JP2004070271A - Electrophotographic photoreceptor and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which is extremely highly resistant to wear, has a surface resistance to scratching, does not crack, has good electrostatic chargeability, reduces the residual potential during photoirradiation, is less fluctuated in electrostatic charge potential in spite of repeated use, hardly forms abnormal images, attains the compatibility of the wear resistance with high image quality stability, and is long in lifetime. <P>SOLUTION: The electrophotographic photoreceptor has a layer containing a composition bonded with a charge transferable group by a reaction of an epoxy group and a silanol group in a crosslinked body formed by a condensation reaction of the silanol group. <P>COPYRIGHT: (C)2004,JPO

Description

（式中、Ｒ^１は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表す。Ａｒ^１は少なくとも１個の３級アミノ基を有するアリール基、少なくとも１個の３級アミノ基を有する複素環基を表す。Ａｒ^２、Ａｒ^３は置換もしくは無置換のアリレン基を表す。但し、Ａｒ^２とＡｒ^３は同一でも異なっていてもよい。ｎは０〜１００の整数を表す。）
（９）前記エポキシ基含有アミン化合物が下記一般式（２）で表される化合物であることを特徴とする前記（２）〜（８）のいずれかに記載の電子写真感光体。
【化１０】

（式中、Ｒ^４〜Ｒ^２５は水素原子、ハロゲン原子、置換もしくは無置換のアルキル基を表し、それぞれ同一でも異なっていてもよい。ｎは０〜１００の整数を表す。）
（１０）前記アルコキシシラン化合物が下記一般式（３）で表される化合物であることを特徴とする前記（２）、（４）〜（９）のいずれかに記載の電子写真感光体。
【化１１】
（Ｒ）_ｎ−Ｓｉ−（Ｘ）_４−ｎ　　　　　　　　　　　　　（３）
（式中、Ｒはケイ素原子に炭素原子が直接結合した形の有機基を表し、Ｘは加水分解性基を表し、少なくとも１個はアルコキシ基であり、ｎは０〜３の整数を表す。）
（１１）前記シラノール化合物が下記一般式（４）で表される化合物であることを特徴とする前記（３）、（４）、（６）〜（９）のいずれかに記載の電子写真感光体。
【化１２】
（Ｒ）_ｎ−Ｓｉ−（Ｙ）_４−ｎ　　　　　　　　　　　（４）
（式中、Ｒはケイ素原子に炭素原子が直接結合した形の有機基を表し、ｎは０〜３の整数を表し、ｎが３の場合Ｙは水酸基を表し、ｎが０〜２の場合Ｙは一つが水酸基で残りが水酸基又は加水分解性基を表す。）
（１２）前記アルコキシシラン化合物及び／又はシラノール化合物が２種以上の混合物からなることを特徴とする前記（２）〜（１１）のいずれかに記載の電子写真感光体。
（１３）前記アルコキシシラン化合物及び／又はシラノール化合物が少なくとも１個の芳香族基を有する化合物であることを特徴とする前記（２）〜（１２）のいずれかに記載の電子写真感光体。
（１４）下記の成分Ａ、Ｂ、Ｃを含み、且つ成分Ａ、Ｂの混合割合が、固形分重量比で、（成分Ｂ）／（成分Ａ＋成分Ｂ）＝０．１〜０．７、である硬化被覆組成物を表面に有する電子写真感光体。
Ａ：分子中にケイ素原子に結合した水酸基を有するシラン化合物
Ｂ：下記一般式（１）で表されるエポキシ化合物
【化１３】

（式中、Ｒ^１は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表す。Ａｒ^１は少なくとも１個の３級アミノ基を有するアリール基、少なくとも１個の３級アミノ基を有する複素環基を表す。Ａｒ^２、Ａｒ^３は置換もしくは無置換のアリレン基を表す。但し、Ａｒ^２とＡｒ^３は同一でも異なっていてもよい。ｎは０〜１００の整数を表す。）
Ｃ：一般式、ＡｌＸ_ｎＹ_３−ｎで示されるアルミニウムキレート化合物
（式中、Ｘは低級アルコキシル基、ＹはＭ^１ＣＯＣＨ_２ＣＯＭ^２、及びＭ^３ＣＯＣＨ_２ＣＯＯＭ^４からなる群から選ばれた化合物から生じる配位子、Ｍ^１、Ｍ^２、Ｍ^３およびＭ^４は低級アルキル基、ｎは０、１または２である。）
（１５）下記の成分Ａ、Ｂ、Ｃ、Ｄを含み、且つ成分Ａ、Ｂ、Ｄの混合割合が、固形分重量比で、（成分Ｂ）／（成分Ａ＋成分Ｂ＋成分Ｄ）＝０．１〜０．６、（成分Ｄ）／（成分Ａ＋成分Ｂ＋成分Ｄ）＝０．０１〜０．３、である硬化被覆組成物を表面に有する電子写真感光体。
Ａ：分子中にケイ素原子に結合した水酸基を有するシラン化合物
Ｂ：下記一般式（１）で表されるエポキシ化合物
【化１４】

（式中、Ｒ^１は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表す。Ａｒ^１は少なくとも１個の３級アミノ基を有するアリール基、少なくとも１個の３級アミノ基を有する複素環基を表す。Ａｒ^２、Ａｒ^３は置換もしくは無置換のアリレン基を表す。但し、Ａｒ^２とＡｒ^３は同一でも異なっていてもよい。ｎは０〜１００の整数を表す。）
Ｃ：一般式、ＡｌＸ_ｎＹ_３−ｎで示されるアルミニウムキレート化合物
（式中、Ｘは低級アルコキシル基、ＹはＭ^１ＣＯＣＨ_２ＣＯＭ^２、及びＭ^３ＣＯＣＨ_２ＣＯＯＭ^４からなる群から選ばれた化合物から生じる配位子、Ｍ^１、Ｍ^２、Ｍ^３およびＭ^４は低級アルキル基、ｎは０、１または２である。）
Ｄ：平均粒子径１〜１００ｎｍの微粒子状シリカ
（１６）前記硬化被覆組成物の膜厚が１〜１５μｍであることを特徴とする前記（１４）又は（１５）に記載の電子写真感光体。
【００１３】
（１７）下記の成分Ａ、Ｂ、Ｃを含み、且つ成分Ａ、Ｂの混合割合が、固形分重量比で、（成分Ｂ）／（成分Ａ＋成分Ｂ）＝０．１〜０．７、である組成物を溶媒に溶解または分散させた塗工液を作製し、この塗工液を感光体表面に塗工した後、８０〜１５０℃にて加熱硬化させることを特徴とする電子写真感光体の製造方法。
Ａ：分子中にケイ素原子に結合した水酸基を有するシラン化合物
Ｂ：下記一般式（１）で表されるエポキシ化合物
【化１５】

（式中、Ｒ^１は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表す。Ａｒ^１は少なくとも１個の３級アミノ基を有するアリール基、少なくとも１個の３級アミノ基を有する複素環基を表す。Ａｒ^２、Ａｒ^３は置換もしくは無置換のアリレン基を表す。但し、Ａｒ^２とＡｒ^３は同一でも異なっていてもよい。ｎは０〜１００の整数を表す。）
Ｃ：一般式、ＡｌＸ_ｎＹ_３−ｎで示されるアルミニウムキレート化合物
（式中、Ｘは低級アルコキシル基、ＹはＭ^１ＣＯＣＨ_２ＣＯＭ^２、及びＭ^３ＣＯＣＨ_２ＣＯＯＭ^４からなる群から選ばれた化合物から生じる配位子、Ｍ^１、Ｍ^２、Ｍ^３およびＭ^４は低級アルキル基、ｎは０、１または２である。）
（１８）下記の成分Ａ、Ｂ、Ｃ、Ｄを含み、且つ成分Ａ、Ｂ、Ｄの混合割合が、固形分重量比で、（成分Ｂ）／（成分Ａ＋成分Ｂ＋成分Ｄ）＝０．１〜０．６、（成分Ｄ）／（成分Ａ＋成分Ｂ＋成分Ｄ）＝０．０１〜０．３、である組成物を溶媒に溶解または分散させた塗工液を作製し、この塗工液を感光体表面に塗工した後、８０〜１５０℃にて加熱硬化させることを特徴とする電子写真感光体の製造方法。
Ａ：分子中にケイ素原子に結合した水酸基を有するシラン化合物
Ｂ：下記一般式（１）で表されるエポキシ化合物
【化１６】

