置換メルカプト基またはアリールメルカプト基としては、具体的にはメチルチオ基、エチルチオ基、フェニルチオ基、ｐ−メチルフェニルチオ基等が挙げられる。
（６）下記一般式（２−６）
【０１０９】
【化１１】

【０１１０】
（式中、Ｒ_１１０およびＲ_１１１は各々独立に（２）で定義したアルキル基またはアリール基を表す。アリール基としては、例えばフェニル基、ビフェニル基、またはナフチル基が挙げられ、これらはＣ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有してもよい。またアリール基上の炭素原子と共同で環を形成してもよい。）
具体的には、ジエチルアミノ基、Ｎ−メチル−Ｎ−フェニルアミノ基、Ｎ，Ｎ−ジフェニルアミノ基、Ｎ，Ｎ−ジ（ｐ−トリル）アミノ基、ジベンジルアミノ基、ピペリジノ基、モルホリノ基、ユロリジル基等が挙げられる。
（７）メチレンジオキシ基、またはメチレンジチオ基等のアルキレンジオキシ基またはアルキレンジチオ基、等が挙げられる。
【０１１１】
Ｘは下記一般式（Ｃ）のトリアリールアミノ基を有するジオール化合物をホスゲン法、エステル交換法等を用い重合するとき、下記一般式（Ｂ）のジオール化合物を併用することにより主鎖中に導入される。この場合、製造されるポリカーボネート樹脂はランダム共重合体、またはブロック共重合体となる。また、Ｘは下記一般式（Ｃ）のトリアリールアミノ基を有するジオール化合物と下記一般式（Ｂ）から誘導されるビスクロロホーメートとの重合反応によっても繰り返し単位中に導入される。この場合、製造されるポリカーボネートは交互共重合体となる。
【０１１２】
【化１２】

【０１１３】
一般式（Ｂ）のジオール化合物は一般式（１）と同じものが挙げられる。
【０１１４】
高分子電荷輸送物質の第３の例としては下記一般式（３）で表されるトリアリールアミン構造有するポリカーボネートがある。
【０１１５】
【化１３】

【０１１６】
式中、Ｒ_９，Ｒ_１０は置換もしくは無置換のアリール基、Ａｒ_４，Ａｒ_５，Ａｒ_６は同一または異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、一般式（１）の場合と同じである。
【０１１７】
一般式（３）の具体例
Ｒ_９，Ｒ_１０は置換もしくは無置換のアリール基を表すが、その具体例としては以下のものを挙げることができ、同一であっても異なってもよい。
芳香族炭化水素基としては、フェニル基、縮合多環基としてナフチル基、ピレニル基、２−フルオレニル基、９，９−ジメチル−２−フルオレニル基、アズレニル基、アントリル基、トリフェニレニル基、クリセニル基、フルオレニリデンフェニル基、５Ｈ−ジベンゾ ［ａ，ｄ］シクロヘプテニリデンフェニル基、非縮合多環基としてビフェニリル基、ターフェニリル基などが挙げられる。
複素環基としては、チエニル基、ベンゾチエニル基、フリル基、ベンゾフラニル基、カルバゾリル基などが挙げられる。
【０１１８】
また、Ａｒ_４，Ａｒ_５およびＡｒ_６で示されるアリレン基としては、Ｒ_９およびＲ_１０で示したアリール基の２価基が挙げられ、同一であっても異なってもよい。上述のアリール基およびアリレン基は以下に示す基を置換基として有してもよい。
（１）ハロゲン原子、トリフルオロメチル基、シアノ基、ニトロ基。
（２）アルキル基としては、好ましくは、Ｃ_１〜Ｃ_１２とりわけＣ_１〜Ｃ_８、さらに好ましくはＣ_１〜Ｃ_４の直鎖または分岐鎖のアルキル基であり、これらのアルキル基はさらにフッ素原子、水酸基、シアノ基、Ｃ_１〜Ｃ_４のアルコキシ基、フェニル基、またはハロゲン原子、Ｃ_１〜Ｃ_４のアルキル基もしくはＣ_１〜Ｃ_４のアルコキシ基で置換されたフェニル基を含有してもよい。具体的には、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、トリフルオロメチル基、２−ヒドロキシエチル基、２−シアノエチル基、２−エトキシエチル基、２−メトキシエチル基、ベンジル基、４−クロロベンジル基、４−メチルベンジル基、４−メトキシベンジル基、４−フェニルベンジル基等が挙げられる。
（３）アルコキシ基（−ＯＲ_１１２）、式中のＲ_１１２は（２）で定義したアルキル基を表わす。具体的には、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｔ−ブトキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｉ−ブトキシ基、２−ヒドロキシエトキシ基、２−シアノエトキシ基、ベンジルオキシ基、４−メチルベンジルオキシ基、トリフルオロメトキシ基等が挙げられる。
（４）アリールオキシ基としては、アリール基としてフェニル基、ナフチル基が挙げられる。これは、Ｃ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有してもよい。具体的には、フェノキシ基、１−ナフチルオキシ基、２−ナフチルオキシ基、４−メチルフェノキシ基、４−メトキシフェノキシ基、４−クロロフェノキシ基、６−メチル−２−ナフチルオキシ基等が挙げられる。
（５）置換メルカプト基またはアリールメルカプト基としては、具体的にはメチルチオ基、エチルチオ基、フェニルチオ基、ｐ−メチルフェニルチオ基等が挙げられる。
（６）アルキル置換アミノ基としては、アルキル基は（２）で定義したアルキル基を表す。具体的には、ジメチルアミノ基、ジエチルアミノ基、Ｎ−メチル−Ｎ−プロピルアミノ基、Ｎ，Ｎ−ジベンジルアミノ基等が挙げられる。
（７）アシル基；具体的にはアセチル基、プロピオニル基、ブチリル基、マロニル基、ベンゾイル基等が挙げられる。
【０１１９】
Ｘは下記一般式（Ｄ）のトリアリールアミノ基を有するジオール化合物をホスゲン法、エステル交換法等を用い重合するとき、下記一般式（Ｂ）のジオール化合物を併用することにより主鎖中に導入される。この場合、製造されるポリカーボネート樹脂はランダム共重合体、またはブロック共重合体となる。また、Ｘは下記一般式（Ｄ）のトリアリールアミノ基を有するジオール化合物と下記一般式（Ｂ）から誘導されるビスクロロホーメートとの重合反応によっても繰り返し単位中に導入される。この場合、製造されるポリカーボネートは交互共重合体となる。
【０１２０】
【化１４】

【０１２１】
一般式(Ｂ)のジオール化合物は一般式（１）と同じものが挙げられる。
【０１２２】
高分子電荷輸送物質の第４の例としては下記一般式（４）で表されるトリアリールアミン構造有するポリカーボネートがある。
【０１２３】
【化１５】

【０１２４】
式中、Ｒ_１１，Ｒ_１２は置換もしくは無置換のアリール基、Ａｒ_７，Ａｒ₈，Ａｒ₉は同一または異なるアリレン基、ｓは１〜５の整数を表す。Ｘ，ｋ，ｊおよびｎは、一般式（１）の場合と同じである。
【０１２５】
一般式（４）の具体例
Ｒ_１１，Ｒ_１２は置換もしくは無置換のアリール基を表すが、その具体例としては以下のものを挙げることができ、同一であっても異なってもよい。
芳香族炭化水素基としては、フェニル基、縮合多環基としてナフチル基、ピレニル基、２−フルオレニル基、９，９−ジメチル−２−フルオレニル基、アズレニル基、アントリル基、トリフェニレニル基、クリセニル基、フルオレニリデンフェニル基、５Ｈ−ジベンゾ ［ａ，ｄ］シクロヘプテニリデンフェニル基、非縮合多環基としてビフェニリル基、ターフェニリル基などが挙げられる。
複素環基としては、チエニル基、ベンゾチエニル基、フリル基、ベンゾフラニル基、カルバゾリル基などが挙げられる。
【０１２６】
また、Ａｒ_７，Ａｒ₈およびＡｒ₉で示されるアリレン基としてはＲ_１１およびＲ_１２で示したアリール基の２価基が挙げられ、同一であっても異なってもよい。
上述のアリール基およびアリレン基は以下に示す基を置換基として有してもよい。
（１）ハロゲン原子、トリフルオロメチル基、シアノ基、ニトロ基。
（２）アルキル基としては、好ましくは、Ｃ_１〜Ｃ_１２とりわけＣ_１〜Ｃ_８、さらに好ましくはＣ_１〜Ｃ_４の直鎖または分岐鎖のアルキル基であり、これらのアルキル基はさらにフッ素原子、水酸基、シアノ基、Ｃ_１〜Ｃ_４のアルコキシ基、フェニル基、またはハロゲン原子、Ｃ_１〜Ｃ_４のアルキル基もしくはＣ_１〜Ｃ_４のアルコキシ基で置換されたフェニル基を含有してよい。具体的には、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、トリフルオロメチル基、２−ヒドロキシエチル基、２−シアノエチル基、２−エトキシエチル基、２−メトキシエチル基、ベンジル基、４−クロロベンジル基、４−メチルベンジル基、４−メトキシベンジル基、４−フェニルベンジル基等が挙げられる。
（３）アルコキシ基（−ＯＲ_１１３ ）、式中のＲ_１１３は（２）で定義したアルキル基を表わす。具体的には、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｔ−ブトキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｉ−ブトキシ基、２−ヒドロキシエトキシ基、２−シアノエトキシ基、ベンジルオキシ基、４−メチルベンジルオキシ基、トリフルオロメトキシ基等が挙げられる。
（４）アリールオキシ基としては、アリール基としてフェニル基、ナフチル基が挙げられる。これは、Ｃ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有してもよい。具体的には、フェノキシ基、１−ナフチルオキシ基、２−ナフチルオキシ基、４−メチルフェノキシ基、４−メトキシフェノキシ基、４−クロロフェノキシ基、６−メチル−２−ナフチルオキシ基等が挙げられる。
（５）置換メルカプト基またはアリールメルカプト基としては、具体的にはメチルチオ基、エチルチオ基、フェニルチオ基、ｐ−メチルフェニルチオ基等が挙げられる。
（６）アルキル置換アミノ基としては、アルキル基は（２）で定義したアルキル基を表す。具体的には、ジメチルアミノ基、ジエチルアミノ基、Ｎ−メチル−Ｎ−プロピルアミノ基、Ｎ，Ｎ−ジベンジルアミノ基等が挙げられる。
（７）アシル基としては、具体的にはアセチル基、プロピオニル基、ブチリル基、マロニル基、ベンゾイル基等が挙げられる。
【０１２７】
Ｘは下記一般式（Ｅ）のトリアリールアミノ基を有するジオール化合物をホスゲン法、エステル交換法等を用い重合するとき、下記一般式（Ｂ）のジオール化合物を併用することにより主鎖中に導入される。この場合、製造されるポリカーボネート樹脂はランダム共重合体、またはブロック共重合体となる。また、Ｘは下記一般式（Ｅ）のトリアリールアミノ基を有するジオール化合物と下記一般式（Ｂ）から誘導されるビスクロロホーメートとの重合反応によっても繰り返し単位中に導入される。この場合、製造されるポリカーボネートは交互共重合体となる。
【０１２８】
【化１６】

【０１２９】
一般式（Ｂ）のジオール化合物は一般式（１）と同じものが挙げられる。
【０１３０】
高分子電荷輸送物質の第５の例としては下記一般式（５）で表されるトリアリールアミン構造有するポリカーボネートがある。
【０１３１】
【化１７】

【０１３２】
式中、Ｒ_１３，Ｒ_１４は置換もしくは無置換のアリール基、Ａｒ_１０，Ａｒ_１１，Ａｒ_１２は同一または異なるアリレン基、Ｘ_１，Ｘ_２ は置換もしくは無置換のエチレン基、または置換もしくは無置換のビニレン基を表す。Ｘ，ｋ，ｊおよびｎは、一般式（１）の場合と同じである。
【０１３３】
一般式（５）の具体例
Ｒ_１３，Ｒ_１４ は置換もしくは無置換のアリール基を表すが、その具体例としては以下のものを挙げることができ、同一であっても異なってもよい。
芳香族炭化水素基としては、フェニル基、縮合多環基としてナフチル基、ピレニル基、２−フルオレニル基、９，９−ジメチル−２−フルオレニル基、アズレニル基、アントリル基、トリフェニレニル基、クリセニル基、フルオレニリデンフェニル基、５Ｈ−ジベンゾ ［ａ，ｄ］シクロヘプテニリデンフェニル基、非縮合多環基としてビフェニリル基、ターフェニリル基などが挙げられる。
複素環基としては、チエニル基、ベンゾチエニル基、フリル基、ベンゾフラニル基、カルバゾリル基などが挙げられる。
【０１３４】
また、Ａｒ_１０，Ａｒ_１１，Ａｒ_１２で示されるアリレン基としてはＲ_１３およびＲ_１４で示したアリール基の２価基が挙げられ、同一であっても異なってもよい。
上述のアリール基およびアリレン基は以下に示す基を置換基として有してもよい。
（１）ハロゲン原子、トリフルオロメチル基、シアノ基、ニトロ基。
（２）アルキル基としては、好ましくは、Ｃ_１〜Ｃ_１２とりわけＣ_１〜Ｃ_８ 、さらに好ましくはＣ_１〜Ｃ_４の直鎖または分岐鎖のアルキル基であり、これらのアルキル基はさらにフッ素原子、水酸基、シアノ基、Ｃ_１〜Ｃ_４のアルコキシ基、フェニル基、またはハロゲン原子、Ｃ_１〜Ｃ_４ のアルキル基もしくはＣ_１〜Ｃ_４のアルコキシ基で置換されたフェニル基を含有してもよい。具体的には、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、トリフルオロメチル基、２−ヒドロキシエチル基、２−シアノエチル基、２−エトキシエチル基、２−メトキシエチル基、ベンジル基、４−クロロベンジル基、４−メチルベンジル基、４−メトキシベンジル基、４−フェニルベンジル基等が挙げられる。
（３）アルコキシ基（−ＯＲ_１１４ ）、式中のＲ_１１４は（２）で定義したアルキル基を表わす。具体的には、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｔ−ブトキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｉ−ブトキシ基、２−ヒドロキシエトキシ基、２−シアノエトキシ基、ベンジルオキシ基、４−メチルベンジルオキシ基、トリフルオロメトキシ基等が挙げられる。
（４）アリールオキシ基としては、アリール基としてフェニル基、ナフチル基が挙げられる。これは、Ｃ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有してもよい。具体的には、フェノキシ基、１−ナフチルオキシ基、２−ナフチルオキシ基、４−メチルフェノキシ基、４−メトキシフェノキシ基、４−クロロフェノキシ基、６−メチル−2−ナフチルオキシ基等が挙げられる。
（５）置換メルカプト基またはアリールメルカプト基としては、具体的にはメチルチオ基、エチルチオ基、フェニルチオ基、ｐ−メチルフェニルチオ基等が挙げられる。
（６）アルキル置換アミノ基としては、アルキル基は（２）で定義したアルキル基を表す。具体的には、ジメチルアミノ基、ジエチルアミノ基、Ｎ−メチル−Ｎ−プロピルアミノ基、Ｎ，Ｎ−ジベンジルアミノ基等が挙げられる。
（７）アシル基としては、具体的にはアセチル基、プロピオニル基、ブチリル基、マロニル基、ベンゾイル基等が挙げられる。
【０１３５】
Ｘ_１，Ｘ_２は置換もしくは無置換のエチレン基、置換もしくは無置換のビニレン基を表し、この置換基としては、シアノ基、ハロゲン原子、ニトロ基、上記Ｒ_１３，Ｒ_１４のアリール基、上記（２）のアルキル基が挙げられる。
【０１３６】
Ｘは下記一般式（Ｆ）のトリアリールアミノ基を有するジオール化合物をホスゲン法、エステル交換法等を用い重合するとき、下記一般式（Ｂ）のジオール化合物を併用することにより主鎖中に導入される。この場合、製造されるポリカーボネート樹脂はランダム共重合体、またはブロック共重合体となる。また、Ｘは下記一般式（Ｆ）のトリアリールアミノ基を有するジオール化合物と下記一般式（Ｂ）から誘導されるビスクロロホーメートとの重合反応によっても繰り返し単位中に導入される。この場合、製造されるポリカーボネートは交互共重合体となる。
【０１３７】
【化１８】

【０１３８】
一般式（Ｂ）のジオール化合物は一般式（１）と同じものが挙げられる。
【０１３９】
高分子電荷輸送物質の第６の例としては下記一般式（６）で表されるトリアリールアミン構造有するポリカーボネートがある。
【０１４０】
【化１９】

【０１４１】
式中、Ｒ_１５，Ｒ_１６，Ｒ_１７，Ｒ_１８は置換もしくは無置換のアリール基、Ａｒ_１３，Ａｒ_１４，Ａｒ_１５，Ａｒ_１６は同一または異なるアリレン基、Ｙ_１，Ｙ_２，Ｙ_３は単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル基、酸素原子、硫黄原子、ビニレン基を表し同一であっても異なってもよい。Ｘ，ｋ，ｊおよびｎは、一般式（１）の場合と同じである。
【０１４２】
一般式（６）の具体例
Ｒ_１５，Ｒ_１６，Ｒ_１７，Ｒ_１８は置換もしくは無置換のアリール基を表すが、その具体例としては以下のものを挙げることができ同一であっても異なってもよい。
芳香族炭化水素基としては、フェニル基、縮合多環基としてナフチル基、ピレニル基、２−フルオレニル基、９，９−ジメチル−２−フルオレニル基、アズレニル基、アントリル基、トリフェニレニル基、クリセニル基、フルオレニリデンフェニル基、５Ｈ−ジベンゾ ［ａ，ｄ］シクロヘプテニリデンフェニル基、非縮合多環基としてビフェニリル基、ターフェニリル基などが挙げられる。
複素環基としては、チエニル基、ベンゾチエニル基、フリル基、ベンゾフラニル基、カルバゾリル基などが挙げられる。
【０１４３】
また、Ａｒ_１３，Ａｒ_１４，Ａｒ_１５および Ａｒ_１６で示されるアリレン基としては、Ｒ_１５，Ｒ_１６，Ｒ_１７およびＲ_１８で示した上記のアリール基の２価基が挙げられ、同一であっても異なってもよい。
上述のアリール基およびアリレン基は以下に示す基を置換基として有してもよい。
（１）ハロゲン原子、トリフルオロメチル基、シアノ基、ニトロ基。
（２）アルキル基としては、好ましくは、Ｃ_１〜Ｃ_１２とりわけＣ_１〜Ｃ_８ 、さらに好ましくはＣ_１〜Ｃ_４の直鎖または分岐鎖のアルキル基であり、これらのアルキル基はさらにフッ素原子、水酸基、シアノ基、Ｃ_１〜Ｃ_４のアルコキシ基、フェニル基、またはハロゲン原子、Ｃ_１〜Ｃ_４のアルキル基もしくはＣ_１〜Ｃ_４のアルコキシ基で置換されたフェニル基を含有してもよい。具体的には、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、トリフルオロメチル基、２−ヒドロキシエチル基、２−シアノエチル基、２−エトキシエチル基、２−メトキシエチル基、ベンジル基、４−クロロベンジル基、４−メチルベンジル基、４−メトキシベンジル基、４−フェニルベンジル基等が挙げられる。
（３）アルコキシ基（−ＯＲ_１１５）、式中のＲ_１１５は（２）で定義したアルキル基を表わす。具体的には、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｔ−ブトキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｉ−ブトキシ基、２−ヒドロキシエトキシ基、２−シアノエトキシ基、ベンジルオキシ基、４−メチルベンジルオキシ基、トリフルオロメトキシ基等が挙げられる。
（４）アリールオキシ基としては、アリール基としてフェニル基、ナフチル基が挙げられる。これは、Ｃ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有してもよい。具体的には、フェノキシ基、１−ナフチルオキシ基、２−ナフチルオキシ基、４−メチルフェノキシ基、４−メトキシフェノキシ基、４−クロロフェノキシ基、６−メチル−２−ナフチルオキシ基等が挙げられる。
【０１４４】
Ｙ_１，Ｙ_２，Ｙ_３は単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル基、酸素原子、硫黄原子、ビニレン基、を表し同一であっても異なってもよい。
アルキレン基としては、上記（２）で示したアルキル基より誘導される２価基を表す。具体的には、メチレン基、エチレン基、１，３−プロピレン基、１，４−ブチレン基、２−メチル−１，３−プロピレン基、ジフルオロメチレン基、ヒドロキシエチレン基、シアノエチレン基、メトキシエチレン基、フェニルメチレン基、４−メチルフェニルメチレン基、２，２−プロピレン基、２，２−ブチレン基、ジフェニルメチレン基等を挙げることができる。
シクロアルキレン基としては、１，１−シクロペンチレン基、１，１−シクロへキシレン基、１，１−シクロオクチレン基等を挙げることができる。
アルキレンエーテル基としては、ジメチレンエーテル基、ジエチレンエーテル基、エチレンメチレンエーテル基、ビス（トリエチレン）エーテル基、ポリテトラメチレンエーテル基等が挙げられる。
【０１４５】
Ｘは下記一般式（Ｇ）のトリアリールアミノ基を有するジオール化合物をホスゲン法、エステル交換法等を用い重合するとき、下記一般式（Ｂ）のジオール化合物を併用することにより主鎖中に導入される。この場合、製造されるポリカーボネート樹脂はランダム共重合体、またはブロック共重合体となる。また、Ｘは下記一般式（Ｇ）のトリアリールアミノ基を有するジオール化合物と下記一般式（Ｂ）から誘導されるビスクロロホーメートとの重合反応によっても繰り返し単位中に導入される。この場合、製造されるポリカーボネートは交互共重合体となる。
【０１４６】
【化２０】

【０１４７】
一般式(Ｂ)のジオール化合物は一般式（１）と同じものが挙げられる。
【０１４８】
高分子電荷輸送物質の第７の例としては下記一般式（７）で表されるトリアリールアミン構造有するポリカーボネートがある。
【０１４９】
【化２１】

【０１５０】
式中、Ｒ_１９，Ｒ_２０は水素原子、置換もしくは無置換のアリール基を表し，Ｒ_１９とＲ_２０は環を形成していてもよい。Ａｒ_１７，Ａｒ_１８，Ａｒ_１９は同一または異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、一般式（１）の場合と同じである。
【０１５１】
一般式（７）の具体例
Ｒ_１９，Ｒ_２０は置換もしくは無置換のアリール基を表すが、その具体例としては以下のものを挙げることができ、同一であっても異なってもよい。
芳香族炭化水素基としては、フェニル基、縮合多環基としてナフチル基、ピレニル基、２−フルオレニル基、９，９−ジメチル−２−フルオレニル基、アズレニル基、アントリル基、トリフェニレニル基、クリセニル基、フルオレニリデンフェニル基、５Ｈ−ジベンゾ［ａ，ｄ］シクロヘプテニリデンフェニル基、非縮合多環基としてビフェニリル基、ターフェニリル基などが挙げられる。
複素環基としては、チエニル基、ベンゾチエニル基、フリル基、ベンゾフラニル基、カルバゾリル基などが挙げられる。
また、Ｒ_１９，Ｒ_２０は環を形成する場合、９−フルオリニリデン、５Ｈ−ジベンゾ［ａ，ｄ］シクロヘブテニリデンなどが挙げられる。
【０１５２】
また、Ａｒ_１７，Ａｒ_１８，Ａｒ_１９で示されるアリレン基としてはＲ_１９およびＲ_２０で示したアリール基の２価基が挙げられ、同一であっても異なってもよい。
上述のアリール基およびアリレン基は以下に示す基を置換基として有してもよい。
（１）ハロゲン原子、トリフルオロメチル基、シアノ基、ニトロ基。
（２）アルキル基としては、好ましくは、Ｃ_１〜Ｃ_１２とりわけＣ_１〜Ｃ_８、さらに好ましくはＣ_１〜Ｃ_４の直鎖または分岐鎖のアルキル基であり、これらのアルキル基はさらにフッ素原子、水酸基、シアノ基、Ｃ_１〜Ｃ_４のアルコキシ基、フェニル基、またはハロゲン原子、Ｃ_１〜Ｃ_４のアルキル基もしくはＣ_１〜Ｃ_４のアルコキシ基で置換されたフェニル基を含有してもよい。具体的には、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、トリフルオロメチル基、２−ヒドロキシエチル基、２−シアノエチル基、２−エトキシエチル基、２−メトキシエチル基、ベンジル基、４−クロロベンジル基、４−メチルベンジル基、４−メトキシベンジル基、４−フェニルベンジル基等が挙げられる。
（３）アルコキシ基（−ＯＲ_{１１ 6}）、式中のＲ_{１１ 6} は（２）で定義したアルキル基を表わす。具体的には、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｔ−ブトキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｉ−ブトキシ基、２−ヒドロキシエトキシ基、２−シアノエトキシ基、ベンジルオキシ基、４−メチルベンジルオキシ基、トリフルオロメトキシ基等が挙げられる。
（４）アリールオキシ基としては、アリール基としてフェニル基、ナフチル基が挙げられる。これは、Ｃ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有してもよい。具体的には、フェノキシ基、１−ナフチルオキシ基、２−ナフチルオキシ基、４−メチルフェノキシ基、４−メトキシフェノキシ基、４−クロロフェノキシ基、６−メチル−２−ナフチルオキシ基等が挙げられる。
（５）置換メルカプト基またはアリールメルカプト基としては、具体的にはメチルチオ基、エチルチオ基、フェニルチオ基、ｐ−メチルフェニルチオ基等が挙げられる。
（６）アルキル置換アミノ基としては、アルキル基は（２）で定義したアルキル基を表す。具体的には、ジメチルアミノ基、ジエチルアミノ基、Ｎ−メチル−Ｎ−プロピルアミノ基、Ｎ，Ｎ−ジベンジルアミノ基等が挙げられる。
（７）アシル基としては、具体的にはアセチル基、プロピオニル基、ブチリル基、マロニル基、ベンゾイル基等が挙げられる。
【０１５３】
Ｘは下記一般式（Ｈ）のトリアリールアミノ基を有するジオール化合物をホスゲン法、エステル交換法等を用い重合するとき、下記一般式（Ｂ）のジオール化合物を併用することにより主鎖中に導入される。この場合、製造されるポリカーボネート樹脂はランダム共重合体、またはブロック共重合体となる。また、Ｘは下記一般式（Ｈ）のトリアリールアミノ基を有するジオール化合物と下記一般式（Ｂ）から誘導されるビスクロロホーメートとの重合反応によっても繰り返し単位中に導入される。この場合、製造されるポリカーボネートは交互共重合体となる。
【０１５４】
【化２２】

【０１５５】
一般式（Ｂ）のジオール化合物は一般式（１）と同じものが挙げられる。
【０１５６】
高分子電荷輸送物質の第８の例としては下記一般式（８）で表されるトリアリールアミン構造有するポリカーボネートがある。
【０１５７】
【化２３】

【０１５８】
式中、Ｒ_２１は置換もしくは無置換のアリール基、Ａｒ_２０，Ａｒ_２１，Ａｒ_２２，Ａｒ_２３は同一または異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、一般式（１）の場合と同じである。
【０１５９】
一般式（８）の具体例
Ｒ_２１は置換もしくは無置換のアリール基を表すが、その具体例としては以下のものを挙げることができ、同一であっても異なってもよい。
芳香族炭化水素基としては、フェニル基、縮合多環基としてナフチル基、ピレニル基、２−フルオレニル基、９，９−ジメチル−２−フルオレニル基、アズレニル基、アントリル基、トリフェニレニル基、クリセニル基、フルオレニリデンフェニル基、５Ｈ−ジベンゾ ［ａ，ｄ］シクロヘプテニリデンフェニル基、非縮合多環基としてビフェニリル基、ターフェニリル基などが挙げられる。
複素環基としては、チエニル基、ベンゾチエニル基、フリル基、ベンゾフラニル基、カルバゾリル基などが挙げられる。
【０１６０】
また、Ａｒ_２０，Ａｒ_２１，Ａｒ_２２，Ａｒ_２３で示されるアリレン基としてはＲ_２１で示したアリール基の２価基が挙げられ、同一であっても異なってもよい。
上述のアリール基およびアリレン基は以下に示す基を置換基として有してもよい。
（１）ハロゲン原子、トリフルオロメチル基、シアノ基、ニトロ基。
（２）アルキル基としては、好ましくは、Ｃ_１〜Ｃ_１２とりわけＣ_１〜Ｃ_８、さらに好ましくはＣ_１〜Ｃ_４の直鎖または分岐鎖のアルキル基であり、これらのアルキル基はさらにフッ素原子、水酸基、シアノ基、Ｃ_１〜Ｃ_４のアルコキシ基、フェニル基、またはハロゲン原子、Ｃ_１〜Ｃ_４のアルキル基もしくはＣ_１〜Ｃ_４のアルコキシ基で置換されたフェニル基を含有してもよい。具体的には、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、トリフルオロメチル基、２−ヒドロキシエチル基、２−シアノエチル基、２−エトキシエチル基、２−メトキシエチル基、ベンジル基、４−クロロベンジル基、４−メチルベンジル基、４−メトキシベンジル基、４−フェニルベンジル基等が挙げられる。
（３）アルコキシ基（−ＯＲ_１１７）、式中の Ｒ_１１７ は（２）で定義したアルキル基を表す。具体的には、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｔ−ブトキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｉ−ブトキシ基、２−ヒドロキシエトキシ基、２−シアノエトキシ基、ベンジルオキシ基、４−メチルベンジルオキシ基、トリフルオロメトキシ基等が挙げられる。
（４）アリールオキシ基としては、アリール基としてフェニル基、ナフチル基が挙げられる。これは、Ｃ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有してもよい。具体的には、フェノキシ基、１−ナフチルオキシ基、２−ナフチルオキシ基、４−メチルフェノキシ基、４−メトキシフェノキシ基、４−クロロフェノキシ基、６−メチル−２−ナフチルオキシ基等が挙げられる。
（５）置換メルカプト基またはアリールメルカプト基としては、具体的にはメチルチオ基、エチルチオ基、フェニルチオ基、ｐ−メチルフェニルチオ基等が挙げられる。
（６）アルキル置換アミノ基としては、アルキル基は（２）で定義したアルキル基を表す。具体的には、ジメチルアミノ基、ジエチルアミノ基、Ｎ−メチル−Ｎ−プロピルアミノ基、Ｎ，Ｎ−ジベンジルアミノ基等が挙げられる。
（７）アシル基としては、具体的にはアセチル基、プロピオニル基、ブチリル基、マロニル基、ベンゾイル基等が挙げられる。
【０１６１】
Ｘは下記一般式（Ｊ）のトリアリールアミノ基を有するジオール化合物をホスゲン法、エステル交換法等を用い重合するとき、下記一般式（Ｂ）のジオール化合物を併用することにより主鎖中に導入される。この場合、製造されるポリカーボネート樹脂はランダム共重合体、またはブロック共重合体となる。また、Ｘは下記一般式（Ｊ）のトリアリールアミノ基を有するジオール化合物と下記一般式（Ｂ）から誘導されるビスクロロホーメートとの重合反応によっても繰り返し単位中に導入される。この場合、製造されるポリカーボネートは交互共重合体となる。
【０１６２】
【化２４】

【０１６３】
一般式（Ｂ）のジオール化合物は一般式（１）と同じものが挙げられる。
【０１６４】
高分子電荷輸送物質の第９の例としては下記一般式（９）で表されるトリアリールアミン構造有するポリカーボネートがある。
【０１６５】
【化２５】

【０１６６】
式中、Ｒ_２２，Ｒ_２３，Ｒ_２４，Ｒ_２５は置換もしくは無置換のアリール基、Ａｒ_２４，Ａｒ_２５，Ａｒ_２６，Ａｒ_２７，Ａｒ_２８は同一または異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、一般式（１）の場合と同じである。
【０１６７】
一般式（９）の具体例
Ｒ_２２，Ｒ_２３，Ｒ_２４，Ｒ_２５は置換もしくは無置換のアリール基を表すが、その具体例としては以下のものを挙げることができ同一であっても異なってもよい。
芳香族炭化水素基としては、フェニル基、縮合多環基としてナフチル基、ピレニル基、２−フルオレニル基、９，９−ジメチル−２−フルオレニル基、アズレニル基、アントリル基、トリフェニレニル基、クリセニル基、フルオレニリデンフェニル基、５Ｈ−ジベンゾ ［ａ，ｄ］シクロヘプテニリデンフェニル基、非縮合多環基としてビフェニリル基、ターフェニリル基などが挙げられる。
複素環基としては、チエニル基、ベンゾチエニル基、フリル基、ベンゾフラニル基、カルバゾリル基などが挙げられる。
【０１６８】
また、Ａｒ_２４，Ａｒ_２５，Ａｒ_２６，Ａｒ_２７およびＡｒ_２８で示されるアリレン基としては、Ｒ_２２，Ｒ_２３，Ｒ_２４およびＲ_２５で示した上記のアリール基の２価基が挙げられ、同一であっても異なってもよい。
上述のアリール基およびアリレン基は以下に示す基を置換基として有してもよい。
（１）ハロゲン原子、トリフルオロメチル基、シアノ基、ニトロ基。
（２）アルキル基としては、好ましくは、Ｃ_１〜Ｃ_１２とりわけＣ_１〜Ｃ_８、さらに好ましくはＣ_１〜Ｃ_４の直鎖または分岐鎖のアルキル基であり、これらのアルキル基はさらにフッ素原子、水酸基、シアノ基、Ｃ_１〜Ｃ_４のアルコキシ基、フェニル基、またはハロゲン原子、Ｃ_１〜Ｃ_４のアルキル基もしくはＣ_１〜Ｃ_４のアルコキシ基で置換されたフェニル基を含有してもよい。具体的には、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、トリフルオロメチル基、２−ヒドロキシエチル基、２−シアノエチル基、２−エトキシエチル基、２−メトキシエチル基、ベンジル基、４−クロロベンジル基、４−メチルベンジル基、４−メトキシベンジル基、４−フェニルベンジル基等が挙げられる。
（３）アルコキシ基（−ＯＲ_１１８）、式中のＲ_１１８は（２）で定義したアルキル基を表す。具体的には、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｔ−ブトキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｉ−ブトキシ基、２−ヒドロキシエトキシ基、２−シアノエトキシ基、ベンジルオキシ基、４−メチルベンジルオキシ基、トリフルオロメトキシ基等が挙げられる。
（４）アリールオキシ基としては、アリール基としてフェニル基、ナフチル基が挙げられる。これは、Ｃ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有してもよい。具体的には、フェノキシ基、１−ナフチルオキシ基、２−ナフチルオキシ基、４−メチルフェノキシ基、４−メトキシフェノキシ基、４−クロロフェノキシ基、６−メチル−２−ナフチルオキシ基等が挙げられる。
（５）置換メルカプト基またはアリールメルカプト基としては、具体的にはメチルチオ基、エチルチオ基、フェニルチオ基、ｐ−メチルフェニルチオ基等が挙げられる。
（6）アルキル置換アミノ基としては、アルキル基は（２）で定義したアルキル基を表す。具体的には、ジメチルアミノ基、ジエチルアミノ基、Ｎ−メチル−Ｎ−プロピルアミノ基、Ｎ，Ｎ−ジベンジルアミノ基等が挙げられる。
（７）アシル基としては、具体的にはアセチル基、プロピオニル基、ブチリル基、マロニル基、ベンゾイル基等が挙げられる。
【０１６９】
Ｘは下記一般式（Ｌ）のトリアリールアミノ基を有するジオール化合物をホスゲン法、エステル交換法等を用い重合するとき、下記一般式（Ｂ）のジオール化合物を併用することにより主鎖中に導入される。この場合、製造されるポリカーボネート樹脂はランダム共重合体、またはブロック共重合体となる。また、Ｘは下記一般式（Ｌ）のトリアリールアミノ基を有するジオール化合物と下記一般式（Ｂ）から誘導されるビスクロロホーメートとの重合反応によっても繰り返し単位中に導入される。この場合、製造されるポリカーボネートは交互共重合体となる。
【０１７０】
【化２６】

【０１７１】
一般式（Ｂ）のジオール化合物は一般式（１）と同じものが挙げられる。
【０１７２】
高分子電荷輸送物質の第１０の例としては下記一般式（１０）で表されるトリアリールアミン構造有するポリカーボネートがある。
【０１７３】
【化２７】

【０１７４】
式中、Ｒ_２６，Ｒ_２７は置換もしくは無置換のアリール基、Ａｒ_２９，Ａｒ_３０，Ａｒ_３１は同一または異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、一般式（１）の場合と同じである。
【０１７５】
一般式（１０）の具体例
Ｒ_２６，Ｒ_２７は置換もしくは無置換のアリール基を表すが、その具体例としては以下のものを挙げることができ、同一であっても異なってもよい。
芳香族炭化水素基として、フェニル基、縮合多環基としてナフチル基、ピレニル基、２−フルオレニル基、９，９−ジメチル−２−フルオレニル基、アズレニル基、アントリル基、トリフェニレニル基、クリセニル基、フルオレニリデンフェニル基、５Ｈ−ジベンゾ ［ａ，ｄ］シクロヘプテニリデンフェニル基、非縮合多環基としてビフェニリル基、ターフェニリル基などが挙げられる。
複素環基として、チエニル基、ベンゾチエニル基、フリル基、ベンゾフラニル基、カルバゾリル基などが挙げられる。
【０１７６】
また、Ａｒ_２９，Ａｒ_３０，Ａｒ_３１で示されるアリレン基としてはＲ_２６およびＲ_２７で示したアリール基の２価基が挙げられ、同一であっても異なってもよい。
上述のアリール基およびアリレン基は以下に示す基を置換基として有してもよい。
（１）ハロゲン原子、トリフルオロメチル基、シアノ基、ニトロ基。
（２）アルキル基としては、好ましくは、Ｃ_１〜Ｃ_１２とりわけＣ_１〜Ｃ_８、さらに好ましくはＣ_１〜Ｃ_４の直鎖または分岐鎖のアルキル基であり、これらのアルキル基はさらにフッ素原子、水酸基、シアノ基、Ｃ_１〜Ｃ_４のアルコキシ基、フェニル基、またはハロゲン原子、Ｃ_１〜Ｃ_４のアルキル基もしくはＣ_１〜Ｃ_４のアルコキシ基で置換されたフェニル基を含有してもよい。具体的には、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、トリフルオロメチル基、２−ヒドロキシエチル基、２−シアノエチル基、２−エトキシエチル基、２−メトキシエチル基、ベンジル基、４−クロロベンジル基、４−メチルベンジル基、４−メトキシベンジル基、４−フェニルベンジル基等が挙げられる。
（３）アルコキシ基（−ＯＲ_１１９）、式中のＲ_１１９は（２）で定義したアルキル基を表わす。具体的には、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｔ−ブトキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｉ−ブトキシ基、２−ヒドロキシエトキシ基、２−シアノエトキシ基、ベンジルオキシ基、４−メチルベンジルオキシ基、トリフルオロメトキシ基等が挙げられる。
（４）アリールオキシ基としては、アリール基としてフェニル基、ナフチル基が挙げられる。これは、Ｃ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有してもよい。具体的には、フェノキシ基、１−ナフチルオキシ基、２−ナフチルオキシ基、４−メチルフェノキシ基、４−メトキシフェノキシ基、４−クロロフェノキシ基、６−メチル−２−ナフチルオキシ基等が挙げられる。
（５）置換メルカプト基またはアリールメルカプト基としては、具体的にはメチルチオ基、エチルチオ基、フェニルチオ基、ｐ−メチルフェニルチオ基等が挙げられる。
（６）アルキル置換アミノ基としては、アルキル基は（２）で定義したアルキル基を表す。具体的には、ジメチルアミノ基、ジエチルアミノ基、Ｎ−メチル−Ｎ−プロピルアミノ基、Ｎ，Ｎ−ジベンジルアミノ基等が挙げられる。
（７）アシル基としては、具体的にはアセチル基、プロピオニル基、ブチリル基、マロニル基、ベンゾイル基等が挙げられる。
【０１７７】
Ｘは下記一般式（Ｍ）のトリアリールアミノ基を有するジオール化合物をホスゲン法、エステル交換法等を用い重合するとき、下記一般式（Ｂ）のジオール化合物を併用することにより主鎖中に導入される。この場合、製造されるポリカーボネート樹脂はランダム共重合体、またはブロック共重合体となる。また、Ｘは下記一般式（Ｍ）のトリアリールアミノ基を有するジオール化合物と下記一般式（Ｂ）から誘導されるビスクロロホーメートとの重合反応によっても繰り返し単位中に導入される。この場合、製造されるポリカーボネートは交互共重合体となる。
【０１７８】
【化２８】

【０１７９】
一般式（Ｂ）のジオール化合物は一般式（１）と同じものが挙げられる。
【０１８０】
さらに、本発明の保護層には必要に応じてポリカルボン酸化合物等の分散剤が用いられる。分散剤は、塗工液作製時に無機フィラーの分散性を向上させ塗工液の安定性を高める目的で必要に応じて添加される。この分散剤としては無機フィラーを一次粒径に近い値まで分散する、電気的特性・画像特性に悪影響を及ぼさない、などの点でポリカルボン酸化合物が特に有効である。
このポリカルボン酸化合物としては、複数のカルボン酸残基を有する低分子化合物、オリゴマー、高分子化合物があり、例えば有機脂肪酸、高酸化樹脂等が挙げられる。このポリカルボン酸化合物がオリゴマー、高分子化合物であるものとしては、ポリエステル樹脂、アクリル樹脂、アクリル酸やメタクリル酸を用いた共重合体、スチレンアクリル共重合体等が挙げられる。ここで用いられるポリカルボン酸化合物の酸価としては、１０〜４００（ｍｇＫＯＨ／ｇ）のものが有効に使用できる。（酸価とは、１ｇ中に含まれる遊離脂肪酸を中和するのに要する水酸化カリウムのミリグラム数で定義される。）
ポリカルボン酸化合物添加量としては、含有される無機フィラー１００重量部に対し０．０１〜５０重量部、好ましくは０．１〜２０重量部である。
【０１８１】
保護層の形成法としては通常の塗布法が採用される。中でも、スプレー工法は有効な手段である。保護層の厚さは１．０〜１５μｍ、好ましくは２〜１０μｍ程度が適当である。
【０１８２】
＜酸化防止剤の添加について＞
また、本発明においては、耐環境性の改善のため、とりわけ、感度低下、残留電位の上昇を防止する目的で、中間層、電荷発生層、電荷輸送層、保護層等の各層に酸化防止剤を添加することができる。本発明に用いることができる酸化防止剤として、下記フェノ−ル系化合物、パラフェニレンジアミン類、ハイドロキノン類、有機硫黄化合物類、有機燐化合物類等が挙げられる。
【０１８３】
フェノ−ル系化合物：
２，６−ジ−ｔ−ブチル−ｐ−クレゾール、ブチル化ヒドロキシアニソール、２，６−ジ−ｔ−ブチル−４−エチルフェノール、ステアリル−β−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、２，２’−メチレン−ビス−（４−メチル−６−ｔ−ブチルフェノール）、２，２’−メチレン−ビス−（４−エチル−６−ｔ−ブチルフェノール）、４，４’−チオビス−（３−メチル−６−ｔ−ブチルフェノール）、４，４’−ブチリデンビス−（３−メチル−６−ｔ−ブチルフェノール）、１，１，３−トリス−（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、テトラキス−［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン、ビス［３，３’−ビス（４’−ヒドロキシ−３’−ｔ−ブチルフェニル）ブチリックアッシド］クリコ−ルエステル、トコフェロール類など。
【０１８４】
パラフェニレンジアミン類：
Ｎ−フェニル−Ｎ’−イソプロピル−ｐ−フェニレンジアミン、Ｎ，Ｎ’−ジ−ｓｅｃ−ブチル−ｐ−フェニレンジアミン、Ｎ−フェニル−Ｎ−ｓｅｃ−ブチル−ｐ−フェニレンジアミン、Ｎ，Ｎ’−ジ−イソプロピル−ｐ−フェニレンジアミン、Ｎ，Ｎ’−ジメチル−Ｎ，Ｎ’−ジ−ｔ−ブチル−ｐ−フェニレンジアミンなど。
【０１８５】
ハイドロキノン類：
２，５−ジ−ｔ−オクチルハイドロキノン、２，６−ジドデシルハイドロキノン、２−ドデシルハイドロキノン、２−ドデシル−５−クロロハイドロキノン、２−ｔ−オクチル−５−メチルハイドロキノン、 ２−（２−オクタデセニル）−５−メチルハイドロキノンなど。
【０１８６】
有機硫黄化合物類：
ジラウリル−３，３’−チオジプロピオネ−ト、ジステアリル−３，３’−チオジプロピオネ−ト、ジテトラデシル−３，３’−チオジプロピオネ−トなど。
【０１８７】
有機燐化合物類：
トリフェニルホスフィン、トリ（ノニルフェニル）ホスフィン、トリ（ジノニルフェニル）ホスフィン、トリクレジルホスフィン、トリ（２，４−ジブチルフェノキシ）ホスフィンなど。
【０１８８】
上記例示化合物は、ゴム、プラスチック、油脂類などの酸化防止剤として知られており、市販品から容易に入手できる。
本発明における酸化防止剤の添加量は、添加する層の総重量に対して０．０１〜１０重量％である。
【０１８９】
【実施例】
次に、実施例によって本発明をさらに詳細に説明するが本発明は以下の実施例に限定されるものではない。尚、実施例中使用する部は、すべて重量部を表す。
【０１９０】
感光体作製例１
φ３０ｍｍのアルミニウムドラム上に、下記組成の中間層用塗工液、電荷発生層用塗工液、電荷輸送層用塗工液、保護層用塗工液を順次、塗布乾燥することにより、０．３μｍの中間層、０．２μｍの電荷発生層、２５μｍの電荷輸送層を形成した。
次いでα−アルミナ粒子含有の保護層用塗工液を電荷輸送層上にスプレー塗工し、保護層を５μｍ設け、本発明の電子写真感光体（感光体）を作製した。

【０１９１】
【化２９】

【０１９２】
【化３０】

【０１９３】
感光体作製例２
感光体作製例１における保護層用塗工液を下記組成のものに変更した以外は、感光体作製例１と同様に感光体を作製した。

【０１９４】
感光体作製例３
感光体作製例１における保護層用塗工液を下記組成のものに変更した以外は、感光体作製例１と同様に感光体を作製した。
〔保護層用塗工液〕

【０１９５】
感光体作製例４
感光体作製例１における保護層用塗工液を下記組成のものに変更した以外は、感光体作製例１と同様に感光体を作製した。

【０１９６】
感光体作製例５
感光体作製例１における保護層用塗工液を下記組成のものに変更した以外は、感光体作製例１と同様に感光体を作製した。

【０１９７】
感光体作製例６
感光体作製例１における保護層用塗工液を下記組成のものに変更した以外は、感光体作製例１と同様に感光体を作製した。

【０１９８】
感光体作製例７
感光体作製例１における保護層用塗工液を下記組成のものに変更した以外は、感光体作製例１と同様に感光体を作製した。

【０１９９】
感光体作製例８
感光体作製例１における保護層用塗工液を下記組成のものに変更した以外は、感光体作製例１と同様に感光体を作製した。

【０２００】
感光体作製例９
感光体作製例１における保護層用塗工液を下記組成のものに変更した以外は、感光体作製例１と同様に感光体を作製した。

【０２０１】
感光体作製例１０
感光体作製例１における保護層用塗工液を下記組成のものに変更した以外は、感光体作製例１と同様に感光体を作製した。

（本塗工液は保護層形成のためのスプレー塗工の際、作製した分散液に凝集物が多く、スプレー吐出量が不安定であった。）
【０２０２】
感光体作製例１１
感光体作製例１における保護層用塗工液を下記組成のものに変更した以外は、感光体作製例１と同様に感光体を作製した。

（本塗工液は作製した感光体表面の凹凸が確認され表面平滑性に劣っていた。）
【０２０３】
感光体作製例１２
感光体作製例１における中間層用塗工液を以下の組成のものに変更し、中間層の膜厚を０．３μｍに変更した以外は、感光体作製例１と同様に感光体を作製した。
〔中間層用塗工液〕
ポリアミド樹脂（ＣＭ８０００：東レ社製） ４部メタノール ７０部ブタノール ３０部
【０２０４】
感光体作製例１３
感光体作製例１における中間層用塗工液を以下の組成のものに変更し、中間層の膜厚を３．５μｍに変更した以外は、感光体作製例１と同様に感光体を作製した。

【０２０５】
感光体作製例１４
感光体作製例１において、導電性支持体に以下の陽極酸化皮膜処理を行い、さらに中間層を形成せずに、陽極酸化皮膜上に電荷発生層、電荷輸送層、保護層を形成し、感光体作製例１と同様に感光体を作製した。
（陽極酸化皮膜処理）
導電性支持体表面の鏡面研磨仕上げを行い、脱脂洗浄、水洗浄を行った後、液温２０℃、硫酸１５ｖｏｌ％の電解浴に浸し、電解電圧１５Ｖにて３０分間陽極酸化皮膜処理を行った。さらに、水洗浄を行った後、７％の酢酸ニッケル水溶液（５０℃）にて封孔処理を行った。さらに、水洗浄を行った後、７％の酢酸ニッケル水溶液（５０℃）にて封孔処理を行った。その後純水による洗浄を経て、６μｍの陽極酸化皮膜が形成された導電性支持体を得た。
【０２０６】
感光体作製例１５
感光体作製例１における保護層用塗工液を下記組成のものに変更した以外は、感光体作製例１と同様に感光体を作製した。
〔保護層用塗工液〕
α−アルミナ粒子（スミコランダムＡＡ−０３：住友化学工業製） ２部
ポリカルボン酸化合物（ＢＹＫ−Ｐ１０４：ビックケミー製） ０．０２部
下記構造（Ｔ−１）の高分子電荷輸送物質 ７部
【０２０７】
【化３１】

シクロヘキサノン ６０部
テトラヒドロフラン ２００部
【０２０８】
感光体作製例１６
感光体作製例１において、電荷輸送層を３０μｍとし、保護層を設けない以外は感光体作製例１と同様に感光体を作製した。
【０２０９】
上記のように作製した感光体について、感光体Ｎｏ．と保護層に含有されるフィラー名および特性値の一覧を表１に示す。
【０２１０】
【表１】

【０２１１】
実施例１、参考例１〜６、比較例１〜３
感光体作製例１、３、５〜１１、１５に示される感光体を図２に示すようなプロセス用カートリッジに装着し、図２に示すようなタンデム方式のフルカラー画像形成装置に搭載した。帯電電位を−８５０Vになるように帯電バイアスを設定し、６５５ｎｍのＬＤを用いて、画像書き込みを行った。出力原稿として、黒文字書き込み率５％、赤文字書き込み率１％の文字チャートを連続１０００枚、さらに４色フルカラーモードで書き込み率６％の斜め格子チャートを連続９０００枚、計１万枚の出力を１セットとして、合計５セット（５万枚）の画像出力を常温常湿（２０℃／５０％ＲＨ）環境下で行った。
【０２１２】
評価方法としては、初期および５万枚通紙後に膜厚の標準偏差、摩耗量、露光部電位の測定と画像評価を行った。それぞれの評価方法および評価結果を以下に示す。
感光体の膜厚と摩耗量：
感光体ドラムの長手方向について、等間隔で２０点、周方向４点の合計８０点から膜厚の標準偏差と平均値（平均膜厚とした）を求めた。
摩耗量は、初期状態における感光体平均膜厚と５万枚通紙後の平均膜厚の差により求めた。膜厚の標準偏差と摩耗量の結果を表２に示す。
露光部電位：
図１の装置の現像部に電位計プローブを装着し、帯電、画像露光後、現像部位まで移動した際の感光体表面電位を測定した。初期および５万枚通紙後の露光部電位の測定結果を表３に示す。
初期および５万枚通紙後の画像：
（１）ハーフトーン、（２）解像度、（３）色再現性の画像品質評価を行った果を表４に示す。以下に各評価について示す。
（１）ハーフトーンの画像評価：初期および５万枚通紙後に各画像形成要素について単色ハーフトーン画像を出力し、目視及び顕微鏡で画質を評価した。画質評価ランクは下記による。
◎・・・良好
○・・・局所的にやや濃度ムラがある
△・・・濃度ムラが発生するが、実使用上問題なし
×・・・濃度ムラが目立つ
（２）解像度の画像評価：初期および５万枚通紙後に各画像形成要素について単色の１００μｍ幅の細線画像を出力し、目視及び顕微鏡を用いて評価した。評価ランクは下記による。
◎・・・良好
○・・・局所的に線幅の太りが見られる
△・・・線太りがやや目立つ
×・・・線幅の太りに加え、トナー飛散が見られる
（３）色再現性の評価：初期および５万枚通紙後のフルカラー画像出力を行い、それぞれのフルカラー画像について、以下のように５〜１の５段階で色再現性のランク付けを行った。５は色再現性が良好であることを示し、１に向かうにつれて再現性が低下することを示す。なお、４以上は実使用上問題ないレベルである。
【０２１３】
【表２】

【０２１４】
【表３】

【０２１５】
【表４】

【０２１６】
また、常温常湿（２０℃／５０％ＲＨ）環境下にて、上記連続５万枚の画像出力を行った後、さらに高温高湿（３０゜C／９０％ＲＨ）環境下で、連続１００枚のフルカラー画像出力を行った。
常温常湿（２０℃／５０％ＲＨ）環境下における連続５万枚通紙後の画像と、高温高湿（３０゜C／９０％ＲＨ）環境下にて連続１００枚のフルカラー画像出力後の画像についての評価結果を表５に示す。
【０２１７】
【表５】

【０２１８】
〈評価結果〉
実施例１、参考例１〜６の結果より、保護層にα−アルミナ粒子を用いることで耐摩耗性、環境特性、静電特性、摩耗特性に対し、タンデム方式のフルカラー画像形成装置用感光体として極めて均質な特性を示すことが分かる。中でも、粒径の揃った、粒度分布の狭い、高純度のα−アルミナを用いることで特に良好な特性を示すことが分かる。一方、比較例１〜３は保護層に含有されるフィラーをα−アルミナ粒子からそれぞれ酸化チタン、シリカ、ポリテトラフルオロエチレンに変えたものである。比較例１からは、フィラーとして用いた酸化チタンにより書き込み光の散乱が生じ解像度が低下し、トナー飛散が見られた。比較例２のシリカを用いた場合には、特に高温高湿の環境下でプリント全面に画像流れが発生した。比較例３では、ポリテトラフルオロエチレンを用いた場合、耐摩耗性の効果が十分でなく、表面の傷や削れによる画像欠陥が認められた。
【０２１９】
実施例２、参考例７、比較例４〜７
次に、感光体作製例２、３、１２〜１４、１６に示される感光体を図２に示すようなプロセス用カートリッジに装着し、図１に示すようなタンデム方式のフルカラー画像形成装置に搭載した。帯電電位を−８５０Vになるように帯電バイアスを設定し、６５５ｎｍのＬＤを用いて画像書き込みを行った。出力原稿として、書き込み率６％の斜め格子チャートのフルカラー画像出力を常温常湿（２０℃／５０％ＲＨ）環境下で連続５万枚行い、初期および５万枚通紙後の地肌部の地汚れを目視にて評価し、以下のようにランク付けを行った。評価結果を表６に示す。
◎・・・良好
○・・・僅かに汚れが認められる
△・・・地汚れが認められるが、実使用上問題なし
×・・・地汚れが目立ち、画質が低下
【０２２０】
【表６】

【０２２１】
実施例３、参考例８、比較例８〜１１
また、感光体作製例２、３、１２〜１４、１６に示される感光体を図２に示すようなプロセス用カートリッジに装着し、図１に示すようなタンデム方式のフルカラー画像形成装置に搭載した。帯電電位を−８５０Vになるように帯電バイアスを設定し、６５５ｎｍのＬＤを用いて画像書き込みを行った。フルカラー画像出力を低温低湿（１０゜C／１５％ＲＨ）環境下で連続５００枚行い、初期および５００枚通紙後のフルカラー画像について画質評価を行った結果を表７に示す。
【０２２２】
【表７】

【０２２３】
〈評価結果〉
表６、７の実施例８〜１１の結果から明らかなように、中間層に本発明のゾルゲル法による無機系の硬化膜を用いた場合、常温常湿、および低温低湿の環境下での繰り返し使用においても優れた画像品質が安定して得られた。
感光体１２の中間層にポリアミドよりなる樹脂層を用いた場合には、中間層の電気抵抗の増大を招くために画像濃度の低下を引き起こし、所望の画質が継続的に得られない。感光体１３のように導電性フィラーをバインダー樹脂中に分散した中間層を用いた場合、フィラー分散性の問題や、露光部電位の上昇により、安定した画像が得られない。感光体１４のように中間層の代わりにアルマイトを用いた場合、使用初期において画像の地汚れや黒ポチ等の画像欠陥が見られた。感光体１６のように保護層を設けない場合、耐久性を有しないことが分かる。
【０２２４】
【発明の効果】
以上のように本発明により、あらゆる環境下において、使用初期状態の各感光体間が均一な特性を有し、タンデム方式特有の様々なプリントモードで繰り返し使用された場合においても、耐摩耗性、静電疲労安定性が高く、複数の電子写真感光体間での特性変化やバラツキの小さい極めて均質な電子写真感光体が提供できる。また、該電子写真感光体を用いることにより、あらゆる環境下において、同一原稿の多数枚のカラー画像を形成した場合においても、常に色再現性の良好な画像を形成することができる小型で、かつ高速のタンデム方式のフルカラー画像形成装置および該画像形成装置用プロセスカートリッジを提供できる。
【図面の簡単な説明】
【図１】本発明のタンデム方式のフルカラー画像形成装置を説明するための概略図である。
【図２】本発明のフルカラー画像形成装置用プロセスカートリッジを説明するための概略図である。
【図３】本発明の電子写真感光体の感光層が単層構成の構成例を示す断面模式図である。
【図４】本発明の電子写真感光体の感光層が積層構成された別の構成例を示す断面模式図である。
【図５】本発明の電子写真感光体の感光層が積層構成されたさらに別の構成例を示す断面模式図である。
【符号の説明】
１Ｃ、１Ｍ、１Ｙ、１Ｋ 感光体
２Ｃ、２Ｍ、２Ｙ、２Ｋ 帯電部材
３Ｃ、３Ｍ、３Ｙ、３Ｋ レーザー光
４Ｃ、４Ｍ、４Ｙ、４Ｋ 現像部材
５Ｃ、５Ｍ、５Ｙ、５Ｋ クリーニング部材
６Ｃ、６Ｍ、６Ｙ、６Ｋ 画像形成要素
７ 転写紙
８ 供給コロ
９ レジストローラ
１０ 転写搬送ベルト
１１Ｃ、１１Ｍ、１１Ｙ、１１Ｋ 転写ブラシ
１２ 定着装置
１６ 感光体
１７ 帯電チャージャ
１８ クリーニングブラシ
１９ 画像露光部
２０ 現像ローラ
３１ 導電性支持体
３２ 中間層
３３ 感光層
３４ 電荷発生層
３５ 電荷輸送層
３６ 保護層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a tandem full color image forming apparatus having high durability and realizing high image quality over a long period of time, and a process cartridge for the full color image forming apparatus.
[0002]
[Prior art]
An electrophotographic method using an electrophotographic photosensitive member applied to a copying machine, a facsimile, a laser printer, or the like is a toner image after at least the electrophotographic photosensitive member (photosensitive member) has undergone charging, image exposure, and development processes. Is a system comprising a process of transferring and fixing to an image holding member (transfer paper). The basic characteristics required of the photoconductor in this electrophotographic system are (1) that it can be charged to an appropriate potential in a dark place, (2) there is little charge dissipation in the dark place, and (3) light irradiation. Can quickly dissipate the charge.
In addition to these characteristics, long-term reliability such as image quality characteristics, low pollution, and low cost are also required.
[0003]
Conventionally, as a photoconductor used in an electrophotographic system, a photoconductive layer mainly composed of selenium or a selenium alloy is provided on a conductive support, and an inorganic photoconductive material such as zinc oxide or cadmium sulfide is used as a binder. In general, those dispersed in the material and those using an amorphous silicon-based material are known. However, in recent years, the cost is low, the degree of freedom in designing the photoconductor, the pollution-free property, etc. Therefore, organic photoreceptors are widely used.
[0004]
For organic photoreceptors, photoconductive resins typified by polyvinylcarbazole (PVK), charge transfer complex types typified by PVK-TNF (2,4,7-trinitrofluorenone), typified by phthalocyanine-binder Pigment dispersion type, functional separation type photoconductor using a combination of charge generation material and charge transport material, etc. are known. Especially, the functional separation type photoconductor has various characteristics such as sensitivity, durability, and stability. And is attracting attention.
[0005]
The mechanism of electrostatic latent image formation in this function-separated type photoreceptor is that when the photoreceptor is charged and irradiated with light, the light passes through the transparent charge transport layer and is absorbed by the charge generation material in the charge generation layer, The charge generating material that has absorbed the light generates charge carriers, which are injected into the charge transport layer and move in the charge transport layer along the electric field generated by charging, neutralizing the charge on the surface of the photoreceptor. Thus, an electrostatic latent image is formed. In the functionally separated photoconductor, a charge transport material that has high mobility without absorption mainly in the visible region and near infrared region, and a charge generation material that absorbs mainly in the visible region and has high quantum efficiency are combined. Are known and useful.
[0006]
However, many charge transport materials for organic electrophotographic photoreceptors used in electrophotography have been developed as low-molecular compounds, and low-molecular compounds alone have no film-forming properties. Used by dispersing and mixing. However, a charge transport layer composed of a low molecular charge transport material and an inert polymer is generally soft and wears due to mechanical load on the surface of the photoreceptor when repeatedly used in an electrophotographic process, resulting in a film thickness of the charge transport layer. The disadvantage is that the thickness of the film becomes thinner. In fact, the electric field strength increases due to wear of the photoconductor, and abnormal images such as black spots due to local leaks, image density decrease due to sensitivity deterioration, and background stains may occur, which may shorten the life of the photoconductor.
[0007]
Further, in recent years, colorization of image forming apparatuses has progressed, and the following two systems are generally proposed as color image forming apparatuses using an electrophotographic system.
One is a so-called single method or single drum method, in which one photosensitive member is mounted in the apparatus and four color developing members are mounted. In this method, four colors (cyan, magenta, yellow, and black) on the photosensitive member or on the transfer target member (directly transferred to the output paper or once transferred to the intermediate transfer member and then transferred to the paper) are used. A toner image is formed. In this case, the charging member, the exposure member, the transfer member, and the fixing member arranged around the photoconductor can be shared, and can be designed to be smaller and less expensive than the tandem method described later. is there.
[0008]
On the other hand, there is a system called a tandem system or a tandem drum system as another system. This is one in which a plurality of photoconductors are mounted at least in the apparatus. In general, one charging member, one exposure member, and one developing member are arranged on one photoconductor to form one image forming element, and a plurality of (generally, four) members are mounted. ing. In this method, one color toner image is formed by one image forming element, and the toner image is sequentially transferred to a transfer target to form a color image. An advantage of this method is that high-speed image formation is possible. This is because the toner images of the respective colors can be produced by parallel processing as described above. For this reason, compared with the single method, the image forming processing time is about one-fourth, and it is possible to cope with four times higher speed printing.
[0009]
However, this tandem system has an advantage that it can cope with high-speed color recording, but has several problems because it has a plurality of image forming elements. For example, the size of the apparatus can be increased and the characteristics can be made uniform among a plurality of image forming elements. In other words, in the conventional single method, only one photoconductor is used, and in the simplest configuration, a charger and a writing system are shared, and a configuration in which a plurality of developing devices are arranged is limited. It is.
[0010]
However, in order to realize high-speed color recording, it is indispensable to produce toner images of each color in parallel as described above, and at least a charger, a writing system, and a developer corresponding to a plurality of photosensitive members are individually exposed to light. It is necessary to place it around the body. In order to reduce the size of one image forming element, it is important to reduce the charger, the writing system, and the developer arranged around the photoconductor, but the diameter of the photoconductor at the center is reduced. It is most important.
[0011]
On the other hand, when a toner image is simultaneously formed using a plurality of image forming elements as described above, all the conditions in which the electrostatic latent image is formed must be the same. That is, if any one of a plurality of conditions is different, problems such as color reproducibility and color unevenness occur. This is a significant difference from the single method. What influences this condition most is the characteristic change and variation of the photoreceptor.
[0012]
From the above, a photoreceptor used in a tandem image forming apparatus is required to have a small diameter and high durability at the same time. That is, for the reduction in diameter corresponding to high-speed color recording, high sensitivity and high-speed response of the photosensitive member are required. Further, high durability that does not cause a difference between a plurality of photoconductors, that is, wear resistance and potential stability is required. In particular, regarding wear resistance and potential stability, (1) elimination of variations in electrostatic characteristics and film thickness in the initial state of use of a plurality of photoconductors, and (2) profile of electrostatic fatigue characteristics in repeated use of photoconductors. (3) It is an extremely important point to make the wear amount and wear distribution of the photoreceptor uniform in repeated use.
[0013]
However, since the development of the photoreceptors up to now has been carried out on the image forming apparatus using the single color method or monochrome development, the electrostatic characteristics and wear characteristics of a plurality of photoreceptors are initially and repeatedly used. Until later, the idea of uniformization was rare, and there were very few technologies that could cope with it.
[0014]
In response to such problems, image forming apparatuses using amorphous silicon, which is a representative inorganic photoconductive material, are proposed as tandem image forming apparatus photoconductors (Japanese Patent Laid-Open Nos. 12-19809 and 13-13). However, the photoconductor using amorphous silicon for the photoconductive layer has a problem that the charging ability is low, and contrast cannot be obtained in each color of cyan, magenta, and yellow. There are also problems such as being easily affected and high production costs. Also, other materials such as selenium-based materials and CdS as inorganic photoconductive materials are considered difficult to develop due to toxicity problems. In contrast, in the present application, the photoconductive material constituting the photoconductor is an organic photoconductive material.
[0015]
As a means for improving the abrasion resistance, there is a concept of providing a protective layer on the outermost surface of the photoreceptor. Examination of a protective layer as a surface layer of a photoreceptor starts with an inorganic photoreceptor, and is described in, for example, Japanese Patent Publication No. 2-3171, Japanese Patent Publication No. 2-7058, Japanese Patent Publication No. 3-43618, and the like. Yes. When the protective layer is thus provided on the surface of the inorganic photoreceptor, a filler having a relatively low electric resistance is used for the protective layer (Japanese Patent Laid-Open Nos. 63-254462 and 63-254463). Publication). For this reason, when the photosensitive member is charged, the protective layer bulk or the protective layer / inorganic photosensitive layer interface is often charged rather than charged on the surface of the photosensitive member. Thus, when the latent image is formed not on the surface of the photoreceptor but inside the protective layer (including the interface with the inorganic photosensitive layer), there is an advantage that the influence of the shape (such as scratches) on the surface of the photoreceptor is reduced. However, when an attempt is made to give the surface layer a function as a protective layer, it is necessary to add a large amount of a conductive metal oxide as a filler to be added to the surface layer (protective layer). In this case, even if the transparency of the surface layer is ensured by appropriate selection of the material, the bulk or surface resistance of the surface layer (protective layer) becomes low, so that the disadvantage of image blur may appear during repeated use. there were. In order to eliminate such drawbacks, Japanese Patent Publication No. 2-7057 and Japanese Patent No. 2675035 disclose that the conductive metal oxide concentration in the surface layer is changed in the depth direction from the surface of the coating film. A method of eliminating blur / flow is disclosed.
[0016]
Further, as a method for solving the problem with image blur by processing in the process, means for mounting a drum heater for heating the photosensitive member is used. Although the occurrence of image blur can be suppressed by heating the photoconductor, the diameter of the photoconductor must be large in order to mount the drum heater. Therefore, it is applicable to the small-diameter photoconductor used in the tandem system as in the present invention. Therefore, it has been difficult to make the small-diameter photoreceptor highly durable. In addition, the installation of a drum heater inevitably increases the size of the device, which significantly increases power consumption and requires a lot of time to start up the device. It was.
[0017]
On the other hand, a surface layer (protective layer) using a filler with low resistance is laminated on a photoreceptor (commonly called OPC) using an organic charge generating material and charge transporting material by applying the above-mentioned technique. However, when the repeated use test was performed, image flow occurred due to poor matching with OPC. In addition, even when a method of providing a concentration distribution in the surface layer of the conductive metal oxide, which was effective for an inorganic photoreceptor, the results were almost the same. The cause of this is unknown, but in recent electrophotographic processes using organic photoreceptors, digital signals are used by dot-writing on the photoreceptor. Is significantly different from the time when the mainstream of photoconductors. That is, it can be said that the level of resolution required from the image forming apparatus side has changed greatly, and phenomena such as image flow have become prominent.
[0018]
From this situation, the surface layer of the organic photoreceptor is not conductive.ElectricalIt is essential to use a highly resistive filler. However, when a filler having a high electrical resistance is used, there may be a problem that the residual potential increases. The increase in the residual potential that is often observed leads to a high bright portion potential in the electrophotographic apparatus, which leads to a decrease in image density and gradation. In order to compensate for this, it is necessary to increase the dark part potential. However, if the dark part potential is increased, the electric field strength increases, which not only causes image defects such as background stains, but also reduces the life of the photoreceptor. Connected.
In view of such points, the idea of using a mixture of a filler having a high electrical resistance and a filler having a low electrical resistance was also tried, but when many fillers having a low electrical resistance exist on the photoreceptor surface, The problem of image blurring during repeated use has not been solved and has not led to a fundamental solution.
[0019]
As a method of suppressing the increase in residual potential in the prior art, a method using a protective layer as a photoconductive layer (Japanese Patent Publication No. 44-834, Japanese Patent Publication No. 43-16198, Japanese Patent Publication No. 49-10258) is disclosed. ing. However, since the amount of light reaching the photosensitive layer is reduced by the absorption of light by the protective layer, there is a problem that the sensitivity of the photosensitive member is lowered, and the effect is slight.
[0020]
On the other hand, when the average particle size of the metal or metal oxide contained as the filler is 0.3 μm or less (Japanese Patent Laid-Open No. 57-30846), the protective layer becomes substantially transparent and the residual potential is accumulated. A method of suppressing this is disclosed. Although this method has an effect of suppressing an increase in the residual potential, the effect is insufficient, and the actual situation is that the problem has not been solved. This is because the increase in the residual potential caused when the filler is contained is more likely to be caused by charge traps and filler dispersibility due to the presence of the filler than the charge generation efficiency.
[0021]
As another means for suppressing the increase in the residual potential, a method of adding a Lewis acid or the like in the protective layer (Japanese Patent Laid-Open No. 53-133444), a method of adding an organic protonic acid to the protective layer (Japanese Patent Laid-Open No. 55-55). No. 157748), a method of containing an electron-accepting substance (JP-A-2-4275), a method of containing a wax having an acid value of 5 (mgKOH / g) or less (JP-A-12-66434), charge A method of containing a (hole) transport material (Japanese Patent Laid-Open No. 8-15887, Japanese Patent Laid-Open No. 8-123053, etc.), containing a siloxane-based resin having a structural unit having charge transport performance and a crosslinked structure A method for forming a surface protective layer (Japanese Patent Laid-Open No. 12-338704) and the like are disclosed.
These methods are considered to improve the charge injection property at the protective layer / charge transport layer interface, and to form a low resistance portion in the protective layer, so that the charge can easily reach the surface. Yes. According to the above method, the effect of reducing the residual potential is recognized, but it is easy to cause image blur, thereby having a side effect in which the influence on the image is noticeable. Moreover, since it becomes easy to cause the dispersibility fall of a filler when adding an organic acid, the effect is not enough and it is the actual condition that it has not resulted in the solution of a subject.
[0022]
In addition, in the electrophotographic photosensitive member (photosensitive member) containing a filler for high durability, in order to realize high image quality, not only the occurrence of the above-mentioned image blur and the residual potential increase are suppressed, It is also important that the charge reaches the surface of the photoreceptor linearly without being prevented from proceeding by the filler in the protective layer. This is greatly influenced by the dispersibility of the filler in the protective layer film. In the state where the filler is aggregated, when the charge injected into the protective layer from the charge transport layer moves to the surface, the progress is easily hindered by the filler, and as a result, the dots formed by the toner are scattered. The resolution is greatly reduced. In addition, when the protective layer is provided, if the writing light is scattered by the filler and the light transmittance is lowered, the resolution is similarly adversely affected. However, the influence on the light transmittance is also affected by the filler. It is closely related to dispersibility.
[0023]
Further, the dispersibility of the filler greatly affects the wear resistance, the filler causes strong aggregation, and the wear resistance is greatly lowered in a state where the dispersibility is poor. Therefore, in order to achieve high image quality at the same time in the photoreceptor formed with a protective layer containing a filler for high durability, in addition to suppressing the occurrence of image blurring and the increase in residual potential, the protective layer It is important to increase the dispersibility of the filler in the film.
[0024]
Further, in the photoconductor used in the tandem type image forming apparatus as in the present invention, not only the wear resistance is improved, but also the wear speed of a plurality of photoconductors to be used is almost equal. In addition, it is important that the film thicknesses of the plurality of photoconductors are equal. It is also important that the film thickness distribution in each photoconductor mounted on the image forming apparatus and the wear amount distribution in repeated use are extremely flat. Also from such a viewpoint, none of the conventionally used protective layers can satisfy the function.
[0025]
On the other hand, coating of structural defects on the support mainly constituting the photoconductorTheIn order to prevent carrier injection from the support to the photosensitive layer, an intermediate layer is provided between the support and the photosensitive layer.
Conventionally, (1) the middle of a resin thin film alone as seen in thermoplastic resins such as polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyamide, and thermosetting resins such as melamine resin, phenol resin, epoxy resin, and urethane resin Layer (Japanese Patent Laid-Open No. 63-292147, Japanese Patent Laid-Open No. 12-19663, Japanese Patent Laid-Open No. 2-193152, etc.), (2) An intermediate layer in which a conductive filler is dispersed in a binder resin (binder resin) JP-A-6-208238, JP-A-7-271072, JP-A-9-62021, etc.), (3) Method of providing an anodic oxide film on a conductive support (JP-A-7-333881) (4) Intermediate layer using an inorganic cured film by the sol-gel method (Japanese Patent Laid-Open Nos. 12-314975 and 13-42553) And the like have been proposed.
However, in any case, when used in a tandem-type full-color image forming apparatus as in the present invention, the following problems occur.
[0026]
In the case of (1), if a thick film is used to cover defects on the support, most of the resin that can be used is an electrically insulating material, so that the residual potential becomes high in repeated use. In order to prevent this, it is necessary to make the film thickness of the intermediate layer very thin, and in most cases, the film thickness is 1 μm or less. In the case of such a thin film, it is difficult to avoid pinholes in the coating film because the forming method is performed by a wet coating method. When the film thickness is reduced in this way, the barrier property is lowered and local pinholes are likely to occur. In the negative / positive development method which is the current mainstream, there are defects such as background smudges and black spots. Become. This defect may be mistaken for a point in the drawing, a period in the English manuscript, a comma, or the like, and can be said to be a fatal defect as an image. Furthermore, since the volume resistance of the resin often depends on the ionic conductivity, it is significantly affected by the environmental change in which the image forming apparatus is placed, and a stable full-color image cannot always be formed.
[0027]
In the case of the above (2), in order to overcome the disadvantage of the above (1), a conductive filler or an electron conductive filler (because most of the photoconductor is a hole transport type, and an electron transport type photoconductor. In this case, a hole transport type filler is used) to increase the film thickness. At this time, if the dispersibility of the conductive filler is poor, the electrical characteristics such as the electrical resistance and dielectric constant of the intermediate layer change, which may greatly affect the potential characteristics and image characteristics. In addition, in the intermediate layer composed of the filler resin dispersion, the submicron filler made into ultrafine particles is not only costly, but also very bulky and therefore has poor workability and should be used in production. I can't. For this reason, fine particles of submicron (minimum primary particle is about 0.3 μm) are often used. For this reason, reaggregation of the filler occurs during dispersion or coating film formation, and as a result, a coating film defect of 1 μm or more may occur, and for the design of a photoreceptor having uniform charging property and potential holding property. No intermediate layer is formed, and a stable full-color image cannot always be formed as in the case of (1).
[0028]
In the case of (3), an aluminum oxide film typified by alumite is formed on the support surface by anodizing the aluminum substrate, which is a conductive support, using an electrolyte such as sulfuric acid or oxalic acid. is there. The photoconductor having this oxide film has high pressure resistance, little reduction in chargeability even when the photoconductor is repeatedly used in the image forming apparatus, and the above-described increase in point defects in the background portion is hardly observed. This is a film formation using a chemical reaction as described above, and the reaction occurs at the molecular (atomic) level, so the cell structure of the formed film is a very small unit of submicron or less. It seems to be derived from. However, as a fatal defect of a photoreceptor using an anodized film, when used in negative / positive development, which is the mainstream of a full-color image forming apparatus such as the present invention, point defects are present in the initial stage of use of the photoreceptor. There is a problem that there are many. This defect is that the defects gradually decrease when the photoconductor is forcibly used in that state, but the fact that it cannot be used stably from the initial state is recognized as a major problem in practical use. It is.
[0029]
In the case of (4), a cured film is formed from a uniform solution system, a very dense film is formed, and it is possible to make the film slightly thicker than in the case (1). Therefore, the intermediate layer can have a very high function. Depending on the configuration, potential stability during repeated use and low environmental dependency of electrostatic characteristics are recognized as advantages. In the above-mentioned Japanese Patent Application Laid-Open No. 12-314975, the use of such an intermediate layer provides an electrophotographic photosensitive member with less fluctuation in potential due to the environment and excellent electrophotographic characteristics. It is disclosed that a high-resolution image, in particular, a high-gradation and full-color image using a photograph or the like can be provided. From this point, it is considered that the method (4) is most suitable for the intermediate layer used in the photoreceptor mounted in the color image forming apparatus of the present invention.
[0030]
However, in Japanese Patent Laid-Open No. 12-314975, the target is a single-type full-color electrophotographic apparatus, and the uniformity of characteristics in a plurality of photoreceptors necessary for the tandem method and the uniformity after repeated use are guaranteed. However, it cannot be applied to a tandem image forming apparatus as it is. The reason is described below.
[0031]
The difference between the single color system and the tandem color system is in the variety of output systems for input image information. That is, in the case of the single color system, since the image forming speed is slower than that of the tandem system, it is generally used as a dedicated color machine. The copying speed (printing speed) is also used at the highest speed according to the required image quality.
On the other hand, in the case of the tandem method, as described above, the printing speed is increased up to about four times as compared with the single color method, so various usage methods are applied. That is, an output as a monochrome machine, a mode in which speed is given the highest priority as a color machine, a mode in which image quality is given priority as a color machine, and the like. The use as a monochrome machine is because the tandem method can process images of each color in parallel by a plurality of image forming elements, and is achieved by achieving a printing speed equivalent to that of a conventional monochrome image forming apparatus. In addition, as described above, the mode in which speed is given the highest priority as a color machine is one in which image formation is performed at the maximum printing speed of the image forming apparatus, and full color output equivalent to that for monochrome output is performed. It is. On the other hand, the image quality priority mode is a mode in which, for example, the writing resolution is doubled, and as a result, the printing speed is somewhat sacrificed.
[0032]
Under such a usage environment, for example, when monochrome output is performed, a mechanism is provided to prevent image forming elements other than black from coming into contact with the transfer target (intermediate transfer member or direct paper). The forming element will perform more operations compared to other imaging elements. Also, like the grounds on the development of black and red two-color copiers in the past, Japanese manuscripts are written with stamps, etc., and in most cases when checking galley of published manuscripts, black The correction is written in red text on the written basic manuscript. As described above, a specific portion of the magenta or yellow image forming element corresponding to the original document (for example, the edge of the original document) is very large, and image writing / development is performed. As a result, only the edge is fatigued. It also has the potential to become easy and to wear out easily. When the printing speed is different, changing the linear speed of the photoconductor is a conventional means, and the stress applied to a plurality of image forming elements is always different because of the special configuration of tandem full color.
[0033]
Regarding the stress applied to the photoreceptor in the above situation, there are electrostatic stress and mechanical stress. First, electrostatic stress will be described. In general, negative / positive development is used in a tandem full-color image forming apparatus. This is based on the fact that, with the exception of solid images, a normal document has a writing rate of 10% or less, and light fatigue of the photosensitive member is also taken into consideration. In this negative / positive development, development is performed in a portion where the surface potential of the photosensitive member is lower than the developing bias. Therefore, the entire surface is charged when the photosensitive member is used. In addition, writing depends on the original and may or may not be performed depending on the location. In the static elimination process performed after cleaning, photo neutralization and AC static elimination are performed, and in the bulk direction of the photoreceptor. Almost uniform current flows over the entire surface. As described above, with respect to electrostatic fatigue based on charging and exposure (writing and static elimination light), even when various types of images are input, the entire surface of the photoreceptor is uniformly fatigued in most cases. .
[0034]
Next, mechanical stress will be described.
In general, mechanical stress applied to the photoconductor tends to be thought of as wear by the cleaning member, but that is not all. For example, when a contact charging member that is very often used for downsizing of an image forming apparatus in recent years is used, the wearability of the photosensitive member is greatly increased as compared with the case of a corona charger that has been conventionally used. I understand that. When a contact charging member is used for the photoreceptor, it is known that a technique of superimposing an AC component on a DC component is effective in order to prevent uneven charging. At this time, the greater the voltage difference between the AC component frequency and peak to peak, the greater the stress due to charging of the photoreceptor. As the diameter of the photoconductor progresses as in the present invention, it is necessary to increase the frequency of the AC component and / or the voltage difference as the nip width in charging decreases and the linear velocity of the photoconductor increases. As a result, repeated electron transfer between the photosensitive member surface and the charging member surface during charging promotes chemical deterioration of the photosensitive member surface (for example, main chain breakage of the binder resin) and increases the amount of wear. End up. Such a phenomenon also promotes uneven wear rate in the same photoreceptor. That is, non-uniformity of chargeability (charge acceptance) within the same photoconductor caused by various factors causes nonuniformity of stress from the charging member to the photoconductor during contact charging. As a result, a lot of stress is applied to the portion with low chargeability, the wear amount of the portion is locally increased, and the wear amount during repeated use is different from the other portions.
[0035]
In addition, additives such as a fluidizing agent, which are essential for recent color developers, generally have the same polarity as that of toner. In many cases, the toner is developed in the same manner as the toner. For this reason, such an additive remains on the photosensitive member together with the toner, and promotes abrasion of the photosensitive member or conversely promotes filming. Unlike the case of the electrostatic fatigue described above, this situation is not a phenomenon that can occur on the entire surface of the photoconductor but a phenomenon that occurs only at the place where writing is performed. Therefore, in the situation where only a specific image forming element is used as described above, mechanical stress becomes larger than that of the photoconductor used for the image forming elements of other colors.
[0036]
From the above, in the photoreceptor used in the tandem full-color image forming apparatus, in addition to the uniformity of electrostatic characteristics and the uniformity of electrostatic fatigue characteristics in repeated use, the more important point is the film thickness. The uniformity of the wear characteristics, the uniformity of the wear characteristics due to repeated use, and the uniformity of the wear characteristics within each photoconductor are also important, and it is required to satisfy all of them.
Based on such points, regarding the stability of electrostatic characteristics, it is essential that there is little variation in one in the initial stage of use, and that the deterioration of electrostatic characteristics in repeated use is extremely small, and that environmental stability is further improved. It can be seen that this function depends on the properties of the intermediate layer and the protective layer. On the other hand, regarding the uniformity of the wear characteristics, it is essential that the film thickness distribution in the initial use is extremely small and the wear amount in repeated use is extremely small, and this function depends on the characteristics of the protective layer.
[0037]
A publicly known technique having structural requirements that are relatively close to these required items is a photoconductor described in JP-A-12-314975. This publication describes that electrostatic properties are stabilized by using an intermediate layer formed by a sol-gel method, and wear resistance is improved by having a surface protective layer. However, this technique describes a photoconductor intended for a single type image forming apparatus, and does not take into account the stability of wear resistance to various modes in a tandem type image forming apparatus, and is not always satisfactory. It wasn't going to be good.
[0038]
As described above, in a tandem-type full-color image forming apparatus, a photoconductor that satisfies the wear resistance, the potential stability, and the environmental stability at the same time and can obtain a good image for a long time has not yet been found. .
[0039]
[Problems to be solved by the invention]
The present invention has been made in view of the above-described problems, and the object thereof is extremely excellent in that it has good environmental stability and stable high image quality under various environments even for repeated use over a long period of time. By using a highly stable electrophotographic photosensitive member (photosensitive member), a small and high-speed tandem full-color image forming apparatus and a process cartridge for the full-color image forming apparatus are provided. In other words, even when a large number of color images of the same document are formed under any environment, an image with good color reproducibility can always be formed, and the same characteristics can be obtained even after long-term repeated use. Are provided, and a tandem-type full-color image forming apparatus and a process cartridge for the image forming apparatus.
[0040]
[Means for Solving the Problems]
  In order to solve the above problems, a tandem-type full-color image forming apparatus and a process cartridge for a full-color image forming apparatus according to the present invention include an electrophotographic photosensitive member (photosensitive member) mounted (provided) on a plurality of image forming elements. By adopting the following configuration, improvement in wear resistance, potential stability, environmental stability, and durability is achieved. Hereinafter, the present invention will be specifically described. The invention of claim 1 is a tandem full-color image forming apparatus in which a plurality of image forming elements comprising at least a charging means, an image exposing means, a developing means, a transferring means, and an electrophotographic photosensitive member are arranged. The photoreceptor comprises at least an intermediate layer, a photosensitive layer, and a protective layer on a conductive support, the intermediate layer contains an organometallic compound and / or a silane coupling agent, and the protective layer is at leastAluminum ammonium carbonate hydroxide [NH ₄ AlCO ₃ (OH) ₂ Α-alumina particles obtained by thermal decomposition ofAnd a binder resin. A full-color image forming apparatus. The invention of claim 2The average particle size of the α-alumina particles is 0.05 to 1.0 µm.A full-color image forming apparatus. The invention of claim 3The α-alumina particles have a particle size ratio (Db / Da) of 4 or less when the average particle sizes of 10% and 90% from the fine particle side of the cumulative particle size distribution are Da and Db, respectively. 2. The method according to claim 1, whereinA full-color image forming apparatus. The invention of claim 4The sodium content as an impurity contained in the α-alumina particles is 20 ppm or less.A full-color image forming apparatus. The invention of claim 5The organometallic compound contained in the intermediate layer is a metal alkoxide or an organometallic chelate, according to any one of claims 1 to 4.A full-color image forming apparatus. The invention of claim 66. The metal alkoxide or the organometallic chelate is an organometallic compound comprising at least one metal selected from zirconium, titanium, or aluminum.A full-color image forming apparatus. The invention of claim 7The charge transport material is contained in the protective layer.The full-color image forming apparatus according to any one of the above. The invention of claim 88. The charge transport material of claim 7, wherein the charge transport material is a polymer charge transport material.A full-color image forming apparatus. The invention of claim 9The polymer charge transport material contains a polycarbonate having at least a triarylamine structure in a main chain and / or a side chain.A full-color image forming apparatus. The invention of claim 10 is characterized in that the protective layer contains a polycarboxylic acid.The method according to claim 1.A full-color image forming apparatus. The invention of claim 11A detachable tandem system comprising an electrophotographic photosensitive member and at least one of a charging unit, an image exposing unit, a developing unit, a transferring unit, a separating unit, and a cleaning unit. In the process cartridge for a full-color image forming apparatus, the electrophotographic photosensitive member is provided with at least an intermediate layer, a photosensitive layer, and a protective layer on a conductive support, and the intermediate layer comprises an organometallic compound and / or a silane coupling agent. And the protective layer is at least aluminum ammonium carbonate hydroxide [NH ₄ AlCO ₃ (OH) ₂ ], A process cartridge comprising α-alumina particles obtained by pyrolyzing and a binder resinIt is. The invention of claim 12The process cartridge according to claim 11, wherein an average particle diameter of the α-alumina particles is 0.05 to 1.0 μm.It is. The invention of claim 13The α-alumina particles have a particle size ratio (Db / Da) of 4 or less when the average particle sizes of 10% and 90% from the fine particle side of the cumulative particle size distribution are Da and Db, respectively. 12. The method of claim 11, whereinProcess cartridge. The invention of claim 14The sodium content as an impurity contained in the α-alumina particles is 20 ppm or less.Process cartridge. The invention of claim 15The organometallic compound contained in the intermediate layer is a metal alkoxide or an organometallic chelate, according to any one of claims 11 to 14.Process cartridge. The invention of claim 16The metal alkoxide or organometallic chelate is zirconium, titanium, or aluminum. 16. The organometallic compound comprising at least one metal selected from ruminium.Process cartridge. The invention of claim 17The charge transport material is contained in the protective layer, according to any one of claims 11 to 16,Process cartridge. The invention of claim 18 provides18. The charge transport material according to claim 17, wherein the charge transport material is a polymer charge transport material.Process cartridge. The invention according to claim 19 is characterized in that the polymer charge transport material contains a polycarbonate having at least a triarylamine structure in the main chain and / or side chain.Claim 18Process cartridge. The invention of claim 2020. The protective layer according to any one of claims 11 to 19, wherein the protective layer contains a polycarboxylic acid.Process cartridge.
[0041]
Details of means for solving the problems will be described below.
The electrophotographic photoreceptor (photoreceptor) used in the tandem-type full-color image forming apparatus of the present invention is provided with a protective layer containing α-alumina particles and a binder resin on the outermost surface layer of the photoreceptor. Attempts have been made so far to disperse the filler in the protective layer for the purpose of improving the wear resistance, but there are problems caused by the inclusion of the filler as mentioned in the prior art. However, the details of the effect are unknown, but by using the alumina particles in the protective layer, it is possible to obtain a photoreceptor that is excellent in electrostatic characteristics, filler dispersibility, and environmental stability and has little variation in the initial use state. I understood. Furthermore, a tandem-type photoconductor for a full color image forming apparatus can be obtained which has uniform electrostatic characteristics and wear characteristics in repeated use, and has extremely small characteristic variation and variation among a plurality of photoconductors.
This reason is considered to be due to the following characteristics of the alumina particles used in the present invention. (1) shape and particle size distribution, (2) high purity, (3) refractive index, and (4) stability against environmental fluctuations.
[0042]
First, (1) shape and particle size distribution will be described.
The α-alumina particles used in the present invention contain hydrogen chloride using, as a raw material, transition alumina or alumina powder that becomes transition alumina by heat treatment described in JP-A-6-191833, JP-A-6-191836, etc. Obtained in accordance with a production method of firing in an atmosphere. In addition, [NH] described in Japanese Patent Publication No. 51-139810, Japanese Patent No. 2983042, Japanese Patent Publication No. 6-17224, and the like.₄AlCO₃(OH)₂] According to the manufacturing method which carries out low-temperature baking. For this reason, quality problems such as shape non-uniformity and wide particle size distribution, which were disadvantages of α-alumina particles obtained by conventional pulverization methods, have been improved, there is no crushing surface, and the proportion of fine particles is also low. Very few particles are obtained.
The average particle diameter of the α-alumina particles is 0.05 to 1.0 μm, and the average particle diameters of 10% and 90% from the fine particle side of the cumulative particle size distribution are Da and Db, respectively. Those having a particle size ratio (Db / Da) value of 4 or less are particularly preferably used. When α-alumina particles having such characteristics are used, filler aggregation does not occur in the coating solution and the dispersion is good. When a protective layer is formed using such a coating liquid, a filler having a uniform filler concentration distribution and excellent surface smoothness is formed. In the state where the filler is aggregated, the straightness of writing light and the decrease in energy are prevented, and further, the charge generated in the charge generation layer is prevented from proceeding to the surface of the photoreceptor. As a result, the formed toner image is in a state where dots are scattered, causing a decrease in resolution. In addition, by improving the uniformity of the filler particle size and the surface smoothness due to the dispersibility of the filler, there is little film thickness unevenness in the same photoconductor in the initial state, and between multiple photoconductors. Variations in film thickness are also suppressed. Further, since the filler distribution in the protective layer is uniform, the wear characteristics of each photoreceptor over time are equal by repeated use, and the wear resistance is small because of excellent wear resistance characteristics. As a result, even after use, the film thickness variation is extremely small, and uniform color reproducibility with little color shift and unevenness is possible.
[0043]
Next, (2) high purity will be described.
The α-alumina particles used in the present invention have a high purity obtained by the above-described production method and have an impurity sodium content of 20 ppm or less. If impurity ions such as sodium ions mixed in the manufacturing process are contained, charge trapping is likely to occur, and the exposure portion potential is increased. For this reason, by using the high-purity α-alumina particles of the present invention, it is possible to suppress an increase in the exposed portion potential due to repeated use.
[0044]
Next, (3) the refractive index will be described.
When a filler is contained in the surface layer (protective layer) for the purpose of improving the wear resistance, the writing light is reflected by the filler, causing light straightness and energy reduction. Since this reflection is determined by the difference in refractive index inherent to the medium through which light propagates and enters and the filler material constituting the protective layer, it is necessary to select a filler material with a small difference. . The refractive index of the material constituting the protective layer is approximately 1.6, and the alumina particles are 1.76. Conventionally, the filler added to the photosensitive layer or the protective layer for the purpose of increasing durability is 1.55 for silica and 2.71 for titanium oxide, for example. From the difference in refractive index, the influence of reflection is small in alumina and silica, but when titanium oxide is used, the resolution is greatly adversely affected. However, when silica is used, image flow tends to occur. The reason for this is that, when used repeatedly over a long period of time, especially when used under high temperature and high humidity, water and the like are likely to be adsorbed, which causes leakage of charges in the lateral direction of the surface of the photoreceptor, resulting in an image. There is a problem of flow.
Further, regarding the problem of image flow caused by the adsorption of water or the like, not only the filler material but also the surface area of the filler particles affects. As described above, the α-alumina particles used in the present photoreceptor are characterized by a narrow particle size distribution and a small proportion of fine particles, so that it is considered that the occurrence of image flow in repeated use is suppressed. .
[0045]
From the above, it can be seen that the protective layer using α-alumina particles exhibits extremely homogeneous properties. That is, from the above (1), the composition of the protective layer (for example, the filler concentration distribution as a dispersoid, the particle size distribution, etc.) is uniform, and the structural uniformity (homogeneous body) is also achieved in the protective layer as a dispersion film. Is done. From (2), trapping of charges in the bulk of the protective layer is suppressed, trap-free and high-speed charge mobility, which are the electrostatic properties necessary for the protective layer, are achieved, and electrostatic uniformity is achieved even during repeated use. Achieved. From (3), the refractive index difference between the binder as the dispersion medium of the protective layer and the filler as the dispersoid is small, and optical uniformity is also achieved.
As described above, it is considered that the protective layer in which chemical and physical uniformity is achieved is subject to uniform wear and chemical degradation during repeated use. Further, since the protective layer of the present invention has extremely high wear resistance, the amount of wear in repeated use is very small. For this reason, in the tandem image forming apparatus of the present invention, the variation in the amount of wear between the plurality of photoconductors is very small, and the stability of the plurality of image forming elements is increased.
Further, as described above, even when used in various copying (printing) modes, since the wear resistance is high, only the photoconductor of a specific image forming element (for example, for black) has an extremely large wear amount. The possibility of getting lost is very small. Further, even if only the photoconductor of a specific image forming element has a slight increase in wear amount, the physical property value as the protective layer is uniform as described above. Even if a slight difference in film thickness occurs, the effect on the photoreceptor characteristics is small, and as a result, there is an advantage that the possibility of affecting the output full-color image is extremely small.
[0046]
Next, (4) stability against environmental fluctuation will be described.
Although the details of this effect are unknown, the α-alumina particles used in the present invention have a smaller property of adsorbing moisture contained in the air or paper than other fillers, and have no influence on environmental fluctuations. It is considered small. For example, when it is used under high temperature and high humidity, it exhibits an excellent effect for suppressing image blur, and thus problems such as an increase in the size of the apparatus and an increase in power consumption due to the installation of a drum heater or the like are solved.
[0047]
The superiority of the protective layer using α-alumina particles as described above is that an intermediate layer formed using an organometallic compound and / or a silane coupling agent, an intermediate layer formed by a so-called sol-gel method is used in combination. By doing so, it becomes more prominent. As described above, the sol-gel type intermediate layer has a homogeneous structure at the physical and chemical micro level compared to other known intermediate layers. It is based on the fact that it is excellent in barrier properties as a characteristic, has little deterioration in characteristics due to repeated use of a photoreceptor, and is excellent in environmental stability.
The advantage of such a sol-gel type intermediate layer is that it is fully effective when combined with the specific protective layer in the present invention, and is particularly mounted in a tandem full-color image forming apparatus. Therefore, the effect is applied very effectively.
[0048]
Furthermore, in the present invention, the protective layer can contain a charge transport material. As a result, for example, the performance can be improved by suppressing an increase in residual potential. As such a charge transport material, a polymer charge transport material can be used, and among them, a polycarbonate having a triarylamine structure in the main chain and / or side chain is effective.
The protective layer of the present invention can contain a polycarboxylic acid compound as a dispersant. By using a polycarboxylic acid compound, the stability of the coating solution is enhanced, and a uniform and stable coating can be formed.
[0049]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the image forming apparatus of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic diagram for explaining a tandem-type full-color image forming apparatus according to the present invention, and modifications as described below also belong to the category of the present invention.
[0050]
In FIG. 1, reference numerals 1C, 1M, 1Y, and 1K denote drum-shaped photoconductors. The photoconductors 1C, 1M, 1Y, and 1K rotate in the direction of an arrow in the drawing, and at least around the charging member 2C in the order of rotation. , 2M, 2Y, 2K, developing members 4C, 4M, 4Y, 4K, and cleaning members 5C, 5M, 5Y, 5K are arranged. The charging members 2C, 2M, 2Y, and 2K are charging members that constitute a charging device for uniformly charging the surface of the photoreceptor. Laser light 3C, 3M, 3Y, 3K from an exposure member (not shown) is irradiated on the surface of the photosensitive member between the charging members 2C, 2M, 2Y, 2K and the developing members 4C, 4M, 4Y, 4K, and the photosensitive member 1C, Electrostatic latent images are formed at 1M, 1Y, and 1K. Then, four image forming elements 6C, 6M, 6Y, and 6K centering on such photoreceptors 1C, 1M, 1Y, and 1K are juxtaposed along a transfer conveyance belt 10 that is a transfer material conveyance unit. The transfer conveyance belt 10 contacts the photoreceptors 1C, 1M, 1Y, and 1K between the developing members 4C, 4M, 4Y, and 4K of the image forming elements 6C, 6M, 6Y, and 6K and the cleaning members 5C, 5M, 5Y, and 5K. Transfer brushes 11C, 11M, 11Y, and 11K for applying a transfer bias are disposed on a surface (back surface) that is in contact with the back side of the transfer conveyance belt 10 on the photoconductor side. Each of the image forming elements 6C, 6M, 6Y, and 6K has the same configuration except that the toner color inside the developing device is different.
[0051]
In the color image forming apparatus having the configuration shown in FIG. 1, the image forming operation is performed as follows. First, in each of the image forming elements 6C, 6M, 6Y, and 6K, the photoreceptors 1C, 1M, 1Y, and 1K are charged by the charging members 2C, 2M, 2Y, and 2K that rotate in the direction of the arrow (the direction around the photoreceptor). Next, an electrostatic latent image corresponding to each color image to be created is formed by the laser beams 3C, 3M, 3Y, and 3K in the exposure unit. Next, the latent image is developed by developing members 4C, 4M, 4Y, and 4K to form a toner image. The developing members 4C, 4M, 4Y, and 4K are developing members that perform development with toners of C (cyan), M (magenta), Y (yellow), and K (black), respectively, and the four photosensitive members 1C, 1M, and 1Y. , 1K toner images of respective colors are overlaid on the transfer paper 7. The transfer paper 7 is sent out from the tray by a paper feed roller 8, temporarily stopped by a pair of registration rollers 9, and sent to the transfer conveyance belt 10 in synchronism with the image formation on the photosensitive member. The transfer paper 7 held on the transfer conveyance belt 10 is conveyed, and the toner images of the respective colors are transferred at the contact positions (transfer portions) with the photoconductors 1C, 1M, 1Y, 1K. The toner image on the photoconductor is transferred onto the transfer paper 7 by an electric field formed from a potential difference between the transfer bias applied to the transfer brushes 11C, 11M, 11Y, and 11K and the photoconductors 1C, 1M, 1Y, and 1K. The Then, the recording paper 7 on which the four color toner images are passed through the four transfer portions is conveyed to the fixing device 12, where the toner is fixed, and is discharged to a paper discharge portion (not shown). Further, the residual toner remaining on the photoreceptors 1C, 1M, 1Y, and 1K without being transferred by the transfer unit is collected by the cleaning devices 5C, 5M, 5Y, and 5K. In the example of FIG. 1, the image forming elements are arranged in the order of C (cyan), M (magenta), Y (yellow), and K (black) from the upstream side to the downstream side in the transfer paper conveyance direction. However, it is not limited to this order, and the color order is arbitrarily set.
[0052]
The image forming means as described above may be fixedly incorporated in a copying machine, facsimile, or printer, but each image forming element is in the form of a full color image forming process cartridge as shown in FIG. It may be incorporated in these devices. A process cartridge is a single device (component) that contains a photoreceptor and is combined with at least one of charging means, image exposure means, developing means, transfer means, separation means, and cleaning means. It is.
[0053]
Hereinafter, the electrophotographic photosensitive member used in the present invention will be described with reference to the drawings.
FIG. 3 is a cross-sectional view showing a configuration example in which the photosensitive layer 33 of the electrophotographic photosensitive member used in the present invention is formed in a single layer configuration. The intermediate layer 32 and the charge generation material are sequentially formed on the conductive support 31. And a single photosensitive layer 33 mainly composed of a charge transport material, and a protective layer 36 is further laminated thereon.
[0054]
4 and 5 are cross-sectional views showing another configuration example in which the photosensitive layer 33 of the electrophotographic photosensitive member of the present invention is formed in a laminated configuration. In FIG. 4, a charge generation layer 34 mainly composed of a charge generation material and a charge transport layer 35 mainly composed of a charge transport material are stacked on an intermediate layer 32 sequentially on a conductive support 31. Further, the protective layer 36 is laminated thereon. FIG. 5 shows an example in which the charge generation layer 34 and the charge transport layer 35 are stacked opposite to those in FIG.
[0055]
The constituent layers of the electrophotographic photoreceptor (photoreceptor) of the present invention will be described below.
<About conductive support>
The conductive support 31 has a volume resistance of 10^Ten Films having conductivity of Ω · cm or less, for example, metal such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, metal oxide such as tin oxide, indium oxide, etc. are deposited or sputtered. Surface coated with plastic or paper in the shape of a cylinder or paper, or a plate made of aluminum, aluminum alloy, nickel, stainless steel, etc. A treated tube or the like can be used. Further, an endless nickel belt or an endless stainless steel belt disclosed in Japanese Patent Application Laid-Open No. 52-36016 can also be used as the conductive support 31.
In addition, a material obtained by dispersing conductive powder in an appropriate binder resin and coating it on the support can also be used as the conductive support 31 of the present invention.
[0056]
Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc and silver, or metal oxide powder such as conductive tin oxide and ITO. It is done. The binder resin used at the same time includes polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, melamine Examples thereof include thermoplastic, thermosetting resins, and photocurable resins such as resins, urethane resins, phenol resins, and alkyd resins.
[0057]
Such a conductive layer can be provided by dispersing the conductive powder and the binder resin in a suitable solvent, for example, tetrahydrofuran, dichloromethane, methyl ethyl ketone, toluene, and the like.
Furthermore, a conductive layer is provided on a suitable cylindrical substrate by a heat-shrinkable tube containing the conductive powder in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, and Teflon. Can be used favorably as the conductive support 31 of the present invention.
[0058]
<About the intermediate layer>
The photoreceptor of the present invention is characterized in that an intermediate layer 32 containing an organometallic compound and / or a silane coupling agent is provided between the conductive support 31 and the photosensitive layer 33. The intermediate layer is provided mainly for the following purpose.
(1) Prevent unnecessary carrier injection from the conductive support and improve image quality.
(2) Stable image quality can be obtained without causing environmental fluctuations of the photoreceptor.
(3) Appropriate charge transport performance, no charge accumulation even during long-term repeated use, and prevents sensitivity fluctuations.
(4) It has a moderate withstand voltage against the charging voltage and prevents the occurrence of image defects due to dielectric breakdown.
(5) An action as an adhesive layer that integrally adheres and holds the photosensitive layer to the conductive support is shown.
(6) The effect of preventing reflected light from the conductive support is shown.
[0059]
Examples of the organometallic compound used for the intermediate layer include an organozirconium compound, an organotitanium compound, and an organoaluminum compound.
Examples of organic zirconium compounds include zirconium tetraacetylacetonate, zirconium dibutoxybisacetylacetonate, zirconium tributoxyacetylacetonate, zirconium tetrakisethylacetoacetate, zirconium butoxytrisethylacetoacetate, zirconium butoxybisethylacetoacetate, zirconium Zirconium such as tributoxy monoethyl acetoacetate, zirconium tetrakisethyl lactate, zirconium dibutoxy bisethyl lactate, bisacetylacetonate bisethylacetoacetate zirconium, monoacetylacetonate trisethylacetoacetate zirconium, bisacetylacetonate bisethyl lactate zirconium Muchelate, Jill Bromide -n- butylate, zirconium alkoxides such as zirconium -n- propylate is used.
[0060]
Examples of the organic titanium compound include tetramethyl orthotitanate, tetraethyl orthotitanate, tetra-n-propyl orthotitanate, tetraisopropyl titanate, tetrabutyl orthotitanate, tetrabutyl polytitanate, tetraacetylacetonate polytitanate, diisopropoxytitanium. -Bis-octanediol, diisopropoxytitanium-bis- (acetylacetonate), titanium tetralactate, tratriethanolamine titanium chelate, titanium tetraammonium lactate, titanium tetraacetylacetonate ammonium lactate, bis (dioctylbisphosphate) oxy Acetate titanate or the like is used.
[0061]
Examples of the organic aluminum compound include aluminum alcoholates such as aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate, aluminum-sec-butyrate, aluminum ethylate, aluminum ethylacetoacetate diisopropylate, aluminum tris (ethylacetate). Acetate), aluminum tris (acetylacetonate), aluminum bisethylacetoacetate monoacetylacetonate and other aluminum chelate compounds are used. Further, single or complex oligomer derivatives of these organometallic compounds can also be used.
[0062]
Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-gridoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (Aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyl Trimethoxysilane, γ-aminopropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmonomethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, monophenyltrimethoxysilane Lan, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane and the like are used.
[0063]
The intermediate layer in the present invention contains at least one selected from the above organometallic compounds and the above silane coupling agent, and two or more kinds thereof can be mixed and used. The mixing ratio of the silane coupling agent is preferably in the range of 0.1 to 10% by weight with respect to the content of the organometallic compound.
Various solvents can be used as the solvent for forming the coating solution for coating the silane coupling agent such as the organometallic compound alone or the organosilane compound. For example, methanol, ethanol, propanol, butanol, ethyl acetate, toluene and the like can be used alone or in combination. The coating method can be performed using a dip coating method, a spray coating method, a bead coating method, or the like. The film thickness of the intermediate layer is suitably from 0.01 to 10 μm.
[0064]
<About photosensitive layer>
The photosensitive layer may have a laminated structure or a single layer structure. In the case of the laminated structure shown in FIGS. 4 and 5, the photosensitive layer 33 includes a charge generating layer 34 containing a charge generating substance and a charge transporting layer 35 containing a charge transporting substance. Consists of In the case of a single layer structure, the photosensitive layer is composed of a layer containing at least a charge generating substance. Hereinafter, a photosensitive layer having a laminated structure and a photosensitive layer having a single layer structure will be described.
[0065]
[Photosensitive layer when the photosensitive layer has a laminated structure]
Charge generation layer
The charge generation layer 34 is a layer mainly composed of a charge generation material for the purpose of generating and separating a latent image charge by image exposure, and a binder resin can be used in combination as necessary. As the charge generation material, inorganic materials and organic materials can be used.
[0066]
Inorganic materials include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, amorphous silicon, and the like. In amorphous silicon, dangling bonds terminated with hydrogen atoms or halogen atoms, or doped with boron atoms, phosphorus atoms or the like are preferably used.
[0067]
On the other hand, a known material can be used as the organic material. For example, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azulenium salt pigments, squaric acid methine pigments, azo pigments having carbazole skeleton, azo pigments having triphenylamine skeleton, azo pigments having diphenylamine skeleton, dibenzothiophene skeleton Azo pigments having fluorenone skeleton, azo pigments having oxadiazole skeleton, azo pigments having bis-stilbene skeleton, azo pigments having distyryl oxadiazole skeleton, azo pigments having distyrylcarbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinoneimine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine dyes Indigoid pigments, and bisbenzimidazole pigments. These charge generation materials can be used alone or as a mixture of two or more.
[0068]
Examples of the binder resin used for the charge generation layer 34 include polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, polysulfone, poly-N-vinylcarbazole, poly Examples include acrylamide, polyvinyl benzal, polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polyamide, polyvinyl pyridine, cellulosic resin, casein, polyvinyl alcohol, and polyvinyl pyrrolidone. The amount of the binder resin is suitably 0 to 500 parts by weight, preferably 10 to 300 parts by weight with respect to 100 parts by weight of the charge generating material.
[0069]
Examples of the solvent used here include isopropanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, ligroin and the like. In particular, ketone solvents, ester solvents, and ether solvents are preferably used. As a coating method for the coating solution, a dip coating method, spray coating, beat coating, nozzle coating, spinner coating, ring coating, or the like can be used.
The film thickness of the charge generation layer 34 is suitably about 0.01 to 5 μm, preferably 0.1 to 2 μm.
[0070]
Charge transport layer
The charge transport layer 35 is a layer intended to hold a charged charge and to couple the charge generated in the charge generation layer 34 by exposure to the charged charge that has been held. In order to achieve the purpose of holding the charged charge, high electrical resistance is required, and in order to achieve the purpose of obtaining a high surface potential with the held charged charge, the dielectric constant is small and the charge mobility is good. Is required. The charge transport layer for satisfying these requirements can be formed by dissolving or dispersing the charge transport material and the binder resin in a suitable solvent, and applying and drying the solution on the charge generation layer 34.
[0071]
The charge transport material includes an electron transport material and a hole transport material.
Examples of the electron transporting material include chloroanil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-tri Examples thereof include electron-accepting substances such as nitrodibenzothiophene-5,5-dioxide and benzoquinone derivatives.
[0072]
Examples of hole transport materials include poly-N-vinylcarbazole and derivatives thereof, poly-γ-carbazolylethyl glutamate and derivatives thereof, pyrene-formaldehyde condensates and derivatives thereof, polyvinylpyrene, polyvinylphenanthrene, polysilane, oxazole derivatives, Oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, 9-styrylanthracene derivatives, pyrazolines Derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, etc., bisstilbene derivatives, enamine derivatives, etc. Other known materials may be mentioned. These charge transport materials may be used alone or in combination of two or more.
[0073]
Binder resins include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, poly Vinylidene chloride, polyarate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin And thermoplastic or thermosetting resins such as alkyd resins.
The amount of the charge transport material is 20 to 300 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin.
[0074]
As the solvent used for coating the charge transport layer 35, the same solvent as that used for the charge generation layer can be used, but a solvent that dissolves the charge transport material and the binder resin well is suitable. These solvents may be used alone or in combination of two or more. The charge transport layer 35 can be formed by the same coating method as the charge generation layer 34.
[0075]
If necessary, a plasticizer and a leveling agent can be added.
As the plasticizer that can be used in combination with the charge transport layer 35, general-purpose plasticizers such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is suitably about 0 to 30 parts by weight with respect to 100 parts by weight of the binder resin. is there.
Leveling agents that can be used in combination with the charge transport layer 35 include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain. The amount used is a binder resin. About 0 to 1 part by weight is appropriate for 100 parts by weight.
The thickness of the charge transport layer 35 is suitably about 5 to 50 μm, and preferably about 10 to 30 μm in terms of image characteristics such as resolution and background stains and electrical characteristics such as charging potential and sensitivity.
[0076]
[Photosensitive layer when the photosensitive layer has a single layer structure]
Next, the case where the photosensitive layer has a single layer structure will be described.
In the single layer structure, a photosensitive layer 33 in which at least a charge generating substance is dispersed in a binder resin is provided on a conductive support 31 and an intermediate layer 32. The photosensitive layer 33 can be formed by dissolving or dispersing a charge transport material in an appropriate solvent, if necessary, in addition to the charge generation material and the binder resin, and applying and drying the solution. Moreover, a plasticizer, a leveling agent, etc. can also be added as needed. The same charge generating substance, charge transporting substance, plasticizer and leveling agent as those described above can be used.
[0077]
Further, as the binder resin, in addition to the binder resin already mentioned in the charge transport layer 35, the binder resin mentioned in the charge generation layer 34 may be mixed and used. The amount of the charge generating material with respect to 100 parts by weight of the resin component is preferably 1 to 40 parts by weight, and the amount of the charge transporting material is preferably 0 to 190 parts by weight, and more preferably 50 to 150 parts by weight. The photosensitive layer 33 is formed by dip coating or spray coating with a coating solution in which a charge generating material, a binder resin and a charge transporting material are mixed with a solvent such as tetrahydrofuran, dioxane, dichloroethane, or cyclohexane as necessary. It can be formed by coating with bead coat or ring coat.
The film thickness of the photosensitive layer is suitably about 5 to 25 μm.
[0078]
<About protective layer>
In the electrophotographic photoreceptor (photoreceptor) of the present invention, a protective layer 36 is provided for the purpose of protecting the photosensitive layer 33, and the protective layer 36 is composed of a layer containing at least α-alumina particles and a binder resin.
As described above, the α-alumina particles contain hydrogen chloride by using, as a raw material, transition alumina or alumina powder that becomes transition alumina by heat treatment described in JP-A-6-191833 and JP-A-6-191836. Those obtained in accordance with a method of firing in an atmosphere, and those described in JP-A-51-139810, Japanese Patent No. 2983042, Japanese Patent Publication No. 6-17224, etc.₄AlCO₃(OH)₂Are particularly useful in accordance with a method for low-temperature firing.
The average particle size of the α-alumina particles is preferably 0.05 to 1.0 μm. If it is smaller than 0.05 μm, aggregation of α-alumina particles is likely to occur in the coating liquid, and uniform coating becomes difficult. As a result, there may be a problem of uneven wear in repeated use. On the other hand, if it is larger than 1.0 μm, the unevenness of the surface becomes severe due to repeated use, and toner filming and damage to the cleaning blade are induced, which may cause abnormal images such as black streaks and streaky white spots. In addition, an adverse effect on productivity such as an increase in the sedimentation rate of α-alumina particles in the coating solution may be considered.
[0079]
Further, as described above, particles having a particle size ratio (Db / Da) of 4 or less when the average particle sizes of 10% and 90% from the fine particle side of the cumulative particle size distribution are Da and Db, respectively. It is preferable to use particles having a uniform diameter.
The cumulative particle size distribution used here is the value of the cumulative volume ratio obtained from the laser scattering method. For example, a dynamic light scattering device DLS-700 (manufactured by Otsuka Electronics) can be used as the measuring device. Further, a value of 50% of the cumulative volume ratio is used as the average particle diameter.
[0080]
Moreover, the effect is effectively exhibited by using high-purity α-alumina particles having a sodium content of 20 ppm or less by quantifying impurities by emission analysis. The reason why high-purity alumina is suitable is that impurity ions such as sodium ions are eluted, and these ions act as traps of charges and increase the potential of the exposed portion.
As described above, particularly good electrophotographic characteristics are exhibited by using high-purity α-alumina particles having a uniform particle size and a narrow particle size distribution.
[0081]
In addition, another filler can also be used together in the range which does not inhibit the effect of this invention.
For example, as inorganic fillers, metal powder such as copper, tin, aluminum, indium, silica, tin oxide, zinc oxide, titanium oxide, zirconium oxide, indium oxide, antimony oxide, bismuth oxide, calcium oxide, antimony-doped oxide Examples thereof include metal oxides such as tin and tin-doped indium oxide, metal fluorides such as tin fluoride, calcium fluoride, and aluminum fluoride, potassium titanate, and boron nitride.
[0082]
These fillers including α-alumina particles can be subjected to surface treatment for the purpose of improving dispersibility. As the surface treatment agent used at this time, titanate coupling agents, aluminum coupling agents, zirco coupling agents and the like can be used. Aluminate coupling agent, higher fatty acid, silane coupling agent, Al₂O₃TiO₂, ZrO₂, Silicone, aluminum stearate, or a mixed treatment thereof.
The proportion of the filler contained in the protective layer 36 depends on various factors such as the intended wear resistance, the particle size of the filler, and the image forming process used, but the total weight of all the materials constituting the protective layer 36. 5 wt% to 50 wt%, preferably 10 wt% to 40 wt%.
[0083]
As the binder resin used for the protective layer 36, ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, aryl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, Polybutylene, polybutylene terephthalate, polycarbonate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylbenten, polypropylene, polyphenylene oxide, polysulfone, polystyrene, polyarylate, AS resin, butadiene-styrene copolymer, polyurethane, Examples thereof include polyvinyl chloride, polyvinylidene chloride, and epoxy resin. Of these, polycarbonate is particularly preferred.
[0084]
In addition, a charge transport material can be used for the protective layer 36, which is an effective means for suppressing an increase in residual potential due to the lamination of the protective layer. As the charge transport material, the materials mentioned in the description of the charge transport layer can be used. Regarding the proper use of the electron transport material and the hole transport material, it is preferable to make an appropriate selection depending on the polarity of the charge and the layer structure. In addition, a polymer charge transport material can be used as the charge transport material.
Among polymer charge transport materials, polycarbonate having a triarylamine structure in the main chain and / or side chain is effective. In this case, the polymer charge transport material also serves as a binder resin.
Examples of the more useful polycarbonate having a triarylamine structure used in the present invention include polymer charge transport materials represented by the following general formulas (1) to (10).
[0085]
As a first example of the polymer charge transport material, there is a polycarbonate having a triarylamine structure represented by the following general formula (1).
[0086]
[Chemical 1]

[0087]
Where R₁, R₂, R₃Each independently represents a substituted or unsubstituted alkyl group or a halogen atom, R₄Is a hydrogen atom or a substituted or unsubstituted alkyl group, R₅, R₆Is a substituted or unsubstituted aryl group, o, p and q are each independently an integer of 0 to 4, k and j are compositions, and the charge transport structure is adjusted to be 30 wt% to 70 wt% Is done. n represents the number of repeating units and is an integer of 5 to 5000. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula (1-1).
[0088]
[Chemical 2]

(Wherein R₁₀₁, R₁₀₂Each independently represents a substituted or unsubstituted alkyl group, aryl group or halogen atom. l and m are integers of 0 to 4, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-, -SO₂-, -CO-, -CO-O-Z-O-CO- (wherein Z represents an aliphatic divalent group),
Or the following general formula (1-2)
[0089]
[Chemical 3]

(Wherein, a is an integer of 1 to 20, b is an integer of 1 to 2000, R₁₀₃, R₁₀₄Represents a substituted or unsubstituted alkyl group or aryl group. ). Where R₁₀₁And R₁₀₂, R₁₀₃And R₁₀₄May be the same or different. )
[0090]
Specific example of general formula (1)
R₁, R₂, R₃Each independently represents a substituted or unsubstituted alkyl group or a halogen atom. Specific examples thereof include the following, which may be the same or different.
The alkyl group is preferably C₁~ C₁₂ C in particular₁~ C₈, More preferably C₁~ C₄These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄Alkyl group or C₁~ C₄It may contain a phenyl group substituted with an alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
[0091]
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
R₄Represents a hydrogen atom or a substituted or unsubstituted alkyl group. Specific examples of the alkyl group include the above R₁, R₂, R₃The same thing is mentioned.
R₅, R₆Represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.
[0092]
As an aromatic hydrocarbon group, a phenyl group, a condensed polycyclic group as a naphthyl group, a pyrenyl group, a 2-fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group, Examples of the fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups include a biphenylyl group and a terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
[0093]
The above aryl group may have the following groups as substituents.
(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.
(2) As the alkyl group, the above R₁, R₂, R₃The same thing is mentioned.
(3) Alkoxy group (-OR₁₀₅), R in the formula₁₀₅Represents an alkyl group defined in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
(4) As an aryloxy group, a phenyl group and a naphthyl group are mentioned as an aryl group. This is C₁~ C₄ An alkoxy group of₁~ C₄The alkyl group or halogen atom may be contained as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
(5) Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
[0094]
X is introduced into the main chain by using the diol compound of the following general formula (B) together with the diol compound of the following general formula (B) when the diol compound having the triarylamino group of the following general formula (A) is polymerized using the phosgene method, transesterification method or the like. Is done. In this case, the produced polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (A) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.
[0095]
[Formula 4]

[0096]
Specific examples of the diol compound of the general formula (B) include the following.
1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1,3- Aliphatic diols such as propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene ether glycol, and 1,4 -Cycloaliphatic diols such as cyclohexanediol, 1,3-cyclohexanediol, and cyclohexane-1,4-dimethanol.
Examples of the diol having an aromatic ring include 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl). ) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2, 2-bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) pro 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 3, 3′-dimethyl-4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl oxide, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene 9,9-bis (4-hydroxyphenyl) xanthene, ethylene glycol-bis (4-hydroxybenzoate), diethylene glycol-bis (4-hydroxybenzoate), triethylene glycol-bis (4-hydroxybenzoate), 1,3 -Bis (4-H Rokishifeniru) - tetramethyldisiloxane, phenol-modified silicone oils.
[0097]
As a second example of the polymer charge transport material, there is a polycarbonate having a triarylamine structure represented by the following general formula (2).
[0098]
[Chemical formula 5]

[0099]
Where R₇, R₈Is a substituted or unsubstituted aryl group, Ar₁, Ar₂, Ar₃Represent the same or different arylene groups. X, k, j and n are the same as those in the general formula (1).
[0100]
Specific example of general formula (2)
R₇, R₈Represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.
As an aromatic hydrocarbon group, a phenyl group, a condensed polycyclic group as a naphthyl group, a pyrenyl group, a 2-fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group, Fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, non-condensed polycyclic group biphenylyl group, terphenylyl group, or the following general formula (2-1)
[0101]
[Chemical 6]

[0102]
(W is -O-, -S-, -SO-, -SO₂-, -CO- and the following general formulas (2-2), (2-3), (2-4), (2-5);
[0103]
[Chemical 7]

[0104]
[Chemical 8]

[0105]
[Chemical 9]

[0106]
[Chemical Formula 10]

The divalent group represented by these is represented. )
The group represented by these is shown.
[0107]
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
[0108]
Ar₁, Ar₂And Ar₃The arylene group represented by R is R₇And R₈The bivalent group of the aryl group shown by these is mentioned, You may be same or different.
The above aryl group and arylene group may have the following groups as substituents. These substituents are R in the above general formula.₁₀₆, R₁₀₇, R₁₀₈It is expressed as a specific example.
(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.
(2) The alkyl group is preferably C₁~ C₁₂ C in particular₁~ C₁₈, More preferably C₁~ C₄These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄Alkyl group or C₁~ C₄It may contain a phenyl group substituted with an alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
(3) Alkoxy group (-OR₁₀₉), R in the formula₁₀₉Represents an alkyl group defined in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
(4) As an aryloxy group, a phenyl group and a naphthyl group are mentioned as an aryl group. This is C₁~ C₄An alkoxy group of₁~ C₄The alkyl group or halogen atom may be contained as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
(5) Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(6) The following general formula (2-6)
[0109]
Embedded image

[0110]
(Wherein R₁₁₀And R₁₁₁Each independently represents an alkyl group or an aryl group defined in (2). Examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group, and these include C₁~ C₄An alkoxy group of₁~ C₄The alkyl group or halogen atom may be contained as a substituent. A ring may be formed together with a carbon atom on the aryl group. )
Specifically, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (p-tolyl) amino group, dibenzylamino group, piperidino group, morpholino group, Examples include a yurolidyl group.
(7) An alkylenedioxy group or an alkylenedithio group such as a methylenedioxy group or a methylenedithio group.
[0111]
X is introduced into the main chain by using the diol compound of the following general formula (B) together with the diol compound of the following general formula (B) when polymerizing the diol compound having the triarylamino group of the following general formula (C) using the phosgene method, transesterification method or the like. Is done. In this case, the produced polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (C) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.
[0112]
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[0113]
Examples of the diol compound of the general formula (B) are the same as those of the general formula (1).
[0114]
As a third example of the polymer charge transport material, there is a polycarbonate having a triarylamine structure represented by the following general formula (3).
[0115]
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[0116]
Where R₉, R₁₀Is a substituted or unsubstituted aryl group, Ar₄, Ar₅, Ar₆Represent the same or different arylene groups. X, k, j, and n are the same as in the general formula (1).
[0117]
Specific example of general formula (3)
R₉, R₁₀Represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.
As an aromatic hydrocarbon group, a phenyl group, a condensed polycyclic group as a naphthyl group, a pyrenyl group, a 2-fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group, Examples of the fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups include a biphenylyl group and a terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
[0118]
Ar₄, Ar₅And Ar₆The arylene group represented by R is R₉And R₁₀The bivalent group of the aryl group shown by these is mentioned, You may be same or different. The above aryl group and arylene group may have the following groups as substituents.
(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.
(2) The alkyl group is preferably C₁~ C₁₂C in particular₁~ C₈, More preferably C₁~ C₄These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄Alkyl group or C₁~ C₄It may contain a phenyl group substituted with an alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
(3) Alkoxy group (-OR₁₁₂), R in the formula₁₁₂Represents an alkyl group defined in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
(4) As an aryloxy group, a phenyl group and a naphthyl group are mentioned as an aryl group. This is C₁~ C₄An alkoxy group of₁~ C₄The alkyl group or halogen atom may be contained as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
(5) Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
(7) Acyl group; Specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
[0119]
X is introduced into the main chain by using a diol compound of the following general formula (B) together when the diol compound having a triarylamino group of the following general formula (D) is polymerized using the phosgene method, transesterification method or the like. Is done. In this case, the produced polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (D) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.
[0120]
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[0121]
Examples of the diol compound of the general formula (B) include the same compounds as those in the general formula (1).
[0122]
As a fourth example of the polymer charge transport material, there is a polycarbonate having a triarylamine structure represented by the following general formula (4).
[0123]
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[0124]
Where R₁₁, R₁₂Is a substituted or unsubstituted aryl group, Ar₇, Ar₈, Ar₉Are the same or different arylene groups, and s represents an integer of 1 to 5. X, k, j, and n are the same as in the general formula (1).
[0125]
Specific example of general formula (4)
R₁₁, R₁₂Represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.
As an aromatic hydrocarbon group, a phenyl group, a condensed polycyclic group as a naphthyl group, a pyrenyl group, a 2-fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group, Examples of the fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups include a biphenylyl group and a terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
[0126]
Ar₇, Ar₈And Ar₉The arylene group represented by R is R₁₁And R₁₂The bivalent group of the aryl group shown by these is mentioned, You may be same or different.
The above aryl group and arylene group may have the following groups as substituents.
(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.
(2) The alkyl group is preferably C₁~ C₁₂C in particular₁~ C₈, More preferably C₁~ C₄These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄Alkyl group or C₁~ C₄A phenyl group substituted with an alkoxy group of Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
(3) Alkoxy group (-OR₁₁₃ ), R in the formula₁₁₃Represents an alkyl group defined in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
(4) As an aryloxy group, a phenyl group and a naphthyl group are mentioned as an aryl group. This is C₁~ C₄An alkoxy group of₁~ C₄The alkyl group or halogen atom may be contained as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
(5) Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
[0127]
X is introduced into the main chain by using a diol compound of the following general formula (B) together with the diol compound of the following general formula (B) when the diol compound having the triarylamino group of the following general formula (E) is polymerized using the phosgene method, transesterification method or the like. Is done. In this case, the produced polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (E) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.
[0128]
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[0129]
Examples of the diol compound of the general formula (B) are the same as those of the general formula (1).
[0130]
As a fifth example of the polymer charge transport material, there is a polycarbonate having a triarylamine structure represented by the following general formula (5).
[0131]
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[0132]
Where R₁₃, R₁₄Is a substituted or unsubstituted aryl group, Ar₁₀, Ar₁₁, Ar₁₂Are the same or different arylene groups, X₁, X₂ Represents a substituted or unsubstituted ethylene group or a substituted or unsubstituted vinylene group. X, k, j, and n are the same as in the general formula (1).
[0133]
Specific example of general formula (5)
R₁₃, R₁₄ Represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.
As an aromatic hydrocarbon group, a phenyl group, a condensed polycyclic group as a naphthyl group, a pyrenyl group, a 2-fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group, Examples of the fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups include a biphenylyl group and a terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
[0134]
Ar₁₀, Ar₁₁, Ar₁₂The arylene group represented by R is R₁₃And R₁₄The bivalent group of the aryl group shown by these is mentioned, You may be same or different.
The above aryl group and arylene group may have the following groups as substituents.
(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.
(2) The alkyl group is preferably C₁~ C₁₂C in particular₁~ C₈ , More preferably C₁~ C₄These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄ Alkyl group or C₁~ C₄It may contain a phenyl group substituted with an alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
(3) Alkoxy group (-OR₁₁₄ ), R in the formula₁₁₄Represents an alkyl group defined in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
(4) As an aryloxy group, a phenyl group and a naphthyl group are mentioned as an aryl group. This is C₁~ C₄An alkoxy group of₁~ C₄The alkyl group or halogen atom may be contained as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
(5) Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
[0135]
X₁, X₂Represents a substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylene group, and examples of the substituent include a cyano group, a halogen atom, a nitro group, and the above R₁₃, R₁₄And the alkyl group of (2) above.
[0136]
X is introduced into the main chain by using a diol compound of the following general formula (B) together with a diol compound of the following general formula (B) when polymerizing a diol compound having the triarylamino group of the following general formula (F) using a phosgene method, a transesterification method or the like. Is done. In this case, the produced polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (F) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.
[0137]
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[0138]
Examples of the diol compound of the general formula (B) are the same as those of the general formula (1).
[0139]
As a sixth example of the polymer charge transport material, there is a polycarbonate having a triarylamine structure represented by the following general formula (6).
[0140]
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[0141]
Where R₁₅, R₁₆, R₁₇, R₁₈Is a substituted or unsubstituted aryl group, Ar₁₃, Ar₁₄, Ar₁₅, Ar₁₆Are the same or different arylene groups, Y₁, Y₂, Y₃Represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group, which may be the same or different. X, k, j, and n are the same as in the general formula (1).
[0142]
Specific example of general formula (6)
R₁₅, R₁₆, R₁₇, R₁₈Represents a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different.
As an aromatic hydrocarbon group, a phenyl group, a condensed polycyclic group as a naphthyl group, a pyrenyl group, a 2-fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group, Examples of the fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups include a biphenylyl group and a terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
[0143]
Ar₁₃, Ar₁₄, Ar₁₅And Ar₁₆The arylene group represented by R is R₁₅, R₁₆, R₁₇And R₁₈The above-mentioned divalent group of the aryl group shown above is mentioned, and they may be the same or different.
The above aryl group and arylene group may have the following groups as substituents.
(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.
(2) The alkyl group is preferably C₁~ C₁₂C in particular₁~ C₈ , More preferably C₁~ C₄These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄Alkyl group or C₁~ C₄It may contain a phenyl group substituted with an alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
(3) Alkoxy group (-OR₁₁₅), R in the formula₁₁₅Represents an alkyl group defined in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
(4) As an aryloxy group, a phenyl group and a naphthyl group are mentioned as an aryl group. This is C₁~ C₄An alkoxy group of₁~ C₄The alkyl group or halogen atom may be contained as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
[0144]
Y₁, Y₂, Y₃Represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group, which may be the same or different. .
The alkylene group represents a divalent group derived from the alkyl group shown in (2) above. Specifically, methylene group, ethylene group, 1,3-propylene group, 1,4-butylene group, 2-methyl-1,3-propylene group, difluoromethylene group, hydroxyethylene group, cyanoethylene group, methoxyethylene Group, phenylmethylene group, 4-methylphenylmethylene group, 2,2-propylene group, 2,2-butylene group, diphenylmethylene group and the like.
Examples of the cycloalkylene group include 1,1-cyclopentylene group, 1,1-cyclohexylene group, 1,1-cyclooctylene group and the like.
Examples of the alkylene ether group include a dimethylene ether group, a diethylene ether group, an ethylene methylene ether group, a bis (triethylene) ether group, and a polytetramethylene ether group.
[0145]
X is introduced into the main chain by using a diol compound of the following general formula (B) together with a diol compound of the following general formula (B) when polymerizing a diol compound having a triarylamino group of the following general formula (G) using the phosgene method, transesterification method, etc. Is done. In this case, the produced polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group of the following general formula (G) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.
[0146]
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[0147]
Examples of the diol compound of the general formula (B) include the same compounds as those in the general formula (1).
[0148]
As a seventh example of the polymer charge transport material, there is a polycarbonate having a triarylamine structure represented by the following general formula (7).
[0149]
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[0150]
Where R₁₉, R₂₀Represents a hydrogen atom, a substituted or unsubstituted aryl group, and R₁₉And R₂₀May form a ring. Ar₁₇, Ar₁₈, Ar₁₉Represent the same or different arylene groups. X, k, j, and n are the same as in the general formula (1).
[0151]
Specific example of general formula (7)
R₁₉, R₂₀Represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.
As an aromatic hydrocarbon group, a phenyl group, a condensed polycyclic group as a naphthyl group, a pyrenyl group, a 2-fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group, Examples of the fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups include a biphenylyl group and a terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
R₁₉, R₂₀In the case of forming a ring, 9-fluorenylidene, 5H-dibenzo [a, d] cyclohebutenylidene and the like can be mentioned.
[0152]
Ar₁₇, Ar₁₈, Ar₁₉The arylene group represented by R is R₁₉And R₂₀The bivalent group of the aryl group shown by these is mentioned, You may be same or different.
The above aryl group and arylene group may have the following groups as substituents.
(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.
(2) The alkyl group is preferably C₁~ C₁₂C in particular₁~ C₈, More preferably C₁~ C₄These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄Alkyl group or C₁~ C₄It may contain a phenyl group substituted with an alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
(3) Alkoxy group (-OR_{11 6}), R in the formula_{11 6}Represents an alkyl group defined in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
(4) As an aryloxy group, a phenyl group and a naphthyl group are mentioned as an aryl group. This is C₁~ C₄An alkoxy group of₁~ C₄The alkyl group or halogen atom may be contained as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
(5) Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
[0153]
X is introduced into the main chain by using the diol compound of the following general formula (B) together when the diol compound having the triarylamino group of the following general formula (H) is polymerized using the phosgene method, the transesterification method or the like. Is done. In this case, the produced polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (H) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.
[0154]
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[0155]
Examples of the diol compound of the general formula (B) are the same as those of the general formula (1).
[0156]
As an eighth example of the polymer charge transport material, there is a polycarbonate having a triarylamine structure represented by the following general formula (8).
[0157]
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[0158]
Where R₂₁Is a substituted or unsubstituted aryl group, Ar₂₀, Ar₂₁, Ar₂₂, Ar₂₃Represent the same or different arylene groups. X, k, j, and n are the same as in the general formula (1).
[0159]
Specific example of general formula (8)
R₂₁Represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.
As an aromatic hydrocarbon group, a phenyl group, a condensed polycyclic group as a naphthyl group, a pyrenyl group, a 2-fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group, Examples of the fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups include a biphenylyl group and a terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
[0160]
Ar₂₀, Ar₂₁, Ar₂₂, Ar₂₃The arylene group represented by R is R₂₁The bivalent group of the aryl group shown by these is mentioned, You may be same or different.
The above aryl group and arylene group may have the following groups as substituents.
(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.
(2) The alkyl group is preferably C₁~ C₁₂C in particular₁~ C₈, More preferably C₁~ C₄These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄Alkyl group or C₁~ C₄It may contain a phenyl group substituted with an alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
(3) Alkoxy group (-OR₁₁₇), R in the formula₁₁₇ Represents an alkyl group defined in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
(4) As an aryloxy group, a phenyl group and a naphthyl group are mentioned as an aryl group. This is C₁~ C₄An alkoxy group of₁~ C₄The alkyl group or halogen atom may be contained as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
(5) Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
[0161]
X is introduced into the main chain by using the diol compound of the following general formula (B) together when the diol compound having the triarylamino group of the following general formula (J) is polymerized using the phosgene method, the transesterification method or the like. Is done. In this case, the produced polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group of the following general formula (J) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.
[0162]
Embedded image

[0163]
Examples of the diol compound of the general formula (B) are the same as those of the general formula (1).
[0164]
As a ninth example of the polymer charge transport material, there is a polycarbonate having a triarylamine structure represented by the following general formula (9).
[0165]
Embedded image

[0166]
Where R₂₂, R₂₃, R₂₄, R₂₅Is a substituted or unsubstituted aryl group, Ar₂₄, Ar₂₅, Ar₂₆, Ar₂₇, Ar₂₈Represent the same or different arylene groups. X, k, j, and n are the same as in the general formula (1).
[0167]
Specific example of general formula (9)
R₂₂, R₂₃, R₂₄, R₂₅Represents a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different.
As an aromatic hydrocarbon group, a phenyl group, a condensed polycyclic group as a naphthyl group, a pyrenyl group, a 2-fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group, Examples of the fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups include a biphenylyl group and a terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
[0168]
Ar₂₄, Ar₂₅, Ar₂₆, Ar₂₇And Ar₂₈The arylene group represented by R is R₂₂, R₂₃, R₂₄And R₂₅The above-mentioned divalent group of the aryl group shown above is mentioned, and they may be the same or different.
The above aryl group and arylene group may have the following groups as substituents.
(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.
(2) The alkyl group is preferably C₁~ C₁₂C in particular₁~ C₈, More preferably C₁~ C₄These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄Alkyl group or C₁~ C₄It may contain a phenyl group substituted with an alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
(3) Alkoxy group (-OR₁₁₈), R in the formula₁₁₈Represents an alkyl group defined in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
(4) As an aryloxy group, a phenyl group and a naphthyl group are mentioned as an aryl group. This is C₁~ C₄An alkoxy group of₁~ C₄The alkyl group or halogen atom may be contained as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
(5) Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
[0169]
X is introduced into the main chain by using the diol compound of the following general formula (B) together with the diol compound of the following general formula (B) when the diol compound having the triarylamino group of the following general formula (L) is polymerized using the phosgene method, transesterification method or the like. Is done. In this case, the produced polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (L) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.
[0170]
Embedded image

[0171]
Examples of the diol compound of the general formula (B) are the same as those of the general formula (1).
[0172]
A tenth example of the polymer charge transport material is a polycarbonate having a triarylamine structure represented by the following general formula (10).
[0173]
Embedded image

[0174]
Where R₂₆, R₂₇Is a substituted or unsubstituted aryl group, Ar₂₉, Ar₃₀, Ar₃₁Represent the same or different arylene groups. X, k, j, and n are the same as in the general formula (1).
[0175]
Specific example of general formula (10)
R₂₆, R₂₇Represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.
As aromatic hydrocarbon group, phenyl group, as condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fullerene group Examples of the oleenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups include a biphenylyl group and a terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
[0176]
Ar₂₉, Ar₃₀, Ar₃₁The arylene group represented by R is R₂₆And R₂₇The bivalent group of the aryl group shown by these is mentioned, You may be same or different.
The above aryl group and arylene group may have the following groups as substituents.
(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.
(2) The alkyl group is preferably C₁~ C₁₂C in particular₁~ C₈, More preferably C₁~ C₄These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄Alkyl group or C₁~ C₄It may contain a phenyl group substituted with an alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
(3) Alkoxy group (-OR₁₁₉), R in the formula₁₁₉Represents an alkyl group defined in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
(4) As an aryloxy group, a phenyl group and a naphthyl group are mentioned as an aryl group. This is C₁~ C₄An alkoxy group of₁~ C₄The alkyl group or halogen atom may be contained as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
(5) Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
[0177]
X is introduced into the main chain by using a diol compound of the following general formula (B) together with the diol compound of the following general formula (B) when polymerizing a diol compound having a triarylamino group of the following general formula (M) using the phosgene method, transesterification method or the like. Is done. In this case, the produced polycarbonate resin is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group of the following general formula (M) and a bischloroformate derived from the following general formula (B). In this case, the produced polycarbonate becomes an alternating copolymer.
[0178]
Embedded image

[0179]
Examples of the diol compound of the general formula (B) are the same as those of the general formula (1).
[0180]
Furthermore, a dispersant such as a polycarboxylic acid compound is used in the protective layer of the present invention as necessary. The dispersant is added as necessary for the purpose of improving the dispersibility of the inorganic filler and improving the stability of the coating liquid during the preparation of the coating liquid. As the dispersant, a polycarboxylic acid compound is particularly effective in that it disperses the inorganic filler to a value close to the primary particle size and does not adversely affect the electrical characteristics and image characteristics.
Examples of the polycarboxylic acid compound include a low molecular compound, an oligomer, and a high molecular compound having a plurality of carboxylic acid residues, and examples thereof include organic fatty acids and highly oxidized resins. Examples of the polycarboxylic acid compound that is an oligomer or a polymer compound include polyester resins, acrylic resins, copolymers using acrylic acid or methacrylic acid, and styrene-acrylic copolymers. As the acid value of the polycarboxylic acid compound used here, one having 10 to 400 (mg KOH / g) can be used effectively. (The acid value is defined as the number of milligrams of potassium hydroxide required to neutralize the free fatty acid contained in 1 g.)
The addition amount of the polycarboxylic acid compound is 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, with respect to 100 parts by weight of the inorganic filler contained.
[0181]
As a method for forming the protective layer, a normal coating method is employed. Among them, the spray method is an effective means. The thickness of the protective layer is 1.0 to 15 μm, preferably about 2 to 10 μm.
[0182]
<Addition of antioxidant>
In the present invention, in order to improve environmental resistance, an antioxidant is added to each layer such as an intermediate layer, a charge generation layer, a charge transport layer, and a protective layer, particularly for the purpose of preventing a decrease in sensitivity and an increase in residual potential Can be added. Examples of the antioxidant that can be used in the present invention include the following phenol compounds, paraphenylenediamines, hydroquinones, organic sulfur compounds, and organic phosphorus compounds.
[0183]
Phenolic compounds:
2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol), 4, 4'-thiobis- (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-4 -Hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [meth -3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis (4′-hydroxy-3′-t-butylphenyl) buty Rick acid] cricol ester, tocopherols and the like.
[0184]
Paraphenylenediamines:
N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine, N, N'- Di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine and the like.
[0185]
Hydroquinones:
2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2- (2-octadecenyl) ) -5-methylhydroquinone and the like.
[0186]
Organic sulfur compounds:
Dilauryl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, ditetradecyl-3,3'-thiodipropionate and the like.
[0187]
Organophosphorus compounds:
Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine, and the like.
[0188]
The above exemplified compounds are known as antioxidants such as rubbers, plastics, oils and fats, and can be easily obtained from commercial products.
The addition amount of the antioxidant in the present invention is 0.01 to 10% by weight based on the total weight of the layer to be added.
[0189]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to a following example. In addition, all the parts used in an Example represent a weight part.
[0190]
Photoconductor Preparation Example 1
By sequentially coating and drying an intermediate layer coating solution, a charge generation layer coating solution, a charge transport layer coating solution, and a protective layer coating solution having the following composition on a φ30 mm aluminum drum: A 3 μm intermediate layer, a 0.2 μm charge generation layer, and a 25 μm charge transport layer were formed.
Subsequently, the α-alumina particle-containing coating solution for protective layer was spray-coated on the charge transport layer, and a protective layer was provided in a thickness of 5 μm to produce the electrophotographic photosensitive member (photosensitive member) of the present invention.

[0191]
Embedded image

[0192]
Embedded image

[0193]
Photoconductor Preparation Example 2
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the protective layer coating solution in Photoconductor Preparation Example 1 was changed to one having the following composition.

[0194]
Photoconductor Preparation Example 3
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the protective layer coating solution in Photoconductor Preparation Example 1 was changed to one having the following composition.
[Coating liquid for protective layer]

[0195]
Photoconductor Preparation Example 4
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the protective layer coating solution in Photoconductor Preparation Example 1 was changed to one having the following composition.

[0196]
Photoconductor Preparation Example 5
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the protective layer coating solution in Photoconductor Preparation Example 1 was changed to one having the following composition.

[0197]
Photoconductor Preparation Example 6
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the protective layer coating solution in Photoconductor Preparation Example 1 was changed to one having the following composition.

[0198]
Photoconductor Preparation Example 7
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the protective layer coating solution in Photoconductor Preparation Example 1 was changed to one having the following composition.

[0199]
Photoconductor Preparation Example 8
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the protective layer coating solution in Photoconductor Preparation Example 1 was changed to one having the following composition.

[0200]
Photoconductor Preparation Example 9
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the protective layer coating solution in Photoconductor Preparation Example 1 was changed to one having the following composition.

[0201]
Photoconductor Preparation Example 10
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the protective layer coating solution in Photoconductor Preparation Example 1 was changed to one having the following composition.

(This spray solution was agglomerated in the produced dispersion during spray coating for forming the protective layer, and the spray discharge amount was unstable.)
[0202]
Photoconductor Preparation Example 11
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the protective layer coating solution in Photoconductor Preparation Example 1 was changed to one having the following composition.

(This coating solution was found to have irregularities on the surface of the produced photoreceptor and was inferior in surface smoothness.)
[0203]
Photoconductor Preparation Example 12
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the intermediate layer coating solution in Photoconductor Preparation Example 1 was changed to one having the following composition, and the film thickness of the intermediate layer was changed to 0.3 μm. .
[Coating liquid for intermediate layer]
Polyamide resin (CM8000: manufactured by Toray Industries, Inc.) 4 parts Methanol 70 parts Butanol 30 parts
[0204]
Photoconductor Preparation Example 13
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1, except that the intermediate layer coating solution in Photoconductor Preparation Example 1 was changed to one having the following composition and the thickness of the intermediate layer was changed to 3.5 μm. .

[0205]
Photoconductor Preparation Example 14
In Photoconductor Preparation Example 1, the following anodic oxide film treatment was performed on the conductive support, and a charge generation layer, a charge transport layer, and a protective layer were formed on the anodic oxide film without forming an intermediate layer. A photoconductor was prepared in the same manner as in Example 1 of the photoconductor.
(Anodized film treatment)
The surface of the conductive support was mirror-polished, degreased and washed with water, then immersed in an electrolytic bath with a liquid temperature of 20 ° C. and sulfuric acid of 15 vol%, and an anodized film treatment was performed at an electrolysis voltage of 15 V for 30 minutes. . Further, after washing with water, sealing treatment was performed with a 7% nickel acetate aqueous solution (50 ° C.). Further, after washing with water, sealing treatment was performed with a 7% nickel acetate aqueous solution (50 ° C.). Thereafter, washing with pure water was performed to obtain a conductive support on which a 6 μm anodic oxide film was formed.
[0206]
Photoconductor Preparation Example 15
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the protective layer coating solution in Photoconductor Preparation Example 1 was changed to one having the following composition.
[Coating liquid for protective layer]
α-alumina particles (Sumicorundum AA-03: manufactured by Sumitomo Chemical) 2 parts
Polycarboxylic acid compound (BYK-P104: manufactured by Big Chemie) 0.02 parts
7 parts of a polymer charge transport material having the following structure (T-1)
[0207]
Embedded image

60 parts of cyclohexanone
Tetrahydrofuran 200 parts
[0208]
Photoconductor Preparation Example 16
In Photoconductor Preparation Example 1, a photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the charge transport layer was 30 μm and no protective layer was provided.
[0209]
For the photoconductors produced as described above, photoconductor No. Table 1 shows a list of filler names and characteristic values contained in the protective layer.
[0210]
[Table 1]

[0211]
Example 1,Reference Examples 1-6Comparative Examples 1 to 3
  The photoconductors shown in Photoconductor Preparation Examples 1, 3, 5 to 11, and 15 were mounted on a process cartridge as shown in FIG. 2 and mounted on a tandem-type full-color image forming apparatus as shown in FIG. The charging bias was set so that the charging potential was −850 V, and image writing was performed using a 655 nm LD. As an output manuscript, output a total of 10,000 sheets, 1000 sheets of continuous character charts with 5% black character writing rate and 1% red character writing rate, and 9000 sheets of diagonal lattice chart with 6% writing rate in full color mode. As one set, a total of 5 sets (50,000 sheets) of image output were performed in a normal temperature and normal humidity (20 ° C./50% RH) environment.
[0212]
As an evaluation method, measurement of standard deviation of film thickness, wear amount, and exposed portion potential and image evaluation were performed at the initial stage and after passing through 50,000 sheets. Each evaluation method and evaluation result are shown below.
Photoreceptor film thickness and wear:
In the longitudinal direction of the photosensitive drum, the standard deviation and the average value (referred to as the average film thickness) of the film thickness were determined from a total of 80 points including 20 points at equal intervals and 4 points in the circumferential direction.
The amount of wear was determined from the difference between the average film thickness of the photoreceptor in the initial state and the average film thickness after passing 50,000 sheets. Table 2 shows the results of the standard deviation of the film thickness and the amount of wear.
Exposure part potential:
An electrometer probe was attached to the developing portion of the apparatus shown in FIG. 1, and the surface potential of the photosensitive member was measured after moving to the developing site after charging and image exposure. Table 3 shows the measurement results of the exposure portion potential at the initial stage and after the passage of 50,000 sheets.
Images after initial and after 50,000 sheets have passed:
Table 4 shows the results of image quality evaluation of (1) halftone, (2) resolution, and (3) color reproducibility. Each evaluation is shown below.
(1) Halftone image evaluation: A single-color halftone image was output for each image forming element at the initial stage and after passing through 50,000 sheets, and the image quality was evaluated visually and with a microscope. The image quality evaluation rank is as follows.
◎ ・ ・ ・ Good
○ ・ ・ ・ Some local density unevenness
Δ: Density unevenness occurs, but there is no problem in actual use
×: Concentration unevenness is conspicuous
(2) Image evaluation of resolution: Monochromatic 100 μm wide thin line images were output for each image forming element at the initial stage and after passing through 50,000 sheets, and evaluated visually and using a microscope. The evaluation rank is as follows.
◎ ・ ・ ・ Good
○ ... There is a local thickening of the line width
△ ・ ・ ・ Line weight is slightly noticeable
× ... In addition to thickening of the line width, toner scattering is seen
(3) Evaluation of color reproducibility: A full color image was output at the initial stage and after passing through 50,000 sheets, and the color reproducibility was ranked for each full color image in five stages of 5 to 1 as follows. . 5 indicates that the color reproducibility is good, and that the reproducibility decreases as it goes to 1. In addition, 4 or more is a level which does not have a problem in actual use.
[0213]
[Table 2]

[0214]
[Table 3]

[0215]
[Table 4]

[0216]
In addition, after the above-described continuous output of 50,000 images in a normal temperature and normal humidity (20 ° C./50% RH) environment, a continuous high temperature and high humidity (30 ° C./90% RH) environment continues to 100 One full color image was output.
After continuous printing of 50,000 sheets under normal temperature and normal humidity (20 ° C / 50% RH) environment, and after 100 full-color images are output continuously under high temperature and high humidity (30 ° C / 90% RH) environment Table 5 shows the evaluation results for the images.
[0217]
[Table 5]

[0218]
<Evaluation results>
  Example 1,Reference Examples 1-6As a result, the use of α-alumina particles in the protective layer shows extremely uniform characteristics as a tandem photoconductor for a full-color image forming apparatus with respect to wear resistance, environmental characteristics, electrostatic characteristics, and wear characteristics. I understand. In particular, it can be seen that the use of α-alumina having a uniform particle size, narrow particle size distribution, and high purity exhibits particularly good characteristics. On the other hand, in Comparative Examples 1 to 3, the filler contained in the protective layer is changed from α-alumina particles to titanium oxide, silica, and polytetrafluoroethylene, respectively. From Comparative Example 1, the writing light was scattered by the titanium oxide used as the filler, the resolution was lowered, and toner scattering was observed. When the silica of Comparative Example 2 was used, image flow occurred on the entire print surface, particularly in a high temperature and high humidity environment. In Comparative Example 3, when polytetrafluoroethylene was used, the effect of abrasion resistance was not sufficient, and image defects due to surface scratches or abrasion were observed.
[0219]
Example2, Reference Example 7,Comparative Examples 4-7
  Next, the photoconductors shown in photoconductor preparation examples 2, 3, 12 to 14 and 16 are mounted on a process cartridge as shown in FIG. 2 and mounted on a tandem type full-color image forming apparatus as shown in FIG. did. The charging bias was set so that the charging potential was −850 V, and image writing was performed using a 655 nm LD. As an output document, a full-color image output of a diagonal grid chart with a writing rate of 6% is performed continuously in an environment of normal temperature and humidity (20 ° C./50% RH) at 50,000 sheets. The dirt was visually evaluated and ranked as follows. The evaluation results are shown in Table 6.
◎ ・ ・ ・ Good
○ ・ ・ ・ Slightly dirty
△ ... Stained on the ground, but no problem in actual use
× ... Soil stains are noticeable and image quality deteriorates
[0220]
[Table 6]

[0221]
Example3, Reference Example 8,Comparative Examples 8-11
  In addition, the photoconductors shown in photoconductor production examples 2, 3, 12 to 14 and 16 are mounted on a process cartridge as shown in FIG. 2 and mounted in a tandem-type full-color image forming apparatus as shown in FIG. . The charging bias was set so that the charging potential was −850 V, and image writing was performed using a 655 nm LD. Table 7 shows the results of image quality evaluation of full-color images that were output continuously for 500 sheets in a low-temperature and low-humidity (10 ° C./15% RH) environment, and the full-color images were initially and after 500 sheets were passed.
[0222]
[Table 7]

[0223]
<Evaluation results>
As is apparent from the results of Examples 8 to 11 in Tables 6 and 7, when the inorganic cured film according to the sol-gel method of the present invention is used for the intermediate layer, it is repeated in an environment of normal temperature and normal humidity and low temperature and low humidity. Excellent image quality was stably obtained even in use.
When a resin layer made of polyamide is used for the intermediate layer of the photoreceptor 12, the electrical resistance of the intermediate layer is increased, causing a decrease in image density, and a desired image quality cannot be obtained continuously. When an intermediate layer in which a conductive filler is dispersed in a binder resin as in the photosensitive member 13 is used, a stable image cannot be obtained due to a problem of filler dispersibility and an increase in exposed portion potential. When alumite was used instead of the intermediate layer as in the photoconductor 14, image defects such as background smudges and black spots were observed in the initial use. It can be seen that when the protective layer is not provided as in the photoconductor 16, it does not have durability.
[0224]
【The invention's effect】
As described above, according to the present invention, even in various environments, the respective photoreceptors in the initial use state have uniform characteristics, and even when repeatedly used in various print modes peculiar to the tandem method, It is possible to provide an extremely homogeneous electrophotographic photosensitive member that has a high electrostatic fatigue stability and has little change in characteristics and variation among a plurality of electrophotographic photosensitive members. Further, by using the electrophotographic photosensitive member, it is small enough to always form an image with good color reproducibility even when a large number of color images of the same document are formed under any environment, and A high-speed tandem full-color image forming apparatus and a process cartridge for the image forming apparatus can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic diagram for explaining a tandem full-color image forming apparatus according to the present invention.
FIG. 2 is a schematic view for explaining a process cartridge for a full-color image forming apparatus according to the present invention.
FIG. 3 is a schematic cross-sectional view showing a configuration example in which the photosensitive layer of the electrophotographic photosensitive member of the present invention has a single layer configuration.
FIG. 4 is a schematic cross-sectional view showing another structural example in which the photosensitive layers of the electrophotographic photosensitive member of the present invention are laminated.
FIG. 5 is a schematic cross-sectional view showing still another structural example in which the photosensitive layers of the electrophotographic photosensitive member of the present invention are laminated.
[Explanation of symbols]
1C, 1M, 1Y, 1K photoconductor
2C, 2M, 2Y, 2K charging member
3C, 3M, 3Y, 3K laser light
4C, 4M, 4Y, 4K development member
5C, 5M, 5Y, 5K Cleaning member
6C, 6M, 6Y, 6K imaging elements
7 Transfer paper
8 Supply roller
9 Registration roller
10 Transfer conveyor belt
11C, 11M, 11Y, 11K transfer brush
12 Fixing device
16 photoconductor
17 Charger charger
18 Cleaning brush
19 Image exposure unit
20 Development roller
31 Conductive support
32 Middle layer
33 Photosensitive layer
34 Charge generation layer
35 Charge transport layer
36 Protective layer

Claims (20)

In a tandem full color image forming apparatus in which a plurality of image forming elements comprising at least a charging means, an image exposure means, a developing means, a transfer means, and an electrophotographic photosensitive member are arranged, the electrophotographic photosensitive member has a conductive support. At least an intermediate layer, a photosensitive layer, and a protective layer are provided on the body, the intermediate layer contains an organometallic compound and / or a silane coupling agent, and the protective layer is at least aluminum ammonium carbonate hydroxide [NH ₄ AlCO ₃ (OH) ₂ ] containing α-alumina particles obtained by pyrolyzing and a binder resin, a full-color image forming apparatus. 2. The full color image forming apparatus according to claim 1, wherein the [alpha] -alumina particles have an average particle size of 0.05 to 1.0 [mu] m. The α-alumina particles have a particle size ratio (Db / Da) of 4 or less when the average particle sizes of 10% and 90% from the fine particle side of the cumulative particle size distribution are Da and Db, respectively. The full-color image forming apparatus according to claim 1, wherein: The full-color image forming apparatus according to claim 1 , wherein a content of sodium as an impurity contained in the α-alumina particles is 20 ppm or less. The full-color image forming apparatus according to any one of claims 1 to 4, wherein the organometallic compound contained in the intermediate layer is a metal alkoxide or an organometallic chelate. 6. The full-color image forming apparatus according to claim 5, wherein the metal alkoxide or organometallic chelate is an organometallic compound comprising at least one metal selected from zirconium, titanium, or aluminum.   The full-color image forming apparatus according to claim 1, wherein the protective layer contains a charge transport material. 8. The full color image forming apparatus according to claim 7, wherein the charge transport material is a polymer charge transport material. 9. The full-color image forming apparatus according to claim 8, wherein the polymer charge transport material contains a polycarbonate having at least a triarylamine structure in the main chain and / or side chain. The full-color image forming apparatus according to claim 1, wherein the protective layer contains a polycarboxylic acid. A detachable tandem system comprising an electrophotographic photosensitive member and at least one of a charging unit, an image exposing unit, a developing unit, a transferring unit, a separating unit, and a cleaning unit. In the process cartridge for a full-color image forming apparatus, the electrophotographic photosensitive member is provided with at least an intermediate layer, a photosensitive layer, and a protective layer on a conductive support, and the intermediate layer comprises an organometallic compound and / or a silane coupling agent. And the protective layer contains at least α-alumina particles obtained by pyrolyzing aluminum ammonium carbonate hydroxide [NH ₄ AlCO ₃ (OH) ₂ ] and a binder resin. cartridge. The process cartridge according to claim 11, wherein an average particle diameter of the α-alumina particles is 0.05 to 1.0 μm. The α-alumina particles have a particle size ratio (Db / Da) of 4 or less when the average particle sizes of 10% and 90% from the fine particle side of the cumulative particle size distribution are Da and Db, respectively. The process cartridge according to claim 11, wherein the process cartridge is provided. The process cartridge according to claim 11, wherein a content of sodium as an impurity contained in the α-alumina particles is 20 ppm or less. The process cartridge according to any one of claims 11 to 14, wherein the organometallic compound contained in the intermediate layer is a metal alkoxide or an organometallic chelate. 16. The process cartridge according to claim 15, wherein the metal alkoxide or the organometallic chelate is an organometallic compound comprising at least one metal selected from zirconium, titanium, or aluminum. The process cartridge according to claim 11, wherein the protective layer contains a charge transport material. The process cartridge according to claim 17, wherein the charge transport material is a polymer charge transport material. 19. The process cartridge according to claim 18, wherein the polymer charge transport material contains a polycarbonate having at least a triarylamine structure in the main chain and / or side chain. The process cartridge according to claim 11, wherein the protective layer contains a polycarboxylic acid.

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