JP3878444B2 - Electrophotographic photosensitive member, image forming method using the same, image forming apparatus, and process unit for image forming apparatus - Google Patents

Description

（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又はハロゲン原子、Ｒ_４は水素原子又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、または下記一般式で表わされる２価基を表わす。
【００５８】
【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わす。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価基を表わす。）または、
【００５９】
【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又はアリール基を表わす。）を表わす。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。
【００６０】
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又はハロゲン原子を表わすが、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、又はハロゲン原子、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良い。
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。
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は水素原子又は置換もしくは無置換のアルキル基を表わ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わすが、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。
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）としては、Ｒ_１０５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良い。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わす。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。
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、又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。
【００６１】
【化４】

【００６２】
【化５】

【００６３】
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’-ジヒドロキシジッフェニルスルホン、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。
【００６４】
【化６】

（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は同一又は異なるアリレン基を表わす。 Ｘ，ｋ，ｊおよびｎは、一般式１の場合と同じである。）
【００６５】
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わすが、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、
【００６６】
【化７】

ここで、Ｗは−Ｏ−，−Ｓ−，−ＳＯ−，−ＳＯ_２−，−ＣＯ−及び以下の２価基を表わす。
【００６７】
【化８】

（式中、ｃは１〜１２の整数を表わす。）
【００６８】
【化９】

（式中、ｄは１〜３の整数を表わす。）
【００６９】
【化１０】

（式中、ｅは１〜３の整数を表わす。）
【００７０】
【化１１】

（式中、ｆは１〜３の整数を表わす。）
で表わされる。
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、 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。
上述のアリール基及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の具体例として表わされる。
（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、又はハロゲン原子、 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良い。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）としては、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良い。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）
【００７１】
【化１２】

式中、Ｒ_１１０及び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し、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良い。またアリール基上の炭素原子と共同で環を形成しても良い。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。
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、又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。
【００７２】
【化１３】

【００７３】
【化１４】

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。
【００７４】
【化１５】

（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 は同一又は異なるアリレン基を表わす。 Ｘ，ｋ，ｊおよびｎは、一般式１の場合と同じである。）
【００７５】
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わすが、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、 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。上述のアリール基及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、又はハロゲン原子、 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良い。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）としては、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良い。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わす。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。
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、又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。
【００７６】
【化１６】

【００７７】
【化１７】

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。
【００７８】
【化１８】

（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は同一又は異なるアリレン基、ｓは１〜５の整数を表わす。 Ｘ，ｋ，ｊおよびｎは、一般式１の場合と同じである。）
【００７９】
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わすが、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、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。
上述のアリール基及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、又はハロゲン原子、 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良い。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 ）としては、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良い。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わす。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。
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、又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。
【００８０】
【化１９】

【００８１】

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。
【００８２】
【化２０】
［一般式５］

（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は同一又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、又は置換もしくは無置換のビニレン基を表わす。 Ｘ，ｋ，ｊおよびｎは、一般式１の場合と同じである。）
【００８３】
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わすが、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、Ａｒ_１０， Ａｒ_１１ および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。
上述のアリール基及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、又はハロゲン原子、 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良い。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 ）としては、 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良い。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わす。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。
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。
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、又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。
【００８４】
【化２１】

【００８５】
【化２２】

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。
【００８６】
【化２３】

（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は同一又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。）
【００８７】
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わすが、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、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。
上述のアリール基及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、又はハロゲン原子、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良い。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）としては、 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良い。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。
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価基を表わす。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。
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、又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。
【００８８】
【化２４】

【００８９】
【化２５】

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。
【００９０】
【化２６】

（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 は同一又は異なるアリレン基を表わす。 Ｘ，ｋ，ｊおよびｎは、一般式１の場合と同じである。）
【００９１】
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わすが、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。
また、Ａｒ_１７，Ａｒ_１８ および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。
上述のアリール基及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、又はハロゲン原子、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良い。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}）としては、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良い。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わす。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。
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、又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。
【００９２】
【化２７】

【００９３】
【化２８】

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。
【００９４】
【化２９】
［一般式８］

（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 は同一又は異なるアリレン基を表わす。 Ｘ，ｋ，ｊおよびｎは、一般式１の場合と同じである。）
【００９５】
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わすが、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、Ａｒ_２０，Ａｒ_２１，Ａｒ_２２ および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。
上述のアリール基及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、又はハロゲン原子、 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良い。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）としては、 Ｒ_１１７ 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良い。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わす。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。
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、又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。
【００９６】
【化３０】

【００９７】
【化３１】

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。
【００９８】
【化３２】

（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は同一又は異なるアリレン基を表わす。 Ｘ，ｋ，ｊおよびｎは、一般式１の場合と同じである。）
【００９９】
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わすが、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、 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。
上述のアリール基及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、又はハロゲン原子、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良い。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）としては、Ｒ_１１８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良い。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わす。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。
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、又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。
【０１００】
【化３３】

【０１０１】
【化３４】

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。
【０１０２】
【化３５】
［一般式１０］

（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は同一又は異なるアリレン基を表わす。 Ｘ，ｋ，ｊおよびｎは、一般式１の場合と同じである。）
【０１０３】
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わすが、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。
また、Ａｒ_２９，Ａｒ_３０ および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。
上述のアリール基及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、又はハロゲン原子、Ｃ_１〜 Ｃ_４ のアルキル基もしくはC１〜C4のアルコキシ基で置換されたフェニル基を含有しても良い。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）としては、 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良い。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わす。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。
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、又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。
【０１０４】
【化３６】

【０１０５】
【化３７】

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。
【０１０６】
ここで用いられるバインダー樹脂は、無機フィラーを固定化し最表面層の強度を維持する目的で含有され、無機フィラー１００重量部に対し２５重量部以上、好ましくは５０重量部以上が最低限必要である。また、電荷輸送物質はじめとする添加物は電荷輸送層（３７）と同じ添加割合で使用できる。
【０１０７】
また、この無機フィラーを含有する表面部分の膜厚としては、電荷輸送層（３７）の全層でも可能であるが画像特性、電気特性上２０μｍ以下が望ましく、更に好ましくは１〜１０μｍの範囲である。
【０１０８】
無機フィラー分散層用塗工液に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を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。
【０１０９】
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、高分子化合物を指し、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。）
この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。
【０１１０】
次に、感光層が単層構成の場合について述べる。
単層構成は導電性支持体上に少なくとも電荷発生物質をバインダー樹脂中に分散した感光層（３３）を設けたものである。感光層（３３）は、電荷発生物質とバインダー樹脂の他に必要に応じて電荷輸送物質を適当な溶剤に溶解ないし分散し、これを塗布、乾燥することによって形成できる。また、必要により可塑剤やレベリング剤等を添加することもできる。それぞれ電荷発生物質、電荷輸送物質、可塑剤、レベリング剤は前記電荷発生層（３５）、電荷輸送層（３７）について既に述べたと同様のものが使用できる。
【０１１１】
バインダー樹脂としては、既に電荷輸送層（３７）で挙げたバインダー樹脂のほかに、電荷発生層（３５）で挙げたバインダー樹脂を混合して用いてもよい。また、先に挙げた高分子電荷輸送物質も良好に使用できる。樹脂成分１００重量部に対する電荷発生物質の量は１〜４０重量部が好ましく、電荷輸送物質の量は０〜１９０重量部が好ましく、さらに好ましくは５０〜１５０重量部である。感光層は、電荷発生物質、バインダー樹脂を必要に応じて電荷輸送物質とともにテトラヒドロフラン、ジオキサン、ジクロロエタン、シクロヘキサン等の溶媒を用いて分散機等で分散した塗工液を、浸漬塗工法やスプレーコート、ビードコート、リングコートなどで塗工して形成できる。
【０１１２】
感光層の膜厚は、５〜２５μｍ程度が適当である。
この単層構成の感光層（３３）が感光体の表面層になる場合、感光層（３３）の全層又はその表面部分に耐摩耗性を向上させる目的で無機フィラ−を含有させる。この無機フィラーとして平均粒径０．０７〜０．３μｍで粒径分布の狭い三方晶系α−アルミナ微粒子を用いることにより、高耐久性を有し且つ繰り返し使用に対して画像流れを発生せず、更に解像度や階調性が高く、地肌汚れや画像濃度低下のない良好な画像が持続して得られる。この単層構成における表面部分に分散される無機フィラーとしては前述のものが使用可能で、バインダー樹脂をはじめその他の構成材料としては基本的に上記単層構成の感光層（３３）に用いられるものが含有可能で、また更に必要に応じて電荷輸送層（３７）で記載のポリカルボン酸化合物、可塑剤、レベリング剤等が添加される。また、これらの含有される材料の添加量、無機フィラー分散層の製造法、膜厚としては前述の電荷輸送層（３７）、単層構成の感光層（３３）について述べたと同様の事項が適用できる。
【０１１３】
本発明の感光体においては、導電性支持体（３１）と感光層との間に下引き層を設けることができる。下引き層は一般には樹脂を主成分とするが、これらの樹脂はその上に感光層を溶剤で塗布することを考えると、一般の有機溶剤に対して耐溶剤性の高い樹脂であることが望ましい。このような樹脂としては、ポリビニルアルコール、カゼイン、ポリアクリル酸ナトリウム等の水溶性樹脂、共重合ナイロン、メトキシメチル化ナイロン等のアルコール可溶性樹脂、ポリウレタン、メラミン樹脂、フェノール樹脂、アルキッド−メラミン樹脂、エポキシ樹脂等、三次元網目構造を形成する硬化型樹脂等が挙げられる。また、下引き層にはモアレ防止、残留電位の低減等のために酸化チタン、シリカ、アルミナ、酸化ジルコニウム、酸化スズ、酸化インジウム等で例示できる金属酸化物の微粉末顔料を加えてもよい。
【０１１４】
これらの下引き層は、前述の感光層の如く適当な溶媒及び塗工法を用いて形成することができる。更に本発明の下引き層として、シランカップリング剤、チタンカップリング剤、クロムカップリング剤等を使用することもできる。この他、本発明の下引き層には、Ａｌ_２Ｏ_３を陽極酸化にて設けたものや、ポリパラキシリレン（パリレン）等の有機物やＳｉＯ_２、ＳｎＯ_２、ＴｉＯ_２、ＩＴＯ、ＣｅＯ_２等の無機物を真空薄膜作成法にて設けたものも良好に使用できる。このほかにも公知のものを用いることができる。下引き層の膜厚は０〜５μｍが適当である。
【０１１５】
本発明の感光体では、感光層保護の目的で、感光層（３３）の表面側に保護層（３９）を設けることができる。保護層（３９）は感光体の最表面側の層で高い耐摩耗性が要求されるため、無機フィラーを含有させることが有効であるが、この無機フィラーとして平均粒径０．０７〜０．３μｍで粒径分布の狭い三方晶系α−アルミナ微粒子を用いることにより、高耐久性を有し且つ繰り返し使用に対して画像流れを発生せず、更に解像度や階調性が高く、地肌汚れや画像濃度低下のない良好な画像が持続して得られる。
【０１１６】
この保護層に用いられるバインダー樹脂としては、ＡＢＳ樹脂、ＡＣＳ樹脂、オレフィン−ビニルモノマー共重合体、塩素化ポリエーテル、アリール樹脂、フェノール樹脂、ポリアセタール、ポリアミド、ポリアミドイミド、ポリアクリレート、ポリアリルスルホン、ポリブチレン、ポリブチレンテレフタレート、ポリカーボネート、ポリエーテルスルホン、ポリエチレン、ポリエチレンテレフタレート、ポリイミド、アクリル樹脂、ポリメチルベンテン、ポリプロピレン、ポリフェニレンオキシド、ポリスルホン、ポリスチレン、ポリアリレート、ＡＳ樹脂、ブタジエン−スチレン共重合体、ポリウレタン、ポリ塩化ビニル、ポリ塩化ビニリデン、エポキシ樹脂等の樹脂を併用することができる。
【０１１７】
この保護層（３９）に分散される無機フィラーとしては前述のものが使用可能でき、必要に応じて電荷輸送層（３７）について述べたと同様にポリカルボン酸化合物、可塑剤、レベリング剤等が添加される。また、これらの材料の添加量、無機フィラーの分散法、保護層（３９）の製造法としては、電荷輸送層（３７）について述べたと同様の事項が適用できる。なお、保護層（３９）の厚さは０．５〜５μｍ程度が適当である。
【０１１８】
本発明の感光体においては、感光層（３３）又は電荷輸送層（３７）と保護層（３９）との間に中間層を設けることも可能である。中間層には、一般にバインダー樹脂を主成分として用いる。これら樹脂としては、ポリアミド、アルコール可溶性ナイロン、水溶性ポリビニルブチラール、ポリビニルブチラール、ポリビニルアルコールなどが挙げられる。中間層の形成法としては、前述のごとく一般的な塗工法が採用できる。なお、中間層の厚さは０．０５〜２μｍ程度が適当である。
【０１１９】
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、電荷発生層、電荷輸送層、下引き層、保護層、中間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、下記のものが挙げられる。
【０１２０】
フェノール系化合物
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］クリコールエステル、トコフェロ−ル類など。
【０１２１】
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。
【０１２２】
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。
【０１２３】
有機硫黄化合物類
ジラウリル−３，３’−チオジプロピオネート、ジステアリル−３，３’−チオジプロピオネート、ジテトラデシル−３，３’−チオジプロピオネートなど。
【０１２４】
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。
【０１２５】
これら化合物は、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、市販品を容易に入手できる。
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。
【０１２６】
次に図面を用いて本発明の画像形成方法ならびに画像形成装置を詳しく説明する。
本発明の画像形成方法ならびに画像形成装置とは、本発明の最表面層が少なくとも無機フィラーとして平均粒径０．０７〜０．３μｍで粒径分布の狭い三方晶系α−アルミナ微粒子を含有する感光体を用い、例えば少なくとも感光体に帯電、画像露光、現像の過程を経た後、画像保持体（転写紙）へのトナー画像の転写、定着及び感光体表面のクリーニングというプロセスよりなる画像形成方法ならびに画像形成装置である。
場合により、静電潜像を直接転写体に転写し現像する画像形成方法等では、感光体に配した上記プロセスを必ずしも有するものではない。
【０１２７】
図６は、画像形成装置の一例を示す概略図である。感光体を平均的に帯電させる手段として、帯電チャージャ（３）が用いられる。この帯電手段としては、コロトロンデバイス、スコロトロンデバイス、固体放電素子、針電極デバイス、ローラー帯電デバイス、導電性ブラシデバイス等が用いられ、公知の方式が全て使用可能である。
【０１２８】
次に、均一に帯電された感光体上に静電潜像を形成するために画像露光部５が用いられる。この光源には、蛍光灯、タングステンランプ、ハロゲンランプ、水銀灯、ナトリウム灯、発光ダイオード（ＬＥＤ）、半導体レーザー（ＬＤ）、エレクトロルミネッセンス（ＥＬ）などの発光物全般を用いることができる。そして、所望の波長域の光のみを照射するために、シャープカットフィルター、バンドパスフィルター、近赤外カットフィルター、ダイクロイックフィルター、干渉フィルター、色温度変換フィルターなどの各種フィルターを用いることもできる。
【０１２９】
次に、感光体上に形成された静電潜像を可視化するために現像ユニット６が用いられる。現像方式としては、乾式トナーを用いた一成分現像法、二成分現像法、湿式トナーを用いた湿式現像法がある。感光体に正(負)帯電を施し、画像露光を行うと、感光体表面上には正(負)の静電潜像が形成される。これを負(正)極性のトナー（検電微粒子）で現像すれば、ポジ画像が得られるし、また正(負)極性のトナーで現像すれば、ネガ画像が得られる。
【０１３０】
次に、感光体上で可視化されたトナー像を転写体上に転写するために転写チャージャ（１０）が用いられる。また、転写をより良好に行なうために転写前チャージャ（７）を用いてもよい。これらの転写手段としては、転写チャージャ、バイアスローラーを用いる静電転写方式、粘着転写法、圧力転写法等の機械転写方式、磁気転写方式が利用可能である。静電転写方式としては、前記帯電手段が利用可能である。
【０１３１】
次に、転写体を感光体より分離する手段として分離チャージャ（１１）、分離爪（１２）が用いられる。その他分離手段としては、静電吸着誘導分離、側端ベルト分離、先端グリップ搬送、曲率分離、等が用いられる。分離チャージャとしては、前記帯電手段が利用可能である。
【０１３２】
次に、転写後感光体上に残されたトナーをクリーニングするためにファーブラシ（１４）、クリーニングブレード（１５）が用いられる。また、クリーニングをより効率的に行うためにクリーニング前チャージャ（１３）を用いてもよい。その他クリーニング手段としては、ウェブ方式、マグネットブラシ方式等があるが、それぞれ単独でまた複数の方式を併用してもよい。
【０１３３】
次に、必要に応じて感光体上の潜像を取り除く目的で除電手段が用いられる。除電手段としては除電ランプ（２）、除電チャージャが用いられ、それぞれ前記露光光源、帯電手段が利用できる。
【０１３４】
その他、感光体に近接していない原稿読み取り、給紙、定着、排紙等のプロセスは公知のものが全て使用できる。
本発明は、このような画像形成手段に本発明に係る電子写真感光体を用いる画像形成方法及び画像形成装置である。
【０１３５】
この画像形成手段は、複写装置、ファクシミリ、プリンター内に固定して組み込まれていてもよいが、プロセスユニットの形態でそれら装置内に組み込まれ、着脱自在としたものであってもよい。図７は、画像形成装置用プロセスユニットの１例を示す概略図である。
【０１３６】
画像形成装置用プロセスユニットとは、感光体を内蔵し、他に帯電手段、現像手段、転写手段、クリーニング手段、除電手段の少なくとも一つを一体化し、着脱可能とした装置（部品）である。本発明は、最表面層が少なくとも無機フィラーとして平均粒径０．０７〜０．３μｍで粒径分布の狭い三方晶系α−アルミナ微粒子を含有する感光体と帯電、現像、転写、クリーニング、除電手段の少なくとも一つを一体化した画像形成装置用プロセスユニットを提供するものである。
【０１３７】
【実施例】
次に、実施例によって本発明を更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、すべて重量部を表わす。
【０１３８】
［実施例１］
φ３０ｍｍのアルミニウムドラム上に、下記組成の下引き層用塗工液、電荷発生層用塗工液、電荷輸送層用塗工液を順次、塗布乾燥することにより、３．５μｍの下引き層、０．２μｍの電荷発生層、２２μｍの電荷輸送層を形成した。最表面層の無機フィラー含有層用塗工液は、下記無機フィラーと溶剤をアルミナボールを用いて２４時間ボールミル分散し、その分散液にバインダー樹脂と電荷輸送物質及び溶剤を加え調整した。この塗工液を電荷輸送層上にスプレー塗工、乾燥し無機フィラー含有の最表面層を３μｍ設け、本発明の電子写真感光体を得た。
【０１３９】
〔下引き層用塗工液〕

【０１４０】
〔電荷発生層用塗工液〕
下記構造のビスアゾ顔料 ２．５部
【０１４１】
【化３８】

ポリビニルブチラール（ＸＹＨＬ、ＵＣＣ製） ０．５部
シクロヘキサノン ２００部
メチルエチルケトン ８０部
【０１４２】
〔電荷輸送層用塗工液〕
ビスフェノールＺポリカーボネート
（パンライトＴＳ−２０５０、帝人化成製） １０部
下記構造の低分子電荷輸送物質（Ｄ−１） ７部
【０１４３】
【化３９】

テトラヒドロフラン １００部
１％シリコーンオイル（ＫＦ５０−１００ＣＳ、信越化学工業製）
テトラヒドロフラン溶液 １部
【０１４４】
〔無機フィラー含有層用塗工液〕

【０１４５】
［実施例２］
実施例１の無機フィラー含有層用塗工液の無機フィラーを三方晶系α−アルミナ微粒子（タイミクロンＴＭ−ＤＡＲ：大明化学工業製）２部に変えた以外は実施例１と同様に電子写真感光体を作製した。
【０１４６】
［実施例３］
実施例１の無機フィラー含有層用塗工液の無機フィラーを三方晶系α−アルミナ微粒子（タイミクロンＴＭ−ＤＡ：大明化学工業製）２部に変えた以外は実施例１と同様に電子写真感光体を作製した。
【０１４７】
［実施例４］
実施例１の無機フィラー含有層用塗工液の無機フィラーとして三方晶系α−アルミナ微粒子粒子（タイミクロンＴＭ−５Ｄ：大明化学工業製化学工業製）２部を用い、塗工液作製行程において無機フィラー分散時に分散剤としてポリカルボン酸化合物（ＢＹＫ−Ｐ１０４，ビックケミー製）０．０２部を含有させ、最表面層の膜厚を５μｍとした以外は実施例１と同様に電子写真感光体を作製した。
【０１４８】
［実施例５］
実施例１の無機フィラー含有層用塗工液の無機フィラーとして三方晶系α−アルミナ微粒子（タイミクロンＴＭ−ＤＡＲ：大明化学工業製）２部を用い、また塗工液作製行程において無機フィラー分散時に分散剤としてポリカルボン酸化合物（ＢＹＫ−Ｐ１０４，ビックケミー製）０．０２部を含有させ、最表面層の膜厚を５μｍとした以外は実施例１と同様に電子写真感光体を作製した。
【０１４９】
［実施例６］
実施例１の無機フィラー含有層用塗工液の無機フィラーとして三方晶系α−アルミナ微粒子（タイミクロンＴＭ−ＤＡ：大明化学工業製）２部を用い、また塗工液作製行程において無機フィラー分散時に分散剤としてポリカルボン酸化合物（ＢＹＫ−Ｐ１０４，ビックケミー製）０．０２部を含有させ、最表面層の膜厚を５μｍとした以外は実施例１と同様に電子写真感光体を作製した。
【０１５０】
［実施例７］
実施例４のバインダー樹脂をポリカーボネート（パンライト Ｃ−１４００，帝人化成製）４部に変えた以外は実施例４と同様に電子写真感光体を作製した。
【０１５１】
［実施例８］
実施例４のバインダー樹脂を下記構造の高分子電荷輸送物質（ＰＤ−１）７部に変え、低分子電荷輸送物質を添加しないこと以外は実施例４と同様に電子写真感光体を作製した。
【０１５２】
【化４０】

ｋ＝０．４０、ｊ＝０．６０、Ｍｗ＝１３５０００（ポリスチレン換算）
【０１５３】
［比較例１］
実施例１の無機フィラー含有層用塗工液の無機フィラーをルチル型−酸化チタン粉末（ＣＲ−ＥＬ：石原産業製）２部を用い、また塗工液作製行程において無機フィラー分散時に分散剤としてポリカルボン酸化合物（ＢＹＫ−Ｐ１０４，ビックケミー製）０．０２部を含有させ、最表面層の膜厚を３μｍとした以外は実施例１と同様に電子写真感光体を作製した。
【０１５４】
［比較例２］
実施例１の無機フィラー含有層用塗工液の無機フィラーを球形シリカ粒子（ＫＥ−Ｐ３０：日本触媒製）１．５部に変えた以外は実施例１と同様に電子写真感光体を作製した。
【０１５５】
［比較例３］
実施例１の無機フィラー含有層用塗工液の無機フィラーを六方稠密格子α−アルミナ粒子（ＡＡ−２：住友化学工業製）２部に変えた以外は実施例１と同様に電子写真感光体を作製した。
【０１５６】
［比較例４］
実施例１の無機フィラー含有層用塗工液の無機フィラーをアルミナ超微粒子（Aluminium Oxide C：日本アエロジル製）２部に変えた以外は実施例１と同様に電子写真感光体を作製した。
【０１５７】
［比較例５］
実施例１の無機フィラー含有層用塗工液の無機フィラーをα−アルミナ粉末（ＡＫＰ−３０：住友化学工業製）２部を用い、また塗工液作製行程において無機フィラー分散時に分散剤としてポリカルボン酸化合物（ＢＹＫ−Ｐ１０４，ビックケミー製）０．０２部を含有させ、最表面層の膜厚を５μｍとした以外は実施例１と同様に電子写真感光体を作製した。
【０１５８】
［比較例６］
実施例１の無機フィラー含有層用塗工液の無機フィラーをα−アルミナ粉末（ＡＬ−Ｍ４１：住友化学工業製）２部に変えた以外は実施例１と同様に電子写真感光体を作製した。
【０１５９】
［比較例７］
実施例１の無機フィラー含有層用塗工液の無機フィラーをα−アルミナ粉末（ＡＭＳ−１２：住友化学工業製）２部に変えた以外は実施例１と同様に電子写真感光体を作製した。
【０１６０】
［比較例８］
実施例１の無機フィラー含有層用塗工液の無機フィラーをθ−アルミナ粉末（ＴＭ−１００Ｄ：大明化学工業製）２部に変えた以外は実施例１と同様に電子写真感光体を作製した。
【０１６１】
［比較例９］
実施例１の無機フィラー含有層用塗工液の無機フィラーをγ−アルミナ粉末（ＴＭ−３００Ｄ：大明化学工業製ＡＭＳ−１２：住友化学工業製）２部に変えた以外は実施例１と同様に電子写真感光体を作製した。
【０１６２】
［比較例１０］
実施例１の無機フィラー含有最表層を設けない以外は実施例１と同様に電子写真感光体を作製した。
【０１６３】
【表１】

【０１６４】
実施例のα−アルミナ粒子は、ＡＳＴＭ Ｘ−ｒａｙ Ｐｏｗｄｅｒ Ｄａｔｅ Ｆｉｌｅ ＮＯ．１０−１７３から結晶形が三方晶系である。また、電界放出型走査線電子顕微鏡ＦＥ−ＳＥＭ（日立製作所製：Ｓ−４２００）による観察から粒子の２軸平均径を測定した結果、０．０７〜０．３μｍのα−アルミナ微粒子であり、個数基準粒径分布が狭く、微粒側からの累積１０％、累積９０％の粒径をそれぞれＤａ、ＤｂとしたときにＤｂ／Ｄａの値が４以下、且つ粒径１μｍ以上の粒子を実質的に含まず、バイヤー法、水熱合成アルミナ等の粉砕粉体と比較して非常に粒径が揃っている。また、本発明に用いられる三方晶系α−アルミナは１次粒子の凝集性が弱く単粒子化しており、これを示す値としてガス吸着量から算出するＢＥＴ比表面積が粒径としては８〜２０ｍ^２／ｇと大きい。更に、この三方晶系α−アルミナ粒子は、発光分析による不純物イオンの定量によりナトリウム含有量が１０ｐｐｍ以下と少なく、不純物量を全体から除いて９９．９９以上の高純度である。
【０１６５】
以上のように作製した実施例１〜８、比較例１〜１０の電子写真感光体を、電子写真装置用プロセスユニットに装着し、画像露光光源を ６５５ｎｍの半導体レーザーに改造したリコー製ｉｍａｇｉｏＭＦ２２００を用いて、画像評価を行った。まず、温度２５゜C、湿度５５％の環境下で初期画像をとり、その後帯電負荷の加速試験として５ｐｐｍのオゾンガス雰囲気下に１０時間放置した後初期と同じ環境にもどし画像変化を確認した。その後、更に３万枚の複写を行い複写終了後の感光体の摩耗量と画像変化を調べた。その結果を表２に示す。
【０１６６】
【表２】

【０１６７】
表２の評価結果より、耐摩耗性の向上を狙い最表面層に無機フィラーを分散させた感光体において、実施例１〜８に示されるように、無機フィラーとして平均粒径０．０７〜０．３μｍで粒径分布の狭い三方晶系α−アルミナ微粒子を用いることにより、比較例１〜９の別のフィラーを用いた場合に比べ、画像流れや地肌汚れが発生せず、階調性と解像度が共に高く且つ画像濃度の低下のない良好な画像が持続して得られることがわかる。また、比較例１０の無機フィラー含有した表面層を用いなかった場合に比べ、耐摩耗性が高く、長寿命の感光体が達成されていることが分かる。
したがって、本発明の最表面層に無機フィラーとして平均粒径０．０７〜０．３μｍで粒径分布の狭い三方晶系α−アルミナ微粒子を用いることにより、高耐久性を有し、繰り返し使用に対しても良好な画像が持続して得られる高性能で信頼性の高い電子写真感光体を提供できることが判明した。また合わせて、本発明の電子写真感光体を用いた画像形成方法、画像形成装置及び画像形成装置用プロセスユニットが高性能、高信頼性を有していることが判明した。
【０１６８】
【発明の効果】
以上、詳細かつ具体的なせつめいより明らかなように、本発明によれば、最表面層に少なくとも無機フィラーとバインダー樹脂とを含有する電子写真感光体において、この無機フィラーとして平均粒径０．０７〜０．３μｍで粒径分布の狭い三方晶系α−アルミナ微粒子を用いることにより、耐摩耗性が高く且つ高画質が持続できる高耐久、高性能で且つ信頼性の高い電子写真感光体を提供できる。また、本発明の電子写真感光体を用いることにより、高性能、高信頼性の画像形成方法、画像形成装置及び画像形成装置用プロセスユニットが提供できる。
【図面の簡単な説明】
【図１】本発明の感光体の一例を示す断面図である。
【図２】本発明の感光体の他の一例を示す断面図である。
【図３】本発明の感光体の他の一例を示す断面図である。
【図４】本発明の感光体の他の一例を示す断面図である。
【図５】本発明の感光体の他の一例を示す断面図である。
【図６】本発明の画像形成装置の一例を示す概略図である。
【図７】本発明の画像形成装置用プロセスユニットの一例を示す概略図である。
【符号の説明】
１ 感光体
２ 除電ランプ
３ 帯電チャージャ
４ イレーサ
５ 画像露光部
６ 現像ユニット
７ 転写前チャージャ
８ レジストローラ
９ 転写紙
１０ 転写チャージャ
１１ 分離チャージャ
１２ 分離爪
１３ クリーニング前チャージャ
１４ ファーブラシ
１５ クリーニングブレード
３１ 導電性支持体
３３ 感光層
３５ 電荷発生層
３７ 電荷輸送層
３９ 保護層
１０１ 感光ドラム
１０２ 帯電装置
１０３ 露光
１０４ 現像装置
１０５ 転写体
１０６ 転写装置
１０７ クリーニングブレード[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member having high durability and realizing high image quality over a long period of time. In addition, the present invention relates to an image forming method, an image forming apparatus, and a process unit for the image forming apparatus using these photosensitive members.
[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 an image holding member (transfer paper) after at least charging, image exposure, and development of the electrophotographic photosensitive member. ) To transfer the toner image to the toner, and fixing the toner image and cleaning the surface of the electrophotographic photosensitive member.
The basic characteristics required for the electrophotographic photosensitive member are as follows: (1) The electrophotographic photosensitive member can be charged to an appropriate potential in the dark.
(2) Less charge dissipation in the dark,
(3) The ability to quickly dissipate charges by light irradiation,
Etc.
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]
Organic electrophotographic photoreceptors include photoconductive resins typified by polyvinylcarbazole (PVK), charge transfer complex types typified by PVK-TNF (2,4,7-trinitrofluorenone), and phthalocyanines. -Pigment dispersion type typified by binder, function separation type photoreceptor using a combination of charge generation material and charge transport material, etc. are known, especially function separation type photoreceptors are sensitive, durable and stable. It is attracting attention because of its excellent properties in various properties.
[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. It is known that a function-separated type photoreceptor uses a combination of a charge transport material having absorption mainly in the ultraviolet region and high mobility, and a charge generation material having absorption mainly in the visible region and high quantum efficiency. It is useful.
[0006]
However, many charge transport materials for organic electrophotographic photoreceptors used in electrophotographic methods have been developed as low molecular weight compounds, and low molecular weight 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 when repeatedly used in an electrophotographic process, the film may be scraped due to a mechanical load on the surface of the photoreceptor by a development system or a cleaning system. The disadvantage is low wear resistance, which is likely to occur. Actually, the film removal of the photoconductor may cause adverse effects such as deterioration of sensitivity and reduction of chargeability, and an abnormal image such as a decrease in image density and background stain may occur, resulting in the life of the photoconductor.
[0007]
2. Description of the Related Art In recent years, the diameter of a photoconductor has been reduced due to downsizing of an image forming apparatus, and high durability of the photoconductor has been eagerly desired due to the increase in machine speed and maintenance-free movement. In order to increase the durability of the photoreceptor, it is a first problem to improve the above-mentioned wear resistance. This technique includes (1) using a curable binder for the surface layer (described in JP-A-56-48637), and (2) improving the binder resin of the photoconductor (JP-A-5-216250). 3) using a polymer type charge transport material (described in JP-A No. 64-1728), 4) an inorganic filler dispersed in a surface layer (JP-A 4-281461) As described in the publication No.).
[0008]
Among these technologies, the one using the curable binder (1) has a poor compatibility with the charge transport material, and the exposed area potential increases due to impurities such as a polymerization initiator and an unreacted residue. A decrease occurs. In addition, the improved binder resin (2) does not exhibit a significant improvement in wear resistance due to the composition ratio of the low molecular charge transport material. In addition, those using the polymer type charge transport material of (3) can improve the abrasion resistance to some extent, but the durability is not sufficient, and it is difficult to polymerize and purify the material and has high purity. Are difficult to obtain, and there are problems in production such as high viscosity of the coating liquid. On the other hand, the dispersion of the inorganic filler of (4) exhibits higher wear resistance and repeatable electrical characteristics compared to a photoreceptor in which a normal low molecular charge transport material is dispersed in an inert polymer. Good and attracts attention.
[0009]
However, the photoreceptor in which the inorganic filler is dispersed in the surface layer also has some problems. For example, there is a drawback that an image flow is generated in repeated use.
The cause of this is that the inorganic filler becomes an adsorption site for the oxidizing gas such as ozone and NOx generated from the charger by dispersing the inorganic filler. As a result of the improvement in wear resistance, the renewal of the surface of the photoreceptor due to wear could not catch up, and filming of toner and paper powder occurred, and this was caused by the adsorption of the oxidizing gas. This image flow occurs vigorously when acidic inorganic silica or low-resistance tin oxide is used as the inorganic filler, and conversely when basic titanium oxide or high-resistance alumina is used. It is.
[0010]
As countermeasures against image flow, hydrophobicity of the surface of the inorganic filler (described in JP-A-60-57346 and JP-A-7-261417) and combined use of an antioxidant (described in JP-A-8-292585). ) Has been studied, but sufficient effects have not been obtained. On the other hand, when titanium oxide or alumina is used as the inorganic filler, on the contrary to the image flow, the exposed portion potential becomes high, and an abnormal image such as insufficient image density or background stain occurs. This is due to the charge trapping on the filler surface due to the aforementioned titanium oxide or alumina material. For this reason, when silica or tin oxide (described in JP-A-57-30846) is used, the exposed portion potential does not increase significantly.
[0011]
Another disadvantage is that the addition of an inorganic filler to the surface layer reduces the straightness of light at the time of exposure, resulting in a decrease in image resolution and gradation. This phenomenon is remarkable when an inorganic filler having high whiteness, for example, titanium oxide (described in JP-A No. 61-251860), alumina or the like is used. For this, it is effective to make the primary particle size of the inorganic filler fine, but if the particle size of the filler becomes too small, the desired wear resistance is not exhibited, the cohesive force increases, and dispersion is difficult. Another problem occurs.
[0012]
Further, the shape of the filler used (described in JP-A-62-250460), the particle size distribution (described in JP-A-59-223445), and the aggregation state in the film (JP-A-59-223443). The problem caused by the
For example, a method using a pulverization method as a method for producing fine particles has a sharp crushing shape, and therefore, the cleaning blade may be cut off by protrusions on the surface of the photoreceptor due to the filler, and streaky cleaning defects may occur. In addition, if a filler containing a large amount of fine powder is used, uneven wear due to the difference in particle size occurs, and abnormal images of density reduction and background stains may occur due to variations in sensitivity and chargeability. Aggregation of filler also causes blade breakage and wear unevenness.
[0013]
Some of these shortcomings in photoreceptors with dispersed inorganic fillers are caused by the inorganic filler material used, but no good inorganic filler that satisfies all the problems has been found. It is.
[0014]
[Problems to be solved by the invention]
An object of the present invention is to provide a high-performance and highly reliable electrophotographic photosensitive member having high durability and capable of continuously obtaining a good image even after repeated use. Another object of the present invention is to provide a highly reliable image forming method, an image forming apparatus, and a process unit for an image forming apparatus that are small and capable of high-speed printing by using the electrophotographic photosensitive member.
[0015]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that the outermost surface layer of the electrophotographic photoreceptor contains at least an inorganic filler and a binder resin, and the inorganic filler has an average particle size of 0.07 to 0.3 μm and a particle size of It has been found that the above object can be achieved by using trigonal α-alumina fine particles having a narrow distribution, and the present invention has been achieved.
[0016]
  That is, the above-mentioned problem is (1) “in an electrophotographic photosensitive member in which at least a photosensitive layer is provided on a conductive support, and the outermost surface layer of the electrophotographic photosensitive member contains at least an inorganic filler and a binder resin. The electrophotographic photosensitive member characterized in that the inorganic filler is trigonal α-alumina ”, (2)“ the α-alumina particles are made of aluminum ammonium carbonate hydroxide [NH₄AlCO₃(OH)₂The electrophotographic photosensitive member according to item (1), wherein the electrophotographic photosensitive member is produced by thermally decomposing](3)“The electrophotographic photosensitive member according to item (1), wherein the α-alumina particles have a sodium content of 20 ppm or less as an impurity”,(4)“The electrophotographic photosensitive member according to (1) above, wherein the α-alumina particles have a purity of 99.99% by weight or more”,(5)“The outermost surface layer contains a polycarboxylic acid compound,” the items (1) to (2) are characterized in that:(4)The electrophotographic photosensitive member according to any one of Items(6)“The binder resin contained in the outermost surface layer is a polymer charge transporting substance,” the items (1) to (2),(4)The electrophotographic photosensitive member according to any one of Items(7)"The binder resin contained in the outermost surface layer is a polycarbonate having a triarylamine structure in the main chain or in the side chain"(4)The electrophotographic photosensitive member according to any one of Items(8)“The outermost surface layer containing at least an inorganic filler and a binder resin is a surface portion of a charge transport layer, wherein the first to third items are characterized in that:(4)The electrophotographic photosensitive member according to any one of the items is achieved.
[0017]
  In addition, the above problem is(9)“An image forming method comprising forming an image on the electrophotographic photosensitive member according to any one of (1) to (8) by repeating at least charging, exposure, development, and transfer”. Achieved.
[0018]
  In addition, the above problem is(10)“An image forming apparatus comprising a charging unit, an exposure unit, a developing unit, and a transfer unit in addition to the electrophotographic photosensitive member according to any one of items (1) to (8)”. Achieved.
[0019]
  In addition, the above problem(11)“At least one selected from the group consisting of a charging means, a developing means, a transferring means, a cleaning means, and a static eliminating means in addition to the electrophotographic photosensitive member according to any one of the above items (1) to (8). This is achieved by an image forming apparatus process unit characterized in that two means are integrated and detachable.
[0020]
Hereinafter, the present invention will be described in detail.
As in the present invention, in the electrophotographic photosensitive member in which the outermost surface layer contains at least an inorganic filler and a binder resin, a trigonal system having an average particle size of 0.07 to 0.3 μm and a narrow particle size distribution as the inorganic filler. By using α-alumina fine particles, for whatever reason, it has high durability, does not generate image flow with repeated use, has higher resolution and gradation, and reduces background stains and image density. Although it has not been clarified at present whether the effect that a good image can be obtained continuously is obtained, the following reasons are conceivable.
[0021]
It is already well known that an electrophotographic photosensitive member containing an inorganic filler in the outermost surface layer of the structure of the present invention has a very high wear resistance, and problems of the photosensitive member having an inorganic filler in the outermost surface layer are as follows. On the other hand, the reason why the photoreceptor of the present invention is particularly effective will be described.
[0022]
The electrophotographic photosensitive member of the present invention suppresses the occurrence of image flow in repeated use. The reason for this is that the inorganic filler contained in the outermost surface layer uses basic and high-resistance trigonal α-alumina, which is different from silica having acidic properties and low-resistance tin oxide. For this image flow, not only the filler material but also the surface area of the particles is greatly influenced by the adsorption action of the oxidizing gas. As the trigonal α-alumina used in the present invention, aluminum ammonium carbonate hydroxide [NH₄AlCO₃(OH)₂It is produced by low-temperature firing at around 1200 ° C., and thus has a feature that the particle size distribution is narrow and the proportion of fine powder is very small.
[0023]
In addition, the electrophotographic photoreceptor of the present invention has a slight increase in the exposed area potential seen in a photoreceptor in which a basic filler or a high resistance filler is contained in the outermost surface layer. The reason for this is that the trigonal α-alumina of the present invention does not contain fine powder, so that the surface area affecting the charge trapping is small, and the sodium content causing an increase in potential as an impurity is 20 ppm or less. It is related to high purity of 99% by weight or more. Furthermore, since the α-alumina of the present invention has a low cohesive force due to the above-mentioned production method and is made into single particles, high energy is not required for pulverization and dispersion, and the amount of impurities mixed at this time can be reduced. As a value representing this single particle formation, the BET specific surface area calculated from the gas adsorption amount is 8 to 20 m as the particle diameter.²/ G is large. For example, when the particles are aggregated, the amount of gas adsorption corresponding to the surface area decreases, and the value of the BET specific surface area becomes small.
[0024]
Further, the electrophotographic photoreceptor of the present invention shows almost no reduction in image resolution or gradation that occurs when a filler with high whiteness such as titanium oxide or alumina is used as the outermost surface layer. A photoconductor containing an inorganic filler in the outermost surface layer is different from a normal photoconductor, and incident light is reflected on the filler surface, absorbed and scattered inside the filler, and the above-mentioned problem occurs. Of these, the reason for the greatest influence is reflection, which is determined by the choice of filler material because it is a relative one that is determined by the difference in refractive index inherent to the medium through which light propagates and enters and the filler material. The refractive index of the photoreceptor is approximately 1.6, the refractive index of the inorganic filler is 1.76 for alumina, 1.55 for silica, and 2.71 for titanium oxide, and the influence of reflection is a problem with silica due to the difference in refractive index. However, it is difficult to avoid the deterioration of the image with titanium oxide. In alumina, the influence of reflection appears as the amount added increases, but it can be suppressed by reducing the particle size. However, α-alumina produced by the buyer method, organoaluminum hydrolysis method, ammonium alum pyrolysis method, ethylene chlorohydrin method, underwater flame method, and vapor phase transfer growth method has a particle size of 0.3 μm or more. In addition, the powder using high energy pulverization contains coarse particles having a particle size of 1 μm or more, and has high reflection. In contrast, the aluminum ammonium carbonate hydroxide [NH₄AlCO₃(OH)₂The α-alumina produced by thermal decomposition of] has a small particle size of 0.07 to 0.3 μm, a narrow particle size distribution, and low reflection in that it does not contain coarse particles of 1 μm or more. Next, as an effect other than reflection, there is absorption inside the filler, but it may be substantially zero in the case of polycrystalline alumina, and only the influence of scattering. The α-alumina of the present invention is composed of a homogeneous trigonal system up to the inside of the particle, does not have pores inside, and is less affected by scattering inside the filler. For these reasons, it is considered that the use of the α-alumina of the present invention can prevent a decrease in resolution and gradation.
[0025]
In addition, a photoconductor using an inorganic filler as the outermost surface layer often causes mechanical problems due to the shape of the filler, the particle size distribution, and the aggregation state in the film. The trigonal α-alumina of the present invention has a polyhedral shape and does not require high energy for dispersion, and therefore does not have a sharp crushing surface. Further, the dispersibility in the coating solution is also good, and the coating film is uniformly dispersed without significant aggregation. For this reason, a black streak-like defect image due to damage to the cleaning blade does not occur. The α-alumina produced by this production method has an average particle size of 0.07 to 0.3 μm, a small amount of fine powder, does not contain coarse particles of 1 μm or more, and has a narrow particle size distribution. Thus, since the dispersion in the film is also good, it has high wear resistance and no wear unevenness occurs.
[0026]
Hereinafter, the structure of the electrophotographic photosensitive member used in the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view showing an example of the electrophotographic photosensitive member of the present invention. A photosensitive layer (33) mainly composed of a charge generating material and a binder resin is provided on a conductive support (31). ing. 1A shows the case where the outermost surface layer containing the inorganic filler is the entire photosensitive layer, and FIG. 1B shows the case where the outermost surface layer containing the inorganic filler is the surface portion of the photosensitive layer. Is shown.
[0027]
FIG. 2 is a cross-sectional view showing another example of the electrophotographic photosensitive member of the present invention. On the conductive support (31), a charge generation layer (35) mainly composed of a charge generation material, and charge transport. It has a structure in which a charge transport layer (37) containing a substance as a main component is laminated. FIG. 2-A shows the case where the outermost surface layer containing the inorganic filler is the entire charge transport layer, and FIG. 2-B shows the outermost surface layer containing the inorganic filler being the surface portion of the charge transport layer. Some cases are shown.
[0028]
FIG. 3 is a sectional view showing another example of the electrophotographic photosensitive member of the present invention. A photosensitive layer (33) mainly composed of a charge generating material and a binder resin is formed on a conductive support (31). The protective layer (39) is further provided on the surface of the photosensitive layer. In this case, the outermost surface layer containing the inorganic filler is the protective layer (39).
[0029]
FIG. 4 is a sectional view showing another example of the electrophotographic photosensitive member of the present invention. On the conductive support (31), a charge generation layer (35) mainly composed of a charge generation material and a charge transport material. The charge transporting layer (37) containing as a main component is laminated, and a protective layer (39) is provided on the charge transporting layer (37). In this case, the outermost surface layer containing the inorganic filler is the protective layer (39).
[0030]
FIG. 5 is a cross-sectional view showing another example of the electrophotographic photosensitive member of the present invention. On the conductive support (31), a charge transport layer (37) mainly composed of a charge transport material and a charge generation material. The charge generation layer (35) containing as a main component is laminated, and a protective layer (39) is further provided on the charge generation layer (35). In this case, the outermost surface layer containing the inorganic filler is the protective layer (39).
[0031]
Hereinafter, the conductive support of the present invention will be described.
The conductive support (31) has a volume resistance of 10¹⁰Films 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. -Like or cylindrical plastic, paper-coated, or aluminum, aluminum alloy, nickel, stainless steel, etc., and the surface after cutting, superfinishing, polishing, etc. A treated tube or the like can be used. Further, an endless nickel belt and an endless stainless steel belt disclosed in Japanese Patent Application Laid-Open No. 52-36016 can be used as the conductive support (31).
[0032]
In addition, the conductive support dispersed in a suitable binder resin and coated on the support can also be used as the conductive support (31) of the present invention.
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 is 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, Examples thereof include thermoplastic, thermosetting resins, and photocurable resins such as melamine resin, urethane resin, phenol resin, and alkyd resin. Such a conductive layer can be provided by dispersing and coating these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, toluene, and the like.
[0033]
Further, a heat shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, polytetrafluoroethylene-based fluororesin on a suitable cylindrical substrate. Those provided with a conductive layer can be used favorably as the conductive support (31) of the present invention.
[0034]
Next, the photosensitive layer will be described.
The photosensitive layer may have a laminated structure or a single layer structure.
In the case of a laminated structure, the photosensitive layer is composed of a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material. In the case of a single layer structure, the photosensitive layer is composed of a layer containing at least a charge generating substance.
Hereinafter, each of the photosensitive layer having a laminated structure and the photosensitive layer having a single layer structure will be described.
[0035]
<When the photosensitive layer consists of multiple layers>
The charge generation layer (35) is a layer mainly composed of a charge generation material, and a binder resin can be used in combination as required. As the charge generation material, inorganic materials and organic materials can be used.
Inorganic materials include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, and amorphous silicon. In amorphous silicon, dangling bonds that are terminated with hydrogen atoms or halogen atoms, or those that are doped with boron atoms, phosphorus atoms, or the like are preferably used.
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 a carbazole skeleton, azo pigments having a triphenylamine skeleton, azo pigments having a 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, Goido based pigments, and bisbenzimidazole pigments. These charge generation materials can be used alone or as a mixture of two or more.
[0036]
The binder resin used as necessary for the charge generation layer (35) includes polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, Poly-N-vinylcarbazole, polyacrylamide and the like can be mentioned. These binder resins can be used alone or as a mixture of two or more. In addition to the binder resin described above as a binder resin for the charge generation layer, a polymer charge transport material (for example, JP-A 64-1728, JP-A 64-13061, JP-A 64-19049). No. 4, JP-A-4-11627, JP-A-4-225014, JP-A-4-230767, JP-A-4-320420, JP-A-5-232727, JP-A-6-234838. JP-A-6-234839, JP-A-6-295077, JP-A-7-56374, JP-A-7-325409, JP-A-9-80772, JP-A-9-80783, Japanese Unexamined Patent Publication Nos. 9-80784, 9-127713, 9-2111877, 9-222740, 9-26519 JP, Hei 9-265201 and JP-described in JP-A-9-297419, JP-A No. 9-304956 Patent Publication) can be used. Among these polymer charge transport materials, polycarbonate having a triarylamine structure in the main chain and / or side chain is effective. The amount of the binder resin used in the charge generation layer (35) is 0 to 500 parts by weight, preferably 0 to 200 parts by weight, with respect to 100 parts by weight of the charge generation material. Furthermore, you may add a low molecular charge transport material as needed.
[0037]
Low molecular charge transport materials that can be used in combination with the charge generation layer (35) include hole transport materials and electron transport materials.
Examples of the electron transporting material include chloroanil, bromanyl, 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 diphenoquinone derivatives. These electron transport materials can be used alone or as a mixture of two or more.
[0038]
Examples of the hole transporting material include the electron donating materials shown below and are used favorably. As hole transport materials, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triaryls Other known materials such as methane derivatives, 9-styrylanthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives, and the like can be given. These hole transport materials can be used alone or as a mixture of two or more. The amount of the low molecular charge transport material used in the charge generation layer (35) is 0 to 500 parts by weight, preferably 0 to 300 parts by weight, per 100 parts by weight of the charge generation material.
[0039]
Methods for forming the charge generation layer (35) include a vacuum thin film preparation method and a casting method from a solution dispersion system.
As the former method, a vacuum deposition method, a glow discharge decomposition method, an ion plating method, a sputtering method, a reactive sputtering method, a CVD method, or the like is used, and the above-described inorganic materials and organic materials can be satisfactorily formed.
[0040]
In addition, in order to provide the charge generation layer by the latter casting method, the inorganic or organic charge generation material described above together with a binder resin, if necessary, tetrahydrofuran, dioxane, dioxolane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, cyclohexane. Can be formed by dispersing with a ball mill, attritor, sand mill, bead mill, etc. using a solvent such as pentanone, anisole, xylene, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, etc. . Moreover, leveling agents, such as a dimethyl silicone oil and a methylphenyl silicone oil, can be added as needed. The coating can be performed using a dip coating method, spray coating, bead coating, ring coating method or the like.
The thickness of the charge generation layer provided as described above is suitably about 0.01 to 5 μm, preferably 0.05 to 2 μm.
[0041]
The charge transport layer (37) can be formed by dissolving or dispersing a charge transport material and a binder resin in an appropriate solvent, and applying and drying the solution on the charge generation layer (35).
As the charge transport material, the electron transport material, hole transport material and polymer charge transport material described in the charge generation layer (35) can be used.
[0042]
As binder resin, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene 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-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, alkyd resin, etc. Or a thermosetting resin is mentioned.
[0043]
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. However, when a polymer charge transport material is used, it can be used alone or in combination with a binder resin.
[0044]
As the solvent used for the coating of the charge transport layer (37), the same solvent as that 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 (37) can be formed by the same coating method as the charge generation layer (35).
[0045]
If necessary, a plasticizer and a leveling agent can be added.
As a plasticizer that can be used in combination with the charge transport layer (37), those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is based on 100 parts by weight of the binder resin. About 0 to 30 parts by weight is appropriate.
Examples of the leveling agent that can be used in the charge transport layer (37) include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain. About 0 to 1 part by weight is appropriate for 100 parts by weight of the binder resin.
[0046]
The film thickness of the charge transport layer (37) is suitably about 5 to 50 μm, and preferably about 10 to 40 μm in terms of image characteristics such as resolution and background stains and electric characteristics such as charging potential and sensitivity.
[0047]
Further, when the charge transport layer (37) is a surface layer of the photoreceptor, an inorganic filler is contained in the entire layer or surface portion of the charge transport layer (37) for the purpose of improving wear resistance. By using trigonal α-alumina fine particles having an average particle size of 0.07 to 0.3 μm and a narrow particle size distribution as this inorganic filler, it has high durability and does not generate an image flow for repeated use. In addition, it is possible to continuously obtain a good image having high resolution and gradation and free from background stains and image density reduction.
[0048]
Examples of the trigonal α-alumina fine particles of the present invention include those described in JP-A-61-201619, JP-B-6-17224, and Japanese Patent No. 2983042. Oxide [NH₄AlCO₃(OH)₂] And is manufactured satisfactorily by a manufacturing method in which this is fired at a low temperature around 1200 ° C. The α-alumina particles of the present invention thus produced are trigonal (ASTM X-ray Powder Date File NO. 10-173), and a field emission scanning electron microscope FE-SEM (manufactured by Hitachi, Ltd.). : As a result of measuring the biaxial average diameter of the particles from observation by S-4200), it has a fine polyhedral shape of 0.07 to 0.3 μm.
[0049]
Further, this trigonal α-alumina has a narrow number-based particle size distribution from FE-SEM observation, and when the cumulative particle size of 10% and 90% from the fine particle side is Da and Db, Db / Da Particles having a value of 4 or less and a particle diameter of 1 μm or more are substantially not included, and the particle diameter is very uniform as compared with the pulverized powder of the Bayer method and hydrothermal synthetic alumina.
[0050]
These polyhedral trigonal α-alumina particles having an average particle size and particle size distribution are optimal for use in the outermost layer of the photoreceptor. Further, as a feature of the trigonal α-alumina used in the present invention, the primary particles are weakly agglomerated and are made into single particles, and the BET specific surface area calculated from the gas adsorption amount as a value indicating this is as the particle size. 8-20m²/ G is large. For this reason, there is an advantage that a high energy pulverization method is not required for dispersion, there is little distribution of fine powder, there is no sharp crushing surface as a particle shape, and there is little mixing of impurities due to dispersion. Furthermore, the α-alumina particles of the present invention have a sodium content as low as 10 ppm or less by quantification of impurity ions by emission analysis, and have a high purity of 99.99% by weight or more excluding the amount of impurities from the whole. Therefore, in the photoreceptor in which the trigonal α-alumina of the present invention is contained in the outermost layer, an increase in the exposed portion potential due to repeated use can be suppressed.
[0051]
As the inorganic filler of the present invention, in addition to the trigonal α-alumina particles, if necessary, metal powder such as copper, tin, aluminum, indium, silica, tin oxide, zinc oxide, titanium oxide, other crystal forms Metal oxides such as alumina, zirconium oxide, indium oxide, antimony oxide, bismuth oxide, calcium oxide, antimony-doped tin oxide, tin-doped indium oxide, metals such as tin fluoride, calcium fluoride, aluminum fluoride Particles such as fluoride, potassium titanate, and boron nitride may be used in combination. In addition, it is possible to perform surface treatment for the purpose of improving dispersibility of these inorganic fillers. As the surface treatment agent used at this time, titanate coupling agents, aluminum coupling agents, zircoaluminate cups are used. Ring agent, higher fatty acid, silane coupling agent, Al₂O₃TiO₂, ZrO₂, Silicone, aluminum stearate, or a mixed treatment thereof.
[0052]
The proportion of the inorganic filler contained in the outermost surface layer depends on various factors such as the intended wear resistance, the particle size of the inorganic filler, the material, and the image forming process used, but the inorganic filler is dispersed. It is 0.5 to 50% by weight, preferably 2 to 40% by weight, based on the total amount of the surface portion.
[0053]
The surface portion containing the inorganic filler is prepared by, for example, combining an inorganic filler with an organic solvent and dispersing it using a conventional method such as a ball mill, attritor, sand mill, bead mill, or ultrasonic wave, and then adding a binder resin and coating. It is done. When the surface layer containing the inorganic filler is the entire layer of the charge transport layer (37), it is directly coated on the charge generation layer (35), and when the surface layer of the charge transport layer (37) is on the charge transport layer. Painted on. As the coating method used at this time, the coating method described in the charge generation layer (35) can be used.
[0054]
In this coating liquid, additives such as a dispersant such as a polycarboxylic acid compound, a charge transport material, a leveling agent, and a plasticizer are used as necessary. These binder resins and additives may be added before, during and after the inorganic filler dispersion treatment. The organic solvent used in this coating solution depends on the dispersibility of the inorganic filler, the coating method, and the like, but generally those described in the charge generation layer (35) can be used, and two or more types can be used. A solvent may be mixed.
[0055]
As the materials such as the binder resin and the charge transport material used for the outermost surface portion in which the inorganic filler is dispersed, those mentioned in the charge transport layer (37) can be used, but the inorganic filler is applied only to the surface portion of the charge transport layer. When contained, the type and composition of the lower layer charge transporting portion not containing the inorganic filler and the material used can be changed as necessary.
[0056]
Further, as the binder resin used together with the inorganic filler, the polymer charge transport material described in the charge generation layer (35) is preferably used, and in particular, a polycarbonate having a triarylamine structure in the main chain or / and the side chain is used. It is valid. Examples of the more useful polycarbonate having a triarylamine structure used in the present invention include polymer charge transport materials of the following general formulas 1 to 10.
[0057]
[Chemical 1]

(Wherein R₁, R₂, R₃ Each independently represents a substituted or unsubstituted alkyl group or a halogen atom, R₄Is a hydrogen atom or a substituted or unsubstituted alkyl group, R₅ , R₆ Is 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% The 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.
[0058]
[Chemical formula 2]

(Wherein R₁₀₁, R₁₀₂ Each 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
[0059]
[Chemical Formula 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 R₁₀₁ And R₁₀₂, R₁₀₃And R₁₀₄May be the same or different.
[0060]
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~ C₁₂C in particular₁~ C₈, More preferably C₁~ C₄ These 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~ C₄ A phenyl group substituted with an alkoxy group may be contained.
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.
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, R₃ The 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.
As an aromatic hydrocarbon group, a phenyl group, a condensed polycyclic group such 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 include fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups such as biphenylyl group and terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
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, R₃ The same thing is mentioned.
(3) Alkoxy group (-OR₁₀₅) As R₁₀₅Represents 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~ C₄ These alkyl groups or halogen atoms 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 dimethylamino group, diethylamino group, N-methyl-N-propylamino group, N, N-dibenzylamino group and the like.
(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
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 manufactured 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.
[0061]
[Formula 4]

[0062]
[Chemical formula 5]

[0063]
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) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4 , 4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy Diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl oxide, 2,2-bis (4-hydroxyphenyl) hexafluoro Propane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) xanthene, ethylene glycol-bis (4-hydroxybenzoate), diethylene glycol-bis (4-hydroxybenzoate), tri Examples include ethylene glycol-bis (4-hydroxybenzoate) 1,3-bis (4-hydroxyphenyl) -tetramethyldisiloxane, phenol-modified silicone oil, and the like.
[0064]
[Chemical 6]

(Wherein 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. )
[0065]
Specific example of general formula 2
R₇, R₈  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, Fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, biphenylyl group, terphenylyl group as non-condensed polycyclic group, or
[0066]
[Chemical 7]

Here, W is -O-, -S-, -SO-, -SO.₂-, -CO- and the following divalent groups are represented.
[0067]
[Chemical 8]

(Wherein c represents an integer of 1 to 12)
[0068]
[Chemical 9]

(In the formula, d represents an integer of 1 to 3.)
[0069]
Embedded image

(In the formula, e represents an integer of 1 to 3.)
[0070]
Embedded image

(In the formula, f represents an integer of 1 to 3.)
It is represented by
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
Ar₁, Ar₂And Ar₃The arylene group represented by R is R₇ And R₈  The 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~ C₄ These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄ An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄ Alkyl group or C₁~ C₄ A phenyl group substituted with an alkoxy group may be contained. 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) As R₁₀₉Represents 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~ C₄ These alkyl groups or halogen atoms 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)
[0071]
Embedded image

Where R₁₁₀And R₁₁₁Each independently represents an alkyl group or an aryl group defined in (2), and examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group,₁~ C₄ An alkoxy group of C₁~ C₄These alkyl groups or halogen atoms 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.
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 manufactured 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.
[0072]
Embedded image

[0073]
Embedded image

Examples of the diol compound of the general formula (B) are the same as those of the general formula 1.
[0074]
Embedded image

(Wherein R₉, R₁₀Is a substituted or unsubstituted aryl group, Ar₄ , Ar₅, Ar₆ Represent the same or different arylene groups. X, k, j and n are the same as those in the general formula 1. )
[0075]
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 such 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 include fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups such as biphenylyl group and terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
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~ C₁₂ C in particular₁~ C₈, More preferably C₁~ C₄ These 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~ C₄ A phenyl group substituted with an alkoxy group may be contained. 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) As R₁₁₂  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~ C₄ An alkoxy group of C₁~ C₄ These alkyl groups or halogen atoms 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 dimethylamino group, diethylamino group, N-methyl-N-propylamino group, N, N-dibenzylamino group and the like.
(7) Acyl group; Specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
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 manufactured 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.
[0076]
Embedded image

[0077]
Embedded image

Examples of the diol compound of the general formula (B) are the same as those in the general formula 1.
[0078]
Embedded image

(Wherein R₁₁, R₁₂ Is 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 those in the general formula 1. )
[0079]
Specific example of general formula 4
R₁₁, R₁₂ 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 such 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 include fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups such as biphenylyl group and terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
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~ C₁₂ C in particular₁~ C₈, More preferably C₁~ C₄ These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄ An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄ Alkyl group or C₁~ C₄ A phenyl group substituted with an alkoxy group may be contained. 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 ) As R₁₁₃Represents 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~ C₄ These alkyl groups or halogen atoms 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 dimethylamino group, diethylamino group, N-methyl-N-propylamino group, N, N-dibenzylamino group and the like.
(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
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 manufactured 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.
[0080]
Embedded image

[0081]

Examples of the diol compound of the general formula (B) are the same as those of the general formula 1.
[0082]
Embedded image
[General formula 5]

(Wherein 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 those in the general formula 1. )
[0083]
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 such 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 include fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups such as biphenylyl group and terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
Ar₁₀, Ar₁₁ And Ar₁₂The arylene group represented by R is R₁₃And R₁₄ The 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~ C₁₂ C in particular₁~ C₈, More preferably C₁~ C₄These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄ An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄ Alkyl group or C₁~ C₄ A phenyl group substituted with an alkoxy group may be contained. 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 ) As R₁₁₄ 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~ C₄ An alkoxy group of₁~ C₄ These alkyl groups or halogen atoms 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 dimethylamino group, diethylamino group, N-methyl-N-propylamino group, N, N-dibenzylamino group and the like.
(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
X₁, X₂ Represents 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.
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 manufactured 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.
[0084]
Embedded image

[0085]
Embedded image

Examples of the diol compound of the general formula (B) are the same as those of the general formula 1.
[0086]
Embedded image

(Wherein 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 those in the general formula 1. )
[0087]
Specific example of general formula 6
R₁₅, R₁₆, R₁₇, R₁₈Represents 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 such 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 include fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups such as biphenylyl group and terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
Ar₁₃, Ar₁₄, Ar₁₅And Ar₁₆The arylene group represented by R is R₁₅, R₁₆, R₁₇ And R₁₈ The 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~ C₁₂ C in particular₁~ C₈ , More preferably C₁~ C₄ These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄ An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄ Alkyl group or C₁~ C₄ A phenyl group substituted with an alkoxy group may be contained. 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) As R₁₁₅Represents 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~ C₄ These alkyl groups or halogen atoms 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.
Y₁, Y₂, Y₃ Represents 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.
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 manufactured 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.
[0088]
Embedded image

[0089]
Embedded image

Examples of the diol compound of the general formula (B) are the same as those in the general formula 1.
[0090]
Embedded image

(Wherein R₁₉, R₂₀ Represents a hydrogen atom, a substituted or unsubstituted aryl group, and R₁₉And R₂₀May form a ring. Ar₁₇, Ar₁₈, Ar₁₉ Represent the same or different arylene groups. X, k, j and n are the same as those in the general formula 1. )
[0091]
Specific example of general formula 7
R₁₉, R₂₀ 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, phenyl group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group as a condensed polycyclic 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, R₂₀ In the case of forming a ring, 9-fluorenylidene, 5H-dibenzo [a, d] cyclohebutenylidene and the like can be mentioned.
Ar₁₇, Ar₁₈ And 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~ C₁₂ C in particular₁~ C₈ , More preferably C₁~ C₄ These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄ An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄ Alkyl group or C₁~ C₄ A phenyl group substituted with an alkoxy group may be contained. 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}) As R_{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~ C₄ An alkoxy group of₁~ C₄ These alkyl groups or halogen atoms 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 dimethylamino group, diethylamino group, N-methyl-N-propylamino group, N, N-dibenzylamino group and the like.
(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
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 manufactured 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.
[0092]
Embedded image

[0093]
Embedded image

Examples of the diol compound of the general formula (B) are the same as those of the general formula 1.
[0094]
Embedded image
[General Formula 8]

(Wherein R₂₁Is a substituted or unsubstituted aryl group, Ar₂₀, Ar₂₁, Ar₂₂, Ar₂₃ Represent the same or different arylene groups. X, k, j and n are the same as those in the general formula 1. )
[0095]
Specific example of general formula 8
R₂₁ 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 such 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 include fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups such as biphenylyl group and terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
Ar₂₀, Ar₂₁, Ar₂₂ And Ar₂₃ The 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~ C₁₂ C in particular₁~ C₈ , More preferably C₁~ C₄ These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄ An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄ Alkyl group or C₁~ C₄ A phenyl group substituted with an alkoxy group may be contained. 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) As R₁₁₇ 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~ C₄ An alkoxy group of₁~ C₄ These alkyl groups or halogen atoms 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 dimethylamino group, diethylamino group, N-methyl-N-propylamino group, N, N-dibenzylamino group and the like.
(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
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 manufactured 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.
[0096]
Embedded image

[0097]
Embedded image

Examples of the diol compound of the general formula (B) are the same as those of the general formula 1.
[0098]
Embedded image

(Wherein 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 those in the general formula 1. )
[0099]
Specific example of general formula 9
R₂₂, R₂₃, R₂₄, R₂₅Represents 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 such 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 include fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups such as biphenylyl group and terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
Ar₂₄, Ar₂₅, Ar₂₆, Ar₂₇And Ar₂₈The arylene group represented by R is R₂₂, R₂₃, R₂₄ And 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~ C₁₂ C in particular₁~ C₈, More preferably C₁~ C₄ These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄ An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄ Alkyl group or C₁~ C₄ A phenyl group substituted with an alkoxy group may be contained. 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) As R₁₁₈Represents 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~ C₄ These alkyl groups or halogen atoms 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 dimethylamino group, diethylamino group, N-methyl-N-propylamino group, N, N-dibenzylamino group and the like.
(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
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 manufactured 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.
[0100]
Embedded image

[0101]
Embedded image

Examples of the diol compound of the general formula (B) are the same as those of the general formula 1.
[0102]
Embedded image
[General formula 10]

(Wherein R₂₆, R₂₇ Is a substituted or unsubstituted aryl group, Ar₂₉, Ar₃₀, Ar₃₁Represent the same or different arylene groups. X, k, j and n are the same as those in the general formula 1. )
[0103]
Specific example of general formula 10
R₂₆, R₂₇ Represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.
Aromatic hydrocarbon group is phenyl group, condensed polycyclic group is naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fullerene group Examples include oleenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and non-condensed polycyclic groups such as biphenylyl group and terphenylyl group.
Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.
Ar₂₉, Ar₃₀ And Ar₃₁  The arylene group represented by R is R₂₆ And 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~ C₁₂ C in particular₁~ C₈ , More preferably C₁~ C₄ These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, C₁~ C₄ An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄ Or a phenyl group substituted with a C1-C4 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) As R₁₁₉Represents 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~ C₄ These alkyl groups or halogen atoms 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 dimethylamino group, diethylamino group, N-methyl-N-propylamino group, N, N-dibenzylamino group and the like.
(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.
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 manufactured 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.
[0104]
Embedded image

[0105]
Embedded image

Examples of the diol compound of the general formula (B) are the same as those of the general formula 1.
[0106]
The binder resin used here is contained for the purpose of fixing the inorganic filler and maintaining the strength of the outermost surface layer, and at least 25 parts by weight, preferably 50 parts by weight or more are required as a minimum with respect to 100 parts by weight of the inorganic filler. . Further, additives such as a charge transport material can be used in the same addition ratio as the charge transport layer (37).
[0107]
Further, the film thickness of the surface portion containing the inorganic filler can be the entire layer of the charge transport layer (37), but is preferably 20 μm or less in view of image characteristics and electrical characteristics, and more preferably in the range of 1 to 10 μm. is there.
[0108]
The dispersant used in the coating liquid for the inorganic filler dispersion layer is added as necessary for the purpose of improving the dispersibility of the inorganic filler and improving the stability of the coating liquid when preparing 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.
[0109]
Examples of the polycarboxylic acid compound include low molecular compounds, oligomers, and high molecular compounds having a plurality of carboxylic acid residues, and examples thereof include organic fatty acids and highly oxidized resins. Examples of oligomers and polymer compounds of this polycarboxylic acid 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 added 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.
[0110]
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. The photosensitive layer (33) can be formed by dissolving or dispersing a charge transport material in an appropriate solvent as required, 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. As the charge generation material, the charge transport material, the plasticizer, and the leveling agent, the same materials as already described for the charge generation layer (35) and the charge transport layer (37) can be used.
[0111]
As the binder resin, in addition to the binder resin already mentioned in the charge transport layer (37), the binder resin mentioned in the charge generation layer (35) may be mixed and used. In addition, the polymer charge transport materials listed above can also be used favorably. 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 is a dip coating method, spray coating, a coating solution in which a charge generating material, a binder resin, and a charge transporting material as necessary together with a solvent such as tetrahydrofuran, dioxane, dichloroethane, and cyclohexane are dispersed with a dispersing machine. It can be formed by coating with bead coat or ring coat.
[0112]
The film thickness of the photosensitive layer is suitably about 5 to 25 μm.
When the photosensitive layer (33) having a single layer structure is a surface layer of the photoreceptor, an inorganic filler is contained in the entire layer of the photosensitive layer (33) or the surface thereof for the purpose of improving the wear resistance. By using trigonal α-alumina fine particles having an average particle size of 0.07 to 0.3 μm and a narrow particle size distribution as this inorganic filler, it has high durability and does not generate an image flow for repeated use. In addition, it is possible to continuously obtain a good image having high resolution and gradation and free from background stains and image density reduction. As the inorganic filler dispersed on the surface portion in this single layer structure, the above-mentioned inorganic fillers can be used, and other constituent materials including a binder resin are basically used for the photosensitive layer (33) having the above single layer structure. In addition, a polycarboxylic acid compound, a plasticizer, a leveling agent and the like described in the charge transport layer (37) are added as necessary. In addition, the amount of these contained materials, the manufacturing method of the inorganic filler dispersion layer, and the film thickness are the same as those described for the charge transport layer (37) and the single layer photosensitive layer (33). it can.
[0113]
In the photoreceptor of the present invention, an undercoat layer can be provided between the conductive support (31) and the photosensitive layer. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is coated with a solvent on these resins, the resin may be a resin having high solvent resistance with respect to a general organic solvent. desirable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, a metal oxide fine powder pigment exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential.
[0114]
These undercoat layers can be formed using an appropriate solvent and a coating method like the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention. In addition, the undercoat layer of the present invention includes Al.₂O₃Anodic oxidation, organic materials such as polyparaxylylene (parylene), and SiO₂, SnO₂TiO₂, ITO, CeO₂A material provided with an inorganic material such as a vacuum thin film can also be used favorably. In addition, known ones can be used. The thickness of the undercoat layer is suitably from 0 to 5 μm.
[0115]
In the photoreceptor of the present invention, a protective layer (39) can be provided on the surface side of the photosensitive layer (33) for the purpose of protecting the photosensitive layer. Since the protective layer (39) is a layer on the outermost surface side of the photoreceptor and requires high wear resistance, it is effective to contain an inorganic filler, but this inorganic filler has an average particle size of 0.07 to 0.00. By using trigonal α-alumina fine particles with a narrow particle size distribution of 3 μm, it has high durability and does not generate an image flow for repeated use, and further has high resolution and gradation, A good image without a decrease in image density can be obtained continuously.
[0116]
Examples of the binder resin used for this protective layer include 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, Resins such as polyvinyl chloride, polyvinylidene chloride, and epoxy resins can be used in combination.
[0117]
As the inorganic filler dispersed in the protective layer (39), those described above can be used, and if necessary, a polycarboxylic acid compound, a plasticizer, a leveling agent, etc. are added in the same manner as described for the charge transport layer (37). Is done. Moreover, the same matters as described for the charge transport layer (37) can be applied to the addition amount of these materials, the dispersion method of the inorganic filler, and the production method of the protective layer (39). In addition, about 0.5-5 micrometers is suitable for the thickness of a protective layer (39).
[0118]
In the photoreceptor of the present invention, an intermediate layer can be provided between the photosensitive layer (33) or the charge transport layer (37) and the protective layer (39). In the intermediate layer, a binder resin is generally used as a main component. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As a method for forming the intermediate layer, a general coating method can be adopted as described above. In addition, about 0.05-2 micrometers is suitable for the thickness of an intermediate | middle layer.
[0119]
In the present invention, in order to improve environmental resistance, each layer such as a charge generation layer, a charge transport layer, an undercoat layer, a protective layer, and an intermediate layer is used to prevent a decrease in sensitivity and an increase in residual potential. An antioxidant can be added to the. The following are mentioned as antioxidant which can be used for this invention.
[0120]
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, etc.
[0121]
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.
[0122]
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.
[0123]
Organic sulfur compounds
Dilauryl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, ditetradecyl-3,3'-thiodipropionate, and the like.
[0124]
Organophosphorus compounds
Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine, and the like.
[0125]
These compounds are known as antioxidants such as rubbers, plastics and fats and oils, and commercially available products can be easily obtained.
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.
[0126]
Next, the image forming method and the image forming apparatus of the present invention will be described in detail with reference to the drawings.
In the image forming method and the image forming apparatus of the present invention, the outermost surface layer of the present invention contains at least trigonal α-alumina fine particles having an average particle size of 0.07 to 0.3 μm and a narrow particle size distribution as an inorganic filler. An image forming method comprising a process using a photoconductor, for example, at least after the process of charging, image exposure, and development to the photoconductor, transfer of a toner image to an image carrier (transfer paper), fixing, and cleaning of the surface of the photoconductor And an image forming apparatus.
In some cases, an image forming method or the like in which an electrostatic latent image is directly transferred to a transfer member and developed does not necessarily have the above-described process arranged on a photosensitive member.
[0127]
FIG. 6 is a schematic diagram illustrating an example of an image forming apparatus. A charging charger (3) is used as a means for charging the photoconductor on average. As the charging means, a corotron device, a scorotron device, a solid discharge element, a needle electrode device, a roller charging device, a conductive brush device, or the like is used, and all known methods can be used.
[0128]
Next, the image exposure unit 5 is used to form an electrostatic latent image on the uniformly charged photoconductor. As the light source, all luminescent materials such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL) can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
[0129]
Next, the developing unit 6 is used to visualize the electrostatic latent image formed on the photoreceptor. Development methods include a one-component development method using a dry toner, a two-component development method, and a wet development method using a wet toner. When the photosensitive member is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. When this is developed with negative (positive) polarity toner (electrodetection fine particles), a positive image can be obtained, and when developed with positive (negative) polarity toner, a negative image can be obtained.
[0130]
Next, a transfer charger (10) is used to transfer the toner image visualized on the photosensitive member onto the transfer member. In addition, a pre-transfer charger (7) may be used for better transfer. As these transfer means, a transfer charger, an electrostatic transfer method using a bias roller, a mechanical transfer method such as an adhesive transfer method and a pressure transfer method, and a magnetic transfer method can be used. As the electrostatic transfer method, the charging means can be used.
[0131]
Next, a separation charger (11) and a separation claw (12) are used as means for separating the transfer member from the photosensitive member. As other separation means, electrostatic adsorption induction separation, side end belt separation, tip grip conveyance, curvature separation, and the like are used. As the separation charger, the charging means can be used.
[0132]
Next, a fur brush (14) and a cleaning blade (15) are used to clean the toner remaining on the photoreceptor after transfer. Further, a pre-cleaning charger (13) may be used in order to perform cleaning more efficiently. Other cleaning means include a web method, a magnet brush method, and the like, but each may be used alone or in combination with a plurality of methods.
[0133]
Next, a neutralizing unit is used for the purpose of removing the latent image on the photoreceptor as required. As the charge removal means, a charge removal lamp (2) and a charge removal charger are used, and the exposure light source and the charging means can be used respectively.
[0134]
In addition, all known processes such as document reading, paper feeding, fixing, and paper ejection that are not close to the photoreceptor can be used.
The present invention is an image forming method and an image forming apparatus using the electrophotographic photoreceptor according to the present invention for such image forming means.
[0135]
The image forming unit may be fixedly incorporated in a copying apparatus, a facsimile, or a printer, but may be incorporated in the apparatus in the form of a process unit and detachable. FIG. 7 is a schematic diagram illustrating an example of a process unit for an image forming apparatus.
[0136]
The process unit for an image forming apparatus is an apparatus (part) in which a photoconductor is incorporated and at least one of a charging unit, a developing unit, a transfer unit, a cleaning unit, and a charge removing unit is integrated and detachable. The present invention relates to a photoconductor containing trigonal α-alumina fine particles having an average particle size of 0.07 to 0.3 μm and a narrow particle size distribution as an inorganic filler at least as an inorganic filler, and charging, development, transfer, cleaning and charge removal. The present invention provides a process unit for an image forming apparatus in which at least one of the means is integrated.
[0137]
【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.
[0138]
[Example 1]
By coating and drying an undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution in the following order on a φ30 mm aluminum drum in sequence, an undercoat layer of 3.5 μm, A 0.2 μm charge generation layer and a 22 μm charge transport layer were formed. The coating solution for the inorganic filler-containing layer of the outermost surface layer was prepared by ball milling the following inorganic filler and solvent using alumina balls for 24 hours and adding a binder resin, a charge transporting substance and a solvent to the dispersion. This coating solution was spray-coated on the charge transport layer and dried to provide 3 μm of the outermost surface layer containing an inorganic filler to obtain the electrophotographic photosensitive member of the present invention.
[0139]
[Coating liquid for undercoat layer]

[0140]
[Coating liquid for charge generation layer]
2.5 parts of bisazo pigment with the following structure
[0141]
Embedded image

Polyvinyl butyral (XYHL, manufactured by UCC) 0.5 part
200 parts of cyclohexanone
80 parts of methyl ethyl ketone
[0142]
[Coating liquid for charge transport layer]
Bisphenol Z polycarbonate
(Panlite TS-2050, manufactured by Teijin Kasei) 10 parts
7 parts of low molecular charge transport material (D-1) having the following structure
[0143]
Embedded image

Tetrahydrofuran 100 parts
1% silicone oil (KF50-100CS, manufactured by Shin-Etsu Chemical)
Tetrahydrofuran solution 1 part
[0144]
[Coating liquid for inorganic filler-containing layer]

[0145]
[Example 2]
Electrophotography as in Example 1 except that the inorganic filler in the coating liquid for the inorganic filler-containing layer of Example 1 was changed to 2 parts of trigonal α-alumina fine particles (Tymicron TM-DAR: manufactured by Daimei Chemical Industries). A photoconductor was prepared.
[0146]
[Example 3]
Electrophotography as in Example 1, except that the inorganic filler in the coating liquid for the inorganic filler-containing layer of Example 1 was changed to 2 parts of trigonal α-alumina fine particles (Tymicron TM-DA: manufactured by Daimei Chemical Industries). A photoconductor was prepared.
[0147]
[Example 4]
In the coating liquid preparation process, 2 parts of trigonal α-alumina fine particles (Tymicron TM-5D: manufactured by Chemical Industry Co., Ltd., manufactured by Daimei Chemical Industry Co., Ltd.) were used as the inorganic filler of the coating liquid for the inorganic filler-containing layer of Example 1. An electrophotographic photoreceptor is prepared in the same manner as in Example 1 except that 0.02 part of a polycarboxylic acid compound (BYK-P104, manufactured by BYK Chemie) is contained as a dispersant when the inorganic filler is dispersed, and the film thickness of the outermost surface layer is 5 μm. Produced.
[0148]
[Example 5]
2 parts of trigonal α-alumina fine particles (Tymicron TM-DAR: manufactured by Daimei Chemical Industry Co., Ltd.) are used as the inorganic filler of the coating liquid for the inorganic filler-containing layer of Example 1, and the inorganic filler is dispersed in the coating liquid preparation process. An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that 0.02 part of a polycarboxylic acid compound (BYK-P104, manufactured by BYK Chemie) was sometimes contained as a dispersant and the film thickness of the outermost surface layer was changed to 5 μm.
[0149]
[Example 6]
2 parts of trigonal α-alumina fine particles (Tymicron TM-DA: manufactured by Daimei Chemical Co., Ltd.) are used as the inorganic filler of the coating liquid for the inorganic filler-containing layer of Example 1, and the inorganic filler is dispersed in the coating liquid preparation process. An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that 0.02 part of a polycarboxylic acid compound (BYK-P104, manufactured by BYK Chemie) was sometimes contained as a dispersant and the film thickness of the outermost surface layer was changed to 5 μm.
[0150]
[Example 7]
An electrophotographic photosensitive member was produced in the same manner as in Example 4 except that the binder resin of Example 4 was changed to 4 parts of polycarbonate (Panlite C-1400, manufactured by Teijin Chemicals).
[0151]
[Example 8]
An electrophotographic photosensitive member was produced in the same manner as in Example 4 except that the binder resin of Example 4 was changed to 7 parts of the polymer charge transporting material (PD-1) having the following structure and no low molecular charge transporting material was added.
[0152]
Embedded image

k = 0.40, j = 0.60, Mw = 15000 (polystyrene conversion)
[0153]
[Comparative Example 1]
The inorganic filler of the coating liquid for the inorganic filler-containing layer of Example 1 using 2 parts of rutile-titanium oxide powder (CR-EL: manufactured by Ishihara Sangyo), and as a dispersing agent when dispersing the inorganic filler in the coating liquid preparation process An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 0.02 part of a polycarboxylic acid compound (BYK-P104, manufactured by BYK Chemie) was contained and the film thickness of the outermost surface layer was 3 μm.
[0154]
[Comparative Example 2]
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the inorganic filler in the coating liquid for the inorganic filler-containing layer of Example 1 was changed to 1.5 parts of spherical silica particles (KE-P30: manufactured by Nippon Shokubai). .
[0155]
[Comparative Example 3]
The electrophotographic photosensitive member is the same as in Example 1 except that the inorganic filler in the coating liquid for the inorganic filler-containing layer of Example 1 is changed to 2 parts of hexagonal close lattice α-alumina particles (AA-2: manufactured by Sumitomo Chemical Co., Ltd.). Was made.
[0156]
[Comparative Example 4]
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the inorganic filler in the coating solution for the inorganic filler-containing layer of Example 1 was changed to 2 parts of alumina ultrafine particles (Aluminium Oxide C: manufactured by Nippon Aerosil).
[0157]
[Comparative Example 5]
The inorganic filler of the coating liquid for the inorganic filler-containing layer of Example 1 using 2 parts of α-alumina powder (AKP-30: manufactured by Sumitomo Chemical Co., Ltd.), and polydispersed as a dispersant when dispersing the inorganic filler in the coating liquid preparation process. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 0.02 part of a carboxylic acid compound (BYK-P104, manufactured by BYK Chemie) was contained and the film thickness of the outermost surface layer was changed to 5 μm.
[0158]
[Comparative Example 6]
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the inorganic filler in the inorganic filler-containing layer coating liquid of Example 1 was changed to 2 parts of α-alumina powder (AL-M41: manufactured by Sumitomo Chemical Co., Ltd.). .
[0159]
[Comparative Example 7]
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the inorganic filler in the inorganic filler-containing layer coating solution of Example 1 was changed to 2 parts of α-alumina powder (AMS-12: manufactured by Sumitomo Chemical Co., Ltd.). .
[0160]
[Comparative Example 8]
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the inorganic filler of the coating liquid for the inorganic filler-containing layer of Example 1 was changed to 2 parts of θ-alumina powder (TM-100D: manufactured by Daimei Chemical Industry). .
[0161]
[Comparative Example 9]
Same as Example 1 except that the inorganic filler of the coating liquid for inorganic filler-containing layer of Example 1 was changed to 2 parts of γ-alumina powder (TM-300D: AMS-12 manufactured by Daimei Chemical Industry, manufactured by Sumitomo Chemical Co., Ltd.). An electrophotographic photosensitive member was prepared.
[0162]
[Comparative Example 10]
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the outermost layer containing the inorganic filler in Example 1 was not provided.
[0163]
[Table 1]

[0164]
The α-alumina particles of the examples are manufactured by ASTM X-ray Powder Date File NO. From 10-173, the crystal form is trigonal. Moreover, as a result of measuring the biaxial average diameter of the particles from observation with a field emission scanning electron microscope FE-SEM (manufactured by Hitachi, Ltd .: S-4200), it was α-alumina fine particles of 0.07 to 0.3 μm, The number-based particle size distribution is narrow. When the cumulative particle size of 10% and 90% from the fine particle side is Da and Db, respectively, the value of Db / Da is 4 or less and the particle size of 1 μm or more is substantially The particle size is very uniform as compared with pulverized powders such as the Bayer method and hydrothermal synthetic alumina. In addition, the trigonal α-alumina used in the present invention has a weak primary particle agglomeration and has become a single particle, and the BET specific surface area calculated from the amount of gas adsorption is 8 to 20 m as a particle size.²Large as / g. Further, the trigonal α-alumina particles have a sodium content as low as 10 ppm or less as determined by impurity analysis by emission analysis, and have a high purity of 99.99 or more excluding the amount of impurities from the whole.
[0165]
Using the photographic photographic photoreceptors of Examples 1 to 8 and Comparative Examples 1 to 10 prepared as described above in a process unit for an electrophotographic apparatus and using an image exposure light source modified to a 655 nm semiconductor laser, magio MF2200 manufactured by Ricoh was used. The image was evaluated. First, an initial image was taken under an environment of a temperature of 25 ° C. and a humidity of 55%. After that, after being left in a 5 ppm ozone gas atmosphere for 10 hours as an acceleration test of the charging load, the image was returned to the same environment as the initial stage to confirm the image change. Thereafter, another 30,000 copies were made, and the amount of wear and image change of the photoreceptor after completion of copying were examined. The results are shown in Table 2.
[0166]
[Table 2]

[0167]
From the evaluation results of Table 2, in the photoreceptor in which the inorganic filler is dispersed in the outermost surface layer aiming at improvement of wear resistance, the average particle size is 0.07-0 as the inorganic filler as shown in Examples 1-8. By using trigonal α-alumina fine particles having a narrow particle size distribution at 3 μm, compared to the case where another filler of Comparative Examples 1 to 9 is used, image flow and background stains are not generated, and gradation is improved. It can be seen that a good image with high resolution and no decrease in image density can be obtained continuously. Further, it can be seen that a photoconductor having a high wear resistance and a long life is achieved as compared with the case where the surface layer containing the inorganic filler of Comparative Example 10 is not used.
Therefore, by using trigonal α-alumina fine particles having an average particle size of 0.07 to 0.3 μm and a narrow particle size distribution as the inorganic filler in the outermost surface layer of the present invention, it has high durability and can be used repeatedly. In contrast, it has been found that it is possible to provide a high-performance and highly reliable electrophotographic photosensitive member capable of continuously obtaining good images. In addition, it has been found that the image forming method, the image forming apparatus, and the process unit for the image forming apparatus using the electrophotographic photosensitive member of the present invention have high performance and high reliability.
[0168]
【The invention's effect】
As described above, as is clear from the detailed and specific description, according to the present invention, in the electrophotographic photosensitive member containing at least the inorganic filler and the binder resin in the outermost surface layer, the average particle size of 0. By using trigonal α-alumina fine particles having a narrow particle size distribution of 07 to 0.3 μm, a highly durable, high-performance and highly reliable electrophotographic photosensitive member capable of maintaining high image quality with high wear resistance. Can be provided. Further, by using the electrophotographic photosensitive member of the present invention, a high-performance and highly reliable image forming method, an image forming apparatus, and a process unit for an image forming apparatus can be provided.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of a photoreceptor of the present invention.
FIG. 2 is a cross-sectional view showing another example of the photoreceptor of the present invention.
FIG. 3 is a cross-sectional view showing another example of the photoreceptor of the present invention.
FIG. 4 is a cross-sectional view showing another example of the photoreceptor of the present invention.
FIG. 5 is a cross-sectional view showing another example of the photoreceptor of the present invention.
FIG. 6 is a schematic diagram illustrating an example of an image forming apparatus according to the present invention.
FIG. 7 is a schematic diagram illustrating an example of a process unit for an image forming apparatus according to the present invention.
[Explanation of symbols]
1 Photoconductor
2 Static elimination lamp
3 Charger charger
4 Eraser
5 Image exposure section
6 Development unit
7 Charger before transfer
8 Registration roller
9 Transfer paper
10 Transcription charger
11 Separate charger
12 Separating nails
13 Charger before cleaning
14 Fur brush
15 Cleaning blade
31 Conductive support
33 Photosensitive layer
35 Charge generation layer
37 Charge transport layer
39 Protective layer
101 Photosensitive drum
102 Charging device
103 exposure
104 Developing device
105 Transcript
106 Transfer device
107 Cleaning blade

Claims (11)

  In an electrophotographic photosensitive member in which at least a photosensitive layer is provided on a conductive support, the outermost surface layer of the electrophotographic photosensitive member contains at least an inorganic filler and a binder resin, and the inorganic filler is a trigonal α An electrophotographic photosensitive member characterized by being alumina. The electrophotographic photosensitive member according to claim 1, wherein the α-alumina particles are produced by thermally decomposing aluminum ammonium carbonate hydroxide [NH ₄ AlCO ₃ (OH) ₂ ].   The electrophotographic photosensitive member according to claim 1, wherein the α-alumina particles have a sodium content of 20 ppm or less as an impurity.   The electrophotographic photosensitive member according to claim 1, wherein the α-alumina particles have a purity of 99.99% by weight or more. The outermost layer is an electrophotographic photosensitive member according to any one of claims 1 to 4, characterized in that those containing the polycarboxylic acid compound. The electrophotographic photosensitive member according to any one of claims 1 to 4 binder resin contained in the outermost layer is characterized in that it is a polymer charge transport material. The binder resin contained in the outermost surface layer, the main chain or, and electrophotographic photosensitive member according to any one of claims 1 to 4, characterized in that a polycarbonate having a triarylamine structure in a side chain. The electrophotographic photosensitive member according to any one of claims 1 to 4 , wherein the outermost surface layer containing at least an inorganic filler and a binder resin is a surface portion of a charge transport layer.   9. An image forming method comprising forming an image on the electrophotographic photosensitive member according to claim 1 by repeating at least charging, exposure, development, and transfer.   9. An image forming apparatus comprising a charging unit, an exposure unit, a developing unit, and a transfer unit in addition to the electrophotographic photosensitive member according to claim 1.   In addition to the electrophotographic photosensitive member according to any one of claims 1 to 8, at least one means selected from the group consisting of a charging means, a developing means, a transfer means, a cleaning means, and a static elimination means is integrated. A process unit for an image forming apparatus, which is detachable.

Images