（式中、Ｒ^１は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表す。Ａｒ^１は少なくとも１個の３級アミノ基を有するアリール基、少なくとも１個の３級アミノ基を有する複素環基を表す。Ａｒ^２、Ａｒ^３は置換もしくは無置換のアリレン基を表す。但し、Ａｒ^２とＡｒ^３は同一でも異なっていてもよい。ｎは０〜１００の整数を表す。）
Ｃ：一般式、ＡｌＸ_ｎＹ_３−ｎで示されるアルミニウムキレート化合物
（式中、Ｘは低級アルコキシル基、ＹはＭ^１ＣＯＣＨ_２ＣＯＭ^２、及びＭ^３ＣＯＣＨ_２ＣＯＯＭ^４からなる群から選ばれた化合物から生じる配位子、Ｍ^１、Ｍ^２、Ｍ^３およびＭ^４は低級アルキル基、ｎは０、１または２である。）
Ｄ：平均粒子径１〜１００ｎｍの微粒子状シリカ
（１９）前記溶媒が、少なくともベンジルアルコール、シクロヘキサノン、酢酸２−メトキシエチル、テトラヒドロフラン、アセチルアセトンから選ばれる１種以上の溶媒を含有していることを特徴とする前記（１７）又は（１８）に記載の電子写真感光体の製造方法。
【００１４】
【発明の実施の形態】
本発明で使用されるシラノール基の縮合反応により形成される架橋体とは、一分子中にケイ素原子に結合した水酸基を一個以上有するシラン化合物またはそれらの混合物であって、少なくとも一分子中にケイ素原子に結合した水酸基を三個以上有するシラン化合物の存在下にシラノール基の縮合反応をさせて３次元的に架橋硬化させた組成物を言う。そして、電荷輸送性基がエポキシ基とシラノール基との反応により結合されているとは、上記シラン化合物中に、エポキシ基を有し、且つ電荷輸送性基も有する化合物を混合し、シラノール基とエポキシ基の付加反応によって化学結合した状態を指す。ここで、エポキシ基を有し、且つ電荷輸送性基も有する化合物の好ましい態様としては、下記エポキシ基含有アミン化合物を挙げることが出来る。また、一分子中にケイ素原子に結合した水酸基を一個以上有するシラン化合物の好ましい態様としては前記一般式（３）で表されるアルコキシシラン化合物の加水分解物、前記一般式（４）で表されるシラノール化合物を挙げることが出来る。
【００１５】
本発明に使用されるエポキシ基含有アミン化合物としては、通常電子写真感光体の電荷輸送物質として使用されるオキサゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、トリフェニルアミン等のトリアリールアミン誘導体、フェニルヒドラゾン誘導体、α−フェニルスチルベン誘導体、スチルベン誘導体、ベンゾイミダゾール誘導体、Ｎ−フェニルカルバゾール誘導体等の電荷輸送性化合物の骨格を有し、その置換基としてエポキシ基を１個以上、好ましくは２個以上有する化合物が挙げられる。十分な電荷輸送能を発揮させるためにはこれらのエポキシ基含有アミン化合物を反応物組成中２０重量％以上含有させることが望ましいが、エポキシ基が少ないと反応物の架橋密度が低下し、十分な耐摩耗性が得られない。エポキシ基を２個以上有する場合は、十分な架橋密度が得られ高い耐摩耗性が得られる。
【００１６】
それらの中で、優れた電荷輸送特性を有する化合物として下記一般式（１）、さらに好ましくは一般式（２）で表されるエポキシ基含有アミン化合物が好適に使用される。
尚、これら一般式（１）及び（２）で表されるエポキシ基含有アミン化合物は新規化合物であり、対応するジヒドロキシ化合物とグリシジル化剤とを反応させることにより製造することができる。
【００１７】
【化１７】

（式中、Ｒ^１は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表す。Ａｒ^１は少なくとも１個の３級アミノ基を有するアリール基、少なくとも１個の３級アミノ基を有する複素環基を表す。Ａｒ^２、Ａｒ^３は置換もしくは無置換のアリレン基を表す。但し、Ａｒ^２とＡｒ^３は同一でも異なっていてもよい。ｎは０〜１００の整数を表す。）
【００１８】
【化１８】

（式中、Ｒ^４〜Ｒ^２５は水素原子、ハロゲン原子、置換もしくは無置換のアルキル基を表し、それぞれ同一でも異なっていてもよい。ｎは０〜１００の整数を表す。）
【００１９】
前記一般式（１）及び（２）で表されるエポキシ基含有アミン化合物において、Ｒ^１、Ｒ^４〜Ｒ^２５の置換もしくは無置換のアルキル基とは、炭素数１〜５の直鎖又は分岐鎖のアルキル基であり、ハロゲン原子やフェニル基で置換されていてもよく、該フェニル基は、さらにハロゲン原子や炭素数１〜５のアルキル基などで置換されていてもよい。具体的にはメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、ｎ−ペンチル基、トリフルオロメチル基、ベンジル基、４−クロロベンジル基、４−メチルベンジル基等が挙げられる。
【００２０】
また、Ｒ^１の置換もしくは無置換のアリール基として、フェニル基、ナフチル基、ビフェニリル基、ターフェニリル基、ピレニル基、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、クリセニル基等が挙げられ、これらのアリール基にはハロゲン原子や前述のアルキル基、フェニル基等が置換していてもよい。また、下記一般式（５）で表される基も挙げることができる。
【化１９】

〔式中、Ｘは−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−及び下記の２価基を表す。
【化２０】

【化２１】

（ここで、Ｒ^２６、Ｒ^２７は水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表し、ａは１〜１２の整数、ｂは１〜３の整数を表す。）〕
尚、前記一般式（５）中のＲ^２６、Ｒ^２７の置換もしくは無置換のアルキル基、及び置換もしくは無置換のアリール基は前記Ｒ^１、Ｒ^４〜Ｒ^２５と、その定義及び具体例は同様である。
【００２１】
また前記一般式（１）で表されるエポキシ基含有アミン化合物において、Ａｒ^１の少なくとも１個の３級アミノ基を有するアリール基の該アリール基としては、前記Ｒ^１の説明において挙げたものと同様のものを挙げることができる。
さらに該３級アミノ基としては、前記Ｒ^１６〜Ｒ^２５で表される基を有するフェニルが２個結合した窒素原子を有する基が挙げられる。
【００２２】
また前記一般式（１）で表されるエポキシ基含有アミン化合物にいおいて、Ａｒ^２、Ａｒ^３の置換もしくは無置換のアリレン基としては、前記Ａｒ^１の説明（即ちＲ^１の説明）において挙げたアリール基から誘導される２価の基が挙げられる。
さらに該アリレン基の置換基としては、前記Ｒ^４〜Ｒ^１１の説明において挙げたものと同様のものを挙げることができる。
【００２３】
またＡｒ^１が少なくとも１個の３級アミノ基を有する置換もしくは無置換の複素環基の該複素環基としては、ピロール、ピラゾール、イミダゾール、トリアゾール、ジオキサゾール、インドール、イソインドール、ベンズイミダゾール、ベンゾトリアゾール、ベンズイソキサジン、カルバゾール、フェノキサジン等が挙げられ、これらの複素環基は前述のＲ^１で定義された置換もしくは無置換のアルキル基、ハロゲン原子、置換もしくは無置換のアリール基で置換されていても良い。
さらに該３級アミノ基としては、前記Ａｒ^１の説明において挙げたものと同様のものが挙げられる。
【００２４】
さらにまた、前記各基におけるハロゲン原子の具体例として、フッ素原子、塩素原子、臭素原子、ヨウ素原子を挙げることができる。
【００２５】
本発明で使用されるアルコキシシラン化合物としては、下記一般式（３）で表される化合物を挙げることができる。
【化２２】
（Ｒ）_ｎ−Ｓｉ−（Ｘ）_４−ｎ　　　　　　　　　　　　　（３）
（式中、Ｒはケイ素原子に炭素原子が直接結合した形の有機基を表し、Ｘは加水分解性基を表し、少なくとも１個はアルコキシ基であり、ｎは０〜３の整数を表す。）
【００２６】
前記一般式（３）において、Ｒで表されるケイ素原子に炭素原子が直接結合した形の有機基としては、メチル、エチル、プロピル、ブチル等のアルキル基、フェニル、トリル、ナフチル、ビフェニル等のアリール基、、γ−クロロプロピル、１，１，１−トリフルオロプロピル、ノナフルオロヘキシル、パーフルオロオクチルエチル等の含ハロゲン基、その他ニトロ基、シアノ置換アルキル基を挙げることができる。またＸの加水分解性基としてはメトキシ、エトキシ、プロポキシ、ブトキシ等のアルコキシ基、ハロゲン基、アシルオキシ基が挙げられる。特に炭素数６以下のアルコキシ基が好ましい。
一般式（３）で表される化合物は、１種単独でも良いし、２種以上を組み合わせて使用しても良い。
【００２７】
本発明で使用されるシラノール化合物としては、下記一般式（４）で表される化合物を挙げることができる。
【化２３】
（Ｒ）_ｎ−Ｓｉ−（Ｙ）_４−ｎ　　　　　　　　　　　　（４）
（式中、Ｒはケイ素原子に炭素原子が直接結合した形の有機基を表し、ｎは０〜３の整数を表し、ｎが３の場合Ｙは水酸基を表し、ｎが０〜２の場合Ｙは一つが水酸基で残りが水酸基又は加水分解性基を表す。）
【００２８】
前記一般式（４）において、Ｒで表されるケイ素原子に炭素原子が直接結合した形の有機基としては、前記一般式（３）の説明において挙げたものと同様のものが挙げられ、またＹの加水分解性基としては、前記一般式（３）のＸの説明において挙げたものと同様のものが挙げられる。
【００２９】
又一般式（３）及び一般式（４）で表される有機ケイ素化合物の具体的化合物で、ｎが２以上の場合、複数のＲは同一でも異なっていても良い。同様に、ｎが２以下の場合、複数のＸ及びＹは同一でも異なっていても良い。又、一般式（３）及び／又は一般式（４）で表される有機ケイ素化合物を２種以上を用いるとき、Ｒ及びＸ及びＹはそれぞれの化合物間で同一でも良く、異なっていても良い。
【００３０】
エポキシ基含有アミン化合物との相溶性を上げて均一な透明膜を得るためには、Ｒに少なくとも１個の芳香族基を有するアルコキシシラン化合物及び／又はシラノール化合物を用いることが好ましく、芳香族基を有しないアルコキシシラン化合物及び／又はシラノール化合物との混合で使用することがさらに好ましい。
【００３１】
また、前記一般式（３）及び一般式（４）において、加水分解性基及び／又は水酸基の数が２以上（ｎ＝２以下）の場合にシラン化合物が縮合してオルガノポリシロキサン樹脂が得られるが、該数が３（ｎ＝１）の場合に３次元に架橋可能な架橋性オルガノポリシロキサン樹脂が得られるため、ｎ＝１の３官能シランモノマーを原料として含むことが好ましい。そして３官能シランモノマーに他の２官能シランモノマー（ｎ＝２）成分や４官能シランモノマー（ｎ＝０）成分を適宜加えることにより、樹脂の性質（安定性、塗膜強度等）を調整することができる。
【００３２】
本発明におけるエポキシ基含有アミン化合物とアルコキシシラン化合物との反応物とは、該アルコキシシラン化合物のアルコキシ基又はアルコキシ基が加水分解して生成したシラノール基同士の縮合反応、及びエポキシ基含有アミン化合物のエポキシ基と前記シラノール基との付加反応、エポキシ基がシラノール基と開環付加反応した後に生成したヒドロキシ基と前記シラノール基の縮合反応により一体となって３次元架橋反応結合した樹脂物を言う。
【００３３】
また、本発明におけるエポキシ基含有アミン化合物とシラノール化合物との反応物とは、該シラノール化合物のシラノール基及び／又はアルコキシ基がさらに加水分解して生成したシラノール基による縮合反応、及びエポキシ基含有アミン化合物のエポキシ基と前記シラノール基との付加反応、エポキシ基がシラノール基と開環付加反応した後に生成したヒドロキシ基と前記シラノール基の縮合反応により一体となって３次元架橋反応結合した樹脂物を言う。
【００３４】
また、本発明の電子写真感光体用塗布液は、前記一般式（３）及び／又は一般式（４）で表される化合物等のケイ素含有モノマーを加水分解するのに必要な水を添加し、酸性条件下〜塩基性条件下で加水分解して用いてもよい。
【００３５】
加水分解は、純水もしくは塩酸または硫酸または酢酸等の酸性水溶液で行うことができ、アルコキシシラン単独あるいは溶媒で希釈して行う。また、複数のアルコキシシラン体を使用する場合は、別々に加水分解して混合することも、混合したアルコキシシラン体を共加水分解することも、一方のアルコキシシラン体を加水分解した後に他のアルコキシシラン体を加え加水分解を継続する逐次加水分解法を適用することもできる。
【００３６】
前記電子写真感光体用塗布液に用いられる溶媒は、ケトン系、エステル系、エーテル系あるいは芳香族系溶媒から選ばれる１種以上の溶媒とアルコール系溶媒との混合溶媒が好ましい。
ケトン系溶媒としてはメチルエチルケトン、メチルイソブチルケトン、アセトン、シクロヘキサノン等が、エステル系溶媒としては酢酸エチル、酢酸ｔ−ブチル等が、エーテル系溶媒としてはメチルセルソルブ、エチルセルソルブ、ジエチルエーテル、ジブチルエーテル、ジプロピルエーテル、テトラヒドロフラン、１，４−ジオキサン、１，３−ジオキソラン等が、芳香族系溶媒としてはトルエン、キシレン等が挙げられる。また、アルコール系溶媒としてはメタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、ｔ−ブタノール等が挙げられる。
【００３７】
このように種々の溶媒が使用可能であるが、各組成物の溶解性と架橋硬化時の均一膜性を達成するためには、溶解性を考慮すると共に沸点の比較的高い溶媒を混合することが好ましい。
好ましい溶媒としては、ブタノール、ベンジルアルコール、シクロヘキサノン、酢酸−２−メトキシエチル、テトラヒドロフラン、アセチルアセトンを挙げることができ、これらの内、ベンジルアルコール、シクロヘキサノンは沸点が比較的高い溶媒として好ましく使用される。これらの溶媒を使用しないときは、均一な塗工液の作製および均一硬化膜の作製が困難になる。
これらの内、エポキシ基含有アミン化合物、アルコキシシラン化合物及びシラノール化合物を溶解させるものが使用される。
【００３８】
前記電子写真感光体用塗布液中の固形分濃度は前記アルコキシシラン化合物、シラノール化合物、エポキシ基含有アミン化合物の構造や塗布方法等により最適なものが選ばれるが、通常２〜５０重量％が好ましい。
【００３９】
また前記電子写真感光体用塗布液には架橋反応を促進する触媒として有機カルボン酸、亜硝酸、亜硫酸、アルミン酸、炭酸及びチオシアン酸の各アルカリ金属塩、有機アミン塩（水酸化テトラメチルアンモニウム、テトラメチルアンモニウムアセテート）、スズ有機酸塩（スタンナスオクトエート、ジブチルチンジアセテート、ジブチルチンジラウレート、ジブチルチンメルカプチド、ジブチルチンチオカルボキシレート、ジブチルチンマリエート等）、アルミニウム、亜鉛のオクテン酸、ナフテン酸塩、アセチルアセトン錯化合物等を使用しても良い。
触媒の量としては前記アルコキシシラン化合物、シラノール化合物１００重量部に対し０．１〜１０重量部を用いることが好ましい。
【００４０】
該触媒としては、特に、一般式、ＡｌＸ_ｎＹ_３−ｎで示されるアルミニウムキレート化合物が好ましい。
（ここでＸは低級アルコキシル基、ＹはＭ^１ＣＯＣＨ_２ＣＯＭ^２、及びＭ^３ＣＯＣＨ_２ＣＯＯＭ^４からなる群から選ばれた化合物から生じる配位子、Ｍ^１、Ｍ^２、Ｍ^３およびＭ^４は低級アルキル基、ｎは０、１または２である。）
このアルミニウムキレート化合物を使用することにより、未加熱時は架橋がほとんど進行せず、加熱時に速やかに架橋が進行するため、塗工液のポットライフが長く、製造時の塗工条件管理が容易になる。
該アルミニウムキレート化合物において、触媒活性、溶解性、安定性の観点から具体的な化合物として以下の例が挙げられる。
アルミニウムアセチルアセトナート、アルミニウムエチルアセトアセテートビスアセチルアセトナート、アルミニウムビスアセトアセテートアセチルアセトナート、アルミニウムジ−ｎ−ブトキシドモノエチルアセトアセテート、アルミニウムジ−ｉ−プロポキシドモノメチルアセトアセテートおよびこれらの混合物。
【００４１】
さらに、前記電子写真感光体用塗布液は、さらにコロイダルシリカ、コロイダルアルミナ等の金属酸化物のコロイドを加えて作製しても良い。コロイダルシリカは水性またはアルコール性のゾルで、粒径が１００ｎｍ以下のものが好ましく、５０ｎｍ以下のものが特に好ましい。
成分Ｄの平均粒子径１〜１００ｎｍの微粒子状シリカも上記コロイダルシリカとして使用される。
コロイダルシリカを加えることで、成膜性が向上し、熱硬化時の亀裂の発生も無くなる。また、硬度が上がり、耐傷性が高まる。
コロイダルシリカの添加量はとくに制限は無いが乾燥後の前記硬化性樹脂層中に１〜３０重量％含有させることが好ましい。
【００４２】
また、前記電子写真感光体用塗布液には、この他、電子写真用の素材として公知の様々な素材、例えばヒンダードアミン、ヒンダードフェノールなどの酸化防止剤、シリコンオイルなどの平滑剤、アミン化合物などの正孔輸送剤、キノン類などの電子輸送剤を添加してもよい。
【００４３】
塗膜の乾燥温度としては使用する溶媒種、触媒の有無によって異なるが、およそ６０〜１６０℃の範囲で１０分〜５時間の加熱が好ましく、さらに８０〜１５０℃の範囲で２０分〜３時間で加熱硬化させるのが好ましく、より好ましくは１００〜１５０℃の範囲で３０分〜２時間の加熱が好ましい。８０℃未満の場合、架橋反応が十分に進行しない場合があり、１５０℃を越える場合は、感光体中の材料劣化により電子写真特性が悪化する傾向がある。
【００４４】
本発明の最表面層を適用させる感光体の層構成には特に限定は無い。しかしながら好ましい態様は従来公知の感光体上に保護層として本発明の最表面層を設けた構成である。
その場合の保護層の膜厚は、通常０．１〜１５μｍ、好ましくは１〜１５μｍ、より好ましくは１〜５μｍである。１μｍより薄い場合は、十分な耐摩耗性が得られず、１５μｍを超える場合は、保護層に亀裂や離脱が発生しやすくなる。
【００４５】
以上のように本発明で使用される組成物及び組成物の製造法について説明したが、より好ましい組成物構成について説明する。
一つは、下記Ａ、Ｂ、Ｃの成分を含み、且つ成分Ａ、Ｂの混合割合が、固形分重量比で、（成分Ｂ）／（成分Ａ＋成分Ｂ）＝０．１〜０．７、である硬化被覆組成物である。
Ａ：分子中にケイ素原子に結合した水酸基を有するシラン化合物
Ｂ：下記一般式（１）で表されるエポキシ化合物
【化２４】

（式中、Ｒ^１は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表す。Ａｒ^１は少なくとも１個の３級アミノ基を有するアリール基、少なくとも１個の３級アミノ基を有する複素環基を表す。Ａｒ^２、Ａｒ^３は置換もしくは無置換のアリレン基を表す。但し、Ａｒ^２とＡｒ^３は同一でも異なっていてもよい。ｎは０〜１００の整数を表す。）
Ｃ：一般式、ＡｌＸ_ｎＹ_３−ｎで示されるアルミニウムキレート化合物
（式中、Ｘは低級アルコキシル基、ＹはＭ^１ＣＯＣＨ_２ＣＯＭ^２、及びＭ^３ＣＯＣＨ_２ＣＯＯＭ^４からなる群から選ばれた化合物から生じる配位子、Ｍ^１、Ｍ^２、Ｍ^３およびＭ^４は低級アルキル基、ｎは０、１または２である。）
【００４６】
成分Ａの分子中にケイ素原子に結合した水酸基を有するシラン化合物とは前記アルコキシシラン化合物の加水分解物である。
成分Ｂは、前記エポキシ基含有アミン化合物が好ましい構造体である。
この成分Ａと成分Ｂの混合割合は成分Ｂの固形分重量比（成分Ｂ）／（成分Ａ＋成分Ｂ）で０．１〜０．７である。０．１よりも小さい場合は、電荷輸送性が殆ど得られなくなり、感光体の残留電位の上昇や感度低下等の特性劣化をもたらす。逆に、０．７を超える場合はシラノール縮合架橋部の減少により膜強度が大幅に下がり、感光体の耐久性持続が図れない。
成分Ｃのアルミニウムキレート化合物は前記と同様の物が使用されるが、成分Ａ及び成分Ｂの総量１００重量部に対して約０．０１〜３０重量部が添加される。これより少ない場合は、硬化が不完全になり、多すぎると膜が脆くなる。
【００４７】
もう一つの好ましい例は、下記の成分Ａ、Ｂ、Ｃ、Ｄを含み、且つ成分Ａ、Ｂ、Ｄの混合割合が、固形分重量比で、（成分Ｂ）／（成分Ａ＋成分Ｂ＋成分Ｄ）＝０．１〜０．６、（成分Ｄ）／（成分Ａ＋成分Ｂ＋成分Ｄ）＝０．０１〜０．３、である組成物である。
Ａ、Ｂ、Ｃの各成分は上記と同様である。
成分Ｄは、平均粒子系１〜１００ｎｍの微粒子状シリカである。
成分Ａ、Ｂ、Ｄの混合割合（固形分重量比）は、成分Ｂが０．１から０．６であり、成分Ｄが０．０１から０．３である。成分Ｂが０．１よりも小さい場合は、電荷輸送性が殆ど得られなくなり、感光体の残留電位の上昇や感度低下等の特性劣化をもたらす。逆に、０．６を超える場合はシラノール縮合架橋部の減少により膜強度が大幅に下がり、感光体の耐久性持続が図れない。
また、成分Ｄが０．０１より小さい場合は、成膜性の向上、塗膜硬度の向上が望めなく、逆に、０．３を超えるとクラッキングのような塗膜欠陥を生じたり、解像度が低下したりする問題を生じる。
成分Ｃのアルミニウムキレート化合物は前記と同様の物が使用されるが、成分Ａ及び成分Ｂ及び成分Ｄの総量１００重量部に対して約０．０１〜３０重量部を添加することが好ましい。これより少ない場合は、硬化が不完全になり、多すぎると膜が脆くなる。
【００４８】
本発明の最表面層を適用させる感光体の層構成には特に限定は無い。しかしながら好ましい態様は従来公知の感光体上に保護層として本発明の最表面層を設けた構成である。
代表的な構成としてはアルミニウムのような導電性支持体上に下引き層、電荷発生層、電荷輸送層、保護層を順次形成したものである。
【００４９】
本発明の電子写真感光体の感光層に用いられる電荷発生物質としては公知のどのようなものでの使用できる。
例えば、Ａ型、Ｂ型及びＹ型のチタニルフタロシアニン、Ｘ型及びτ型の無金属フタロシアニン、銅フタロシアニン等の金属フタロシアニン類、ナフタロシアニン類、またこれら２種のフタロシアニンの混晶、アゾ化合物、ピリリウム化合物、ペリレン系化合物、シアニン系化合物、スクアリウム化合物、多環キノン化合物等が挙げられる。これら電荷発生物質は単独で又は適当なバインダー樹脂中に分散して層形成が行われる。
【００５０】
また本発明の電子写真感光体の感光層に用いられる電荷輸送物質としては公知のどのようなものでも使用できる。
例えば正孔輸送物質の代表的なものとして、オキサゾール、オキサジアゾール、チアゾール、チアジアゾール、イミダゾール等に代表される含窒素複素環核、及びその縮合環核を有する化合物、ポリアリールアルカン型の化合物、ヒドラゾン系化合物、ピラゾリン系化合物、トリアリールアミン系化合物、スチリル系化合物、ポリス（ビス）スチリル系化合物、スチリルトリフェニルアミン系化合物、β−フェニルスチリルトリフェニルアミン系化合物、ブタジエン系化合物、ヘキサトリエン化合物、カルバゾール系化合物、縮合多環系化合物等が挙げられ、電子輸送物質の代表的なものとしては、ベンゾキノン、ナフトキノン、アントラキノン、チオピラノン、フルオレノン、インデノン、インダンジオン系化合物等が挙げられる。これら電荷輸送物質は通常、適当なバインダー樹脂中に溶解して層形成が行われる。
【００５１】
電荷発生物質、電荷輸送物質の分散、溶解の使用される溶媒としては、トルエン、キシレン等の炭化水素類；メチレンクロライド、１，２−ジクロルエタン等のハロゲン化炭化水素；メチルエチルケトン、シクロヘキサノン等のケトン類；酢酸エチル、酢酸ブチル等のエステル類；メタノール、エタノール、メチルセルソルブ、エチルセルソルブ等のアルコール類及びこの誘導体；テトラヒドロフラン、１，４−ジオキサン、１，３−ジオキソラン等のエーテル類；ピリジンやジエチルアミン等のアミン類；Ｎ，Ｎ−ジメチルホルムアミド等のアミド類；その他脂肪酸及びフェノール類；二硫化炭素や燐酸トリエチル等の硫黄、燐化合物等の１種又は２種以上を用いることができる。
【００５２】
本発明の電子写真感光体の感光層の中で表面層以外の感光層には、ポリスチレン、アクリル樹脂、メタクリル樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、ポリビニルブチラール樹脂、エポキシ樹脂、ポリウレタン樹脂、フェノール樹脂、ポリエステル樹脂、アルキッド樹脂、ポリカーボネート樹脂、シリコーン樹脂、メラミン樹脂ならびにこれらの樹脂の繰り返し単位のうちの２つ以上を含む共重合体樹脂が使用できる。また、これらの絶縁性樹脂の他、ポリ−Ｎ−ビニルカルバゾール等の高分子有機半導体が使用できる。
【００５３】
本発明の電子写真感光体の感光層におけるバインダー樹脂と電荷発生物質との割合は、バインダー樹脂１００重量部に対し電荷発生物質５０〜６００重量部が好ましい。またバインダー樹脂と電荷輸送物質との割合は、バインダー樹脂１００重量部に対し電荷輸送物質１０〜１００重量部が好ましい。
【００５４】
本発明の電子写真感光体の感光層の膜厚は、電荷発生層は０．１〜１０μｍ、電荷輸送層は５〜３０μｍが好ましい。また感光層が単層構成の場合は５〜４０μｍが好ましい。
【００５５】
本発明の電子写真感光体において感光層を支持する導電性支持体としては、アルミニウム、ニッケルなどの金属板・金属ドラム、又はアルミニウム、酸化錫、酸化インジウムなどを蒸着したプラスチックフィルム、又は導電性物質を塗布した紙・プラスチックフィルム・ドラムを使用することができる。
【００５６】
本発明の電子写真感光体の下引き層に用いられる材料としては、ポリアミド樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、ならびにこれらの樹脂の繰り返し単位のうちの２つ以上を含む共重合体樹脂が挙げられる。またシランカップリング剤、チタンカップリング剤等の有機金属化合物を熱硬化させた硬化性金属樹脂化合物が挙げられる。
下引き層の膜厚は、０．０１〜１５μｍが好ましい。
【００５７】
また本発明の電子写真感光体には、その他、感色性補正の染料や感光層に酸化防止剤等の添加剤を添加しても良い。
【００５８】
本発明の電子写真感光体を製造するための塗布加工方法としては、各層形成用の塗布液をディップ塗布、スプレー塗布、円形量規制型塗布等が用いることできる。特に感光層の保護層側の塗布加工は下層の膜を極力溶解させないため、また均一塗布加工を達成するためにスプレー塗布、円形量規制型塗布（円形スライドホッパーがその代表例である）を用いるのが好ましい。なお前記スプレー塗布については特開平３−９０２５０号公報、特開平３−２６９２３８号公報にその記載があり、前記円形量規制型塗布については特開昭５８−１８９０６１号公報に詳細が記載されている。
【００５９】
【実施例】
以下、本発明について実施例を挙げて具体的に説明するが、本発明が実施例により制約を受けるものではない。なお、部はすべて重量部である。
【００６０】
合成例
＜エポキシ基含有アミン化合物の合成＞
かき混ぜ装置、温度計、滴下漏斗およびエピクロルヒドリンと水との共沸混合物を凝縮分離して下層のエピクロルヒドリン層を戻すための装置をつけた反応容器に、４−〔２，２−ビス（４−ヒドロキシフェニル）ビニル〕フェニル−ビス（４−メチルフェニル）アミン１９．３４ｇ（４０．０ｍｍｏｌ）とエピクロルヒドリン３７．０１ｇ（４００．０ｍｍｏｌ）を入れ、窒素気流下、１１０℃で加熱攪拌した。これに反応系内の温度が１００℃〜１２０℃を維持するように、２０ｗｔ％水酸化ナトリウム水溶液１９．２０ｇ（９６．０ｍｍｏｌ）を３時間かけて滴下した。反応中に留去された水とエピクロルヒドリンはエピクロルヒドリンのみ反応容器に戻し、水酸化ナトリウム水溶液の滴下終了後、１１０℃でさらに１時間反応させた。これを室温まで放冷し、過剰のエピクロルヒドリンを減圧回収した後、トルエンを加えて有機層を水洗浄し、無水硫酸マグネシウムで乾燥後、減圧下でトルエン溶媒を留去して、黄色の粗生成物２０．７５ｇ（収率８７．１％）、融点１１１．０〜１１６．０℃を得た。これをシリカゲルでカラムクロマト精製（溶離液：トルエン／酢酸エチル＝２０／１ｖｏｌ．）した後、酢酸エチルとエタノールから再結晶を行って淡黄色針状結晶１５．８５ｇ（収率６６．５％）を得た。融点は１２８．０〜１２９．０℃であった。
赤外線吸収スペクトル（ＮａＣｌ液膜法）を図１に示す。
元素分析結果を以下に示す。

【００６１】
実施例１
アルミニウムシリンダー上に下記組成の下引き層塗工液、電荷発生層塗工液、および電荷輸送層塗工液を、浸漬塗工によって順次塗布、乾燥し、３．５μｍの下引き層、０．２μｍの電荷発生層、２６μｍの電荷輸送層を形成した。
＜下引き層塗工液＞
二酸化チタン粉末：　　　　　　　　　　　　　　　　　　　４００部
メラミン樹脂：　　　　　　　　　　　　　　　　　　　　　　４０部
アルキッド樹脂：　　　　　　　　　　　　　　　　　　　　　６０部
２−ブタノン：　　　　　　　　　　　　　　　　　　　　　５００部
＜電荷発生層塗工液＞
下記構造式で表されるビスアゾ顔料：　　　　　　　　　　　　１２部
【化２５】

ポリビニルブチラール：　　　　　　　　　　　　　　　　　　　５部
２−ブタノン：　　　　　　　　　　　　　　　　　　　　　２００部
シクロヘキサノン：　　　　　　　　　　　　　　　　　　　４００部
＜電荷輸送層塗工液＞
ポリカーボネート（Ｚポリカ、帝人化成製）：　　　　　　　　１０部
下記構造式で表される電荷輸送物質：　　　　　　　　　　　　１０部
【化２６】

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
次いで、電荷輸送層上にさらに、下記組成の保護層塗工液をスプレー塗工法によって約３μｍの保護層を形成し、その後、１２０℃で２時間加熱乾燥し、実施例１の電子写真感光体を作製した。
＜保護層塗工液＞
合成例により得られた
下記構造式で表されるエポキシ基含有アミノ化合物：　　　４．２部
【化２７】

メチルトリメトキシシラン：　　　　　　　　　　　　　　　　　５部
フェニルトリエトキシシラン：　　　　　　　　　　　　　　　　５部
１％酢酸水溶液：　　　　　　　　　　　　　　　　　　　５．５７部
テトラヒドロフラン：　　　　　　　　　　　　　　　　　３０．７部
ｎ−ブタノール：　　　　　　　　　　　　　　　　　　　３．６７部
【００６２】
実施例２
実施例１において保護層塗工を以下のように行うこと以外は実施例１と同様にして電子写真感光体を作製した。
予め下記組成の処方液を作製し、６０℃で２時間撹拌し、アルコキシシランをシラノール化した。
＜保護層塗工液の予備処方液＞
メチルトリメトキシシラン：　　　　　　　　　　　　　　　　　５部
フェニルトリエトキシシラン：　　　　　　　　　　　　　　　　５部
１％酢酸水溶液：　　　　　　　　　　　　　　　　　　　５．５７部
テトラヒドロフラン：　　　　　　　　　　　　　　　　　３０．７部
ｎ−ブタノール：　　　　　　　　　　　　　　　　　　　３．６７部
その後、実施例１で使用したエポキシ基含有アミノ化合物４．２部を添加し、塗工液を作製した。この塗工液を用いて実施例１と同様にして保護層を形成し、実施例２の電子写真感光体を作製した。
【００６３】
実施例３
実施例１において保護層塗工を以下のように行うこと以外は実施例１と同様にして電子写真感光体を作製した。
メチルトリメトキシシラン２１部及びフェニルトリエトキシシラン２１部中に氷冷下で１％酢酸水溶液８．１６部を２５分かけて滴下し、その後５℃で３０分撹拌し、さらに室温２４℃で２時間撹拌し、加水分解させた。
その後、下記組成の塗工液を作製した。
＜保護層塗工液＞
上記加水分解液：　　　　　　　　　　　　　　　　　　　　　　３部
実施例１で使用したエポキシ基含有アミノ化合物：　　　　０．９８部
酢酸−２−メトキシエチル：　　　　　　　　　　　　　　２．６２部
シクロヘキサノン：　　　　　　　　　　　　　　　　　　２．４２部
テトラヒドロフラン：　　　　　　　　　　　　　　　　　０．９８部
アセチルアセトン：　　　　　　　　　　　　　　　　　　０．１２部
アルミニウムアセチルアセトナート：　　　　　　　　　　０．１２部
この塗工液を用いてリング塗工法を用いる他は実施例１と同様にして３μｍの保護層を有する実施例３の電子写真感光体を作製した。
【００６４】
実施例４
実施例１において保護層塗工を以下のように行うこと以外は実施例１と同様にして電子写真感光体を作製した。
メチルトリメトキシシラン２１部及びフェニルトリエトキシシラン２１部中に氷冷下で１％酢酸水溶液８．１６部を２５分かけて滴下し、その後５℃で３０分撹拌し、さらに室温２４℃で２時間撹拌し、加水分解させた。
その後、下記組成の塗工液を作製した。

この塗工液を用いてリング塗工法を用い、塗工後のセッティング時間を３０分、硬化時間を１３０℃、１時間とした他は実施例１と同様にして２μｍの保護層を有する実施例４の電子写真感光体を作製した。
【００６５】
比較例１
実施例１においてエポキシ基含有アミノ化合物の代わりに下記構造式で表されるヒドロキシ基含有アミン化合物を使用する以外は実施例１と他は同様にして比較例１の電子写真感光体を作製した。
【化２８】

【００６６】
比較例２
実施例１において保護層を設けない以外は実施例１と同様にして比較例２の電子写真感光体を作製した。
【００６７】
得られた電子写真感光体をリコー製ｉｍａｇｉｏＭＦ２２００（６５５ｎｍＬＤ光源使用改造機）にセットし、１万枚の通紙ランニングを行った後の摩耗量（膜厚変化）測定と感光体表面の顕微鏡観察と、機内電位の暗部電位（ＶＤ）、明部電位（ＶＬ）の電位変動測定を行った。また、テストチャートの出力画像から目視による画質評価を行った。表面観察では、微細な線状傷のみの場合○、一部粒状のへこみを生じる場合△、粒状のへこみが全面に出たり、膜の脱落が見られる場合×とした。画質では、目立った画質低下のない場合○、一部、地汚れ、白抜け、解像度低下等の異常画像を生じる場合△、全面に渡って濃度低下や異常画像の発生する場合×とした。その結果を下記に示す。また、感光体の表面に指紋を付着させ、４８時間放置後のクラック発生の有無を調べた。クラックの発生しない場合○、一部発生する場合△、全面に発生する場合×とした。結果を下記表１に示す。
【００６８】
【表１】

【００６９】
以上のように本発明の電子写真感光体は耐摩耗性が高く、電子写真特性も保護層を設けないものと同等の特性を有し、繰り返し使用時の電位変動が小さく、耐クラック性も良く、高画質安定性と耐摩耗性を両立させた寿命の長い電子写真用感光体を提供しうることがわかる。
【００７０】
【発明の効果】
従来、ポリオルガノシロキサン架橋膜に電荷輸送能を付与するため、縮合反応のみで架橋させており、反応時に膜の収縮が大きくなり、膜中の内部応力が増加し、内部欠陥が発生したり、膜の微少な剥がれが生じたりして、機械的に十分な強度が得られなかった。また、多官能な電荷輸送性化合物の合成が容易ではなく、これらを反応させた膜の架橋密度が低下し、十分硬い膜の作製が困難であった。
本発明では、電子写真感光体において、エポキシ基とシラノール基との開環を伴う付加反応によって電荷輸送性基を導入するため膜の収縮が小さくなり歪みの少ない膜が得られると共に、エポキシ基の開環によって生じたヒドロキシ基も架橋反応に寄与でき、少ない官能基数で多官能体と同じ働きができるため、架橋密度も高く、硬くて傷のつきにくい膜の作製が可能になる。
また、本発明では、上記付加反応の原材料にエポキシ基含有アミン化合物を用い、しかも該エポキシ基含有アミン化合物としてホール移動度の高い前記一般式（１）及び（２）で表される化合物を用いた場合、電荷輸送性化合物を架橋膜中に導入可能としたため、電荷移動に優れ、優れた電子写真特性を示し、高耐久な電子写真感光体の提供が可能になる。
また、該電荷輸送性化合物の電荷輸送性基が前述のように二重に架橋されているため、遊離体が発生しにくく、クラック等にも強い電子写真感光体となる。
【図面の簡単な説明】
【図１】合成例で得られたエポキシ基含有アミン化合物の赤外線吸収スペクトル図（ＮａＣｌ液膜法）。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member used for an image output apparatus such as a printer, a copying machine, and a facsimile by an electrophotographic method. More specifically, it has a small diameter and high abrasion resistance, hardly scratches the surface, does not crack, has good chargeability, has a small residual potential when irradiated with light, and has a charge potential even after repeated use. Also, the present invention relates to a long-life electrophotographic photoreceptor having low fluctuations in residual potential, hardly causing abnormal images such as image blur, and achieving both high image quality stability and abrasion resistance, and a method for producing the same.
[0002]
[Prior art]
2. Description of the Related Art In recent years, there has been a remarkable development of information processing system machines using an electrophotographic system. Particularly, laser printers and digital copiers that convert information into digital signals and record information by light have remarkably improved in print quality and reliability. Further, they have been applied to laser printers or digital copying machines capable of full-color printing by fusing with high-speed technology. From such a background, as a required function of the photoconductor, achieving both high image quality and high durability has become a particularly important issue.
[0003]
As photoreceptors used in these electrophotographic laser printers and digital copiers, those using organic photosensitive materials are widely applied in general because of cost, productivity and pollution-free properties. I have. Organic electrophotographic photoreceptors include a photoconductive resin represented by polyvinyl carbazole (PVK), a charge transfer complex type represented by PVK-TNF (2,4,7-trinitrofluorenone), and a phthalocyanine-binder. And a function-separated type photoconductor using a combination of a charge generating substance and a charge transporting substance.
[0004]
The mechanism of electrostatic latent image formation in a function-separated type photoreceptor is that, when the photoreceptor is charged and irradiated with light, the light passes through the charge transport layer and is absorbed by the charge generating substance in the charge generation layer to generate charges. . The generated charge is injected into the charge transport layer at the interface between the charge generation layer and the charge transport layer, and further moves in the charge transport layer by an electric field to neutralize the surface charge of the photoreceptor, thereby forming an electrostatic latent image. To form.
[0005]
However, organic photoreceptors are susceptible to film shaving due to repeated use, and as the film of the photosensitive layer progresses, ground potential due to lowering of the charging potential of the photoreceptor, deterioration of photosensitivity, scratches on the surface of the photoreceptor, etc. In addition, there is a strong tendency that image quality deterioration such as a decrease in image density is promoted, and the abrasion resistance of the photoreceptor has been conventionally cited as a major problem. Furthermore, in recent years, the high durability of the photoconductor has become an even more important issue due to the reduction in the diameter of the photoconductor along with the increase in the speed of the electrophotographic apparatus or the miniaturization of the apparatus. In addition, foreign matter may adhere to the surface of the photoreceptor, causing crystallization or cracking of the film. In particular, when a person directly touches the photoreceptor, sebum adheres to the surface of the photoreceptor, which may trigger a crack. Cracks cause image defects and shorten the life of the photoreceptor.
[0006]
As a method of realizing high durability of the photoconductor, a method of providing a protective layer on the outermost surface of the photoconductor, imparting lubricity to the protective layer, containing a filler, or curing is known. I have.
For example, JP-A-07-295248, JP-A-07-301936, and JP-A-08-08940 disclose a surface layer containing fluorine-modified silicone oil to improve the surface properties and improve the photoreceptor surface. There are proposals to improve wear resistance. However, such a method of adding the oil component to the photosensitive layer to lower the coefficient of friction does not maintain the abrasion resistance effect because the component transferred to the surface is immediately removed.
[0007]
On the other hand, there has been an attempt to improve the abrasion resistance by adding an inorganic filler or crosslinked resin particles to a photoconductor surface layer. In these cases, although the abrasion resistance is improved, there is a drawback that the influence on the charged potential and the residual potential is large, and the potential fluctuation particularly during repeated use is large.
[0008]
Various studies using a thermosetting resin have been made. In particular, those using a resin in which a skeleton having a charge transporting property is co-crosslinked in a three-dimensional crosslinked film have attracted attention as being able to achieve both electrophotographic characteristics and abrasion resistance.
For example, an organic silicon-modified hole transporting compound in which silicon having a hydrolyzable group is directly introduced into a charge transporting agent is used for an electrophotographic photoreceptor (Japanese Patent Application Laid-Open No. 9-190004 ... Patent Document 1). One using a film in which a charge-transporting compound having a hydroxyl group, amino group or thiol group capable of undergoing a condensation reaction is introduced into a siloxane three-dimensional crosslinked film (Japanese Patent Laid-Open No. 2000-171990 ... Patent Document 2). There is known one using a three-dimensional crosslinked film of an acrylic compound and a charge transporting material having two or more in the molecule (Japanese Patent Application Laid-Open No. 2000-206715).
[0009]
However, in the case of JP-A No. 9-190004, it is difficult to synthesize and purify the organosilicon-modified hole-transporting compound to be used, which causes a decrease in film strength and a decrease in electrophotographic characteristics. Or cause problems. Further, in the case of JP-A-2000-171990, there is a problem in that the use of the charge-transporting compound having a reactive group is limited in terms of compatibility or the strength of the copolymerized crosslinked film is not sufficient. is there. Further, in the case of JP-A-2000-206715, there are problems that the residual chain-polymerizable group adversely affects gas resistance and mechanical strength is not sufficient.
[0010]
[Patent Document 1]
JP-A-9-190004
[Patent Document 2]
JP 2000-171990 A
[0011]
[Problems to be solved by the invention]
An object of the present invention is to solve the above-described problems of the conventional electrophotographic photoreceptor, and particularly has high abrasion resistance, is hardly scratched on the surface, does not crack, has good chargeability, Electrons with low residual potential during irradiation, little change in charged potential and residual potential even after repeated use, less occurrence of abnormal images such as image blur, and long life with both high image quality stability and abrasion resistance It is an object of the present invention to provide a photoreceptor and a method for manufacturing the same.
[0012]
[Means for Solving the Problems]
According to the present invention, the following electrophotographic photoreceptors (1) to (19) and a method for producing the same are provided.
(1) An electrophotographic photoreceptor having a layer containing a composition in which a charge transporting group is bonded by a reaction between an epoxy group and a silanol group in a crosslinked product formed by a condensation reaction of a silanol group. .
(2) An electrophotographic photoreceptor having at least a photosensitive layer provided on a conductive support, wherein the outermost surface layer of the electrophotographic photoreceptor mainly comprises a reaction product of an epoxy group-containing amine compound and an alkoxysilane compound. Electrophotographic photoreceptor.
(3) An electrophotographic photoreceptor having at least a photosensitive layer provided on a conductive support, wherein the outermost surface layer of the electrophotographic photoreceptor mainly comprises a reaction product of an epoxy group-containing amine compound and a silanol compound. Electrophotographic photoreceptor.
(4) The electrophotographic photoreceptor according to (3), wherein the silanol compound is a compound produced by hydrolysis of an alkoxysilane compound.
(5) In an electrophotographic photosensitive member having at least a photosensitive layer provided on a conductive support, a coating solution in which the outermost surface layer of the electrophotographic photosensitive member is composed of at least a mixture of an epoxy group-containing amine compound and an alkoxysilane compound. An electrophotographic photoreceptor, comprising a reaction product obtained by applying and reacting the above.
(6) In an electrophotographic photosensitive member having at least a photosensitive layer provided on a conductive support, the outermost surface layer of the electrophotographic photosensitive member contains at least a silanol compound generated by hydrolysis of an alkoxysilane compound and an epoxy group-containing photosensitive member. An electrophotographic photoreceptor comprising a reaction product obtained by applying a coating solution comprising a mixture of amine compounds and then reacting the coating solution.
(7) The electrophotographic photoreceptor according to (5) or (6), wherein after application of the coating liquid, the coating liquid is cured by heating at 100 ° C. or higher.
(8) The electrophotographic photosensitive member according to any one of (2) to (7), wherein the epoxy group-containing amine compound is a compound represented by the following general formula (1).
Embedded image

(Where R ¹ Represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹ Represents an aryl group having at least one tertiary amino group and a heterocyclic group having at least one tertiary amino group. Ar ² , Ar ³ Represents a substituted or unsubstituted arylene group. Where Ar ² And Ar ³ May be the same or different. n represents an integer of 0 to 100. )
(9) The electrophotographic photoreceptor according to any one of (2) to (8), wherein the epoxy group-containing amine compound is a compound represented by the following general formula (2).
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(Where R ⁴ ~ R ²⁵ Represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, which may be the same or different. n represents an integer of 0 to 100. )
(10) The electrophotographic photosensitive member according to any one of (2) and (4) to (9), wherein the alkoxysilane compound is a compound represented by the following general formula (3).
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(R) _n -Si- (X) _4-n (3)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to a silicon atom, X represents a hydrolyzable group, at least one is an alkoxy group, and n represents an integer of 0 to 3. )
(11) The electrophotographic photosensitive member according to any one of (3), (4), (6) to (9), wherein the silanol compound is a compound represented by the following general formula (4). body.
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(R) _n -Si- (Y) _4-n (4)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to a silicon atom, n represents an integer of 0 to 3, when n is 3, Y represents a hydroxyl group, and when n is 0 to 2, Y represents one hydroxyl group and the remainder represents a hydroxyl group or a hydrolyzable group.)
(12) The electrophotographic photoreceptor according to any one of (2) to (11), wherein the alkoxysilane compound and / or the silanol compound comprises a mixture of two or more kinds.
(13) The electrophotographic photoreceptor according to any one of (2) to (12), wherein the alkoxysilane compound and / or silanol compound is a compound having at least one aromatic group.
(14) The following components A, B and C are contained, and the mixing ratio of the components A and B is (component B) / (component A + component B) = 0.1 to 0.7 in terms of solid content weight ratio, An electrophotographic photoreceptor having on its surface a cured coating composition of the formula:
A: A silane compound having a hydroxyl group bonded to a silicon atom in the molecule
B: an epoxy compound represented by the following general formula (1)
Embedded image

(Where R ¹ Represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹ Represents an aryl group having at least one tertiary amino group and a heterocyclic group having at least one tertiary amino group. Ar ² , Ar ³ Represents a substituted or unsubstituted arylene group. Where Ar ² And Ar ³ May be the same or different. n represents an integer of 0 to 100. )
C: General formula, AlX _n Y _3-n Aluminum chelate compound represented by
(Wherein X is a lower alkoxyl group, Y is M ¹ COCH ₂ COM ² , And M ³ COCH ₂ COOM ⁴ A ligand derived from a compound selected from the group consisting of ¹ , M ² , M ³ And M ⁴ Is a lower alkyl group, and n is 0, 1 or 2. )
(15) It contains the following components A, B, C, and D, and the mixing ratio of the components A, B, and D is (component B) / (component A + component B + component D) = 0. An electrophotographic photoreceptor having on its surface a cured coating composition wherein 1 to 0.6, (Component D) / (Component A + Component B + Component D) = 0.01 to 0.3.
A: A silane compound having a hydroxyl group bonded to a silicon atom in the molecule
B: an epoxy compound represented by the following general formula (1)
Embedded image

(Where R ¹ Represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹ Represents an aryl group having at least one tertiary amino group and a heterocyclic group having at least one tertiary amino group. Ar ² , Ar ³ Represents a substituted or unsubstituted arylene group. Where Ar ² And Ar ³ May be the same or different. n represents an integer of 0 to 100. )
C: General formula, AlX _n Y _3-n Aluminum chelate compound represented by
(Wherein X is a lower alkoxyl group, Y is M ¹ COCH ₂ COM ² , And M ³ COCH ₂ COOM ⁴ A ligand derived from a compound selected from the group consisting of ¹ , M ² , M ³ And M ⁴ Is a lower alkyl group, and n is 0, 1 or 2. )
D: Fine particle silica having an average particle diameter of 1 to 100 nm
(16) The electrophotographic photosensitive member according to (14) or (15), wherein the cured coating composition has a thickness of 1 to 15 μm.
[0013]
(17) The following components A, B, and C are contained, and the mixing ratio of the components A and B is (component B) / (component A + component B) = 0.1 to 0.7 in terms of solid content weight ratio; Preparing a coating solution in which the composition is dissolved or dispersed in a solvent, applying the coating solution on the surface of the photoreceptor, and then heating and curing at 80 to 150 ° C. How to make the body.
A: A silane compound having a hydroxyl group bonded to a silicon atom in the molecule
B: an epoxy compound represented by the following general formula (1)
Embedded image

(Where R ¹ Represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹ Represents an aryl group having at least one tertiary amino group and a heterocyclic group having at least one tertiary amino group. Ar ² , Ar ³ Represents a substituted or unsubstituted arylene group. Where Ar ² And Ar ³ May be the same or different. n represents an integer of 0 to 100. )
C: General formula, AlX _n Y _3-n Aluminum chelate compound represented by
(Wherein X is a lower alkoxyl group, Y is M ¹ COCH ₂ COM ² , And M ³ COCH ₂ COOM ⁴ A ligand derived from a compound selected from the group consisting of ¹ , M ² , M ³ And M ⁴ Is a lower alkyl group, and n is 0, 1 or 2. )
(18) It contains the following components A, B, C, and D, and the mixing ratio of the components A, B, and D is (component B) / (component A + component B + component D) = 0. 1 to 0.6, (Component D) / (Component A + Component B + Component D) = 0.01 to 0.3, to prepare a coating solution prepared by dissolving or dispersing the composition in a solvent. A method for producing an electrophotographic photoreceptor, which comprises applying a liquid to the surface of the photoreceptor, and then heating and curing at 80 to 150 ° C.
A: A silane compound having a hydroxyl group bonded to a silicon atom in the molecule
B: an epoxy compound represented by the following general formula (1)
Embedded image

(Where R ¹ Represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹ Represents an aryl group having at least one tertiary amino group and a heterocyclic group having at least one tertiary amino group. Ar ² , Ar ³ Represents a substituted or unsubstituted arylene group. Where Ar ² And Ar ³ May be the same or different. n represents an integer of 0 to 100. )
C: General formula, AlX _n Y _3-n Aluminum chelate compound represented by
(Wherein X is a lower alkoxyl group, Y is M ¹ COCH ₂ COM ² , And M ³ COCH ₂ COOM ⁴ A ligand derived from a compound selected from the group consisting of ¹ , M ² , M ³ And M ⁴ Is a lower alkyl group, and n is 0, 1 or 2. )
D: Fine particle silica having an average particle diameter of 1 to 100 nm
(19) The solvent according to (17) or (18), wherein the solvent contains at least one solvent selected from benzyl alcohol, cyclohexanone, 2-methoxyethyl acetate, tetrahydrofuran, and acetylacetone. A method for producing an electrophotographic photoreceptor.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
The crosslinked product formed by a condensation reaction of silanol groups used in the present invention is a silane compound having one or more hydroxyl groups bonded to a silicon atom in one molecule or a mixture thereof, and at least one silicon compound in one molecule. A composition obtained by subjecting a silanol group to a condensation reaction in the presence of a silane compound having three or more hydroxyl groups bonded to atoms to three-dimensionally cross-link and cure the composition. And the fact that the charge transporting group is bonded by the reaction between the epoxy group and the silanol group means that, in the silane compound, a compound having an epoxy group and also having a charge transporting group is mixed to form a silanol group. It refers to the state of chemical bonding by the addition reaction of epoxy group. Here, as a preferred embodiment of the compound having an epoxy group and also having a charge transporting group, the following epoxy group-containing amine compound can be mentioned. Preferred embodiments of the silane compound having one or more hydroxyl groups bonded to a silicon atom in one molecule include a hydrolyzate of an alkoxysilane compound represented by the general formula (3) and a hydrolyzate represented by the general formula (4). Silanol compounds.
[0015]
Examples of the epoxy group-containing amine compound used in the present invention include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triarylamine derivatives such as triphenylamine, and phenylhydrazone, which are usually used as charge transport materials for electrophotographic photoreceptors. Compounds having a skeleton of a charge-transporting compound such as a derivative, an α-phenylstilbene derivative, a stilbene derivative, a benzimidazole derivative, an N-phenylcarbazole derivative, and having one or more, preferably two or more epoxy groups as substituents thereof Is mentioned. In order to exhibit a sufficient charge transporting ability, it is desirable to contain these epoxy group-containing amine compounds in an amount of 20% by weight or more in the composition of the reaction product. Abrasion resistance cannot be obtained. When it has two or more epoxy groups, a sufficient crosslinking density can be obtained and high abrasion resistance can be obtained.
[0016]
Among them, an epoxy group-containing amine compound represented by the following general formula (1), more preferably, general formula (2) is preferably used as a compound having excellent charge transporting properties.
The epoxy group-containing amine compounds represented by the general formulas (1) and (2) are novel compounds and can be produced by reacting a corresponding dihydroxy compound with a glycidylating agent.
[0017]
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(Where R ¹ Represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹ Represents an aryl group having at least one tertiary amino group and a heterocyclic group having at least one tertiary amino group. Ar ² , Ar ³ Represents a substituted or unsubstituted arylene group. Where Ar ² And Ar ³ May be the same or different. n represents an integer of 0 to 100. )
[0018]
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(Where R ⁴ ~ R ²⁵ Represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, which may be the same or different. n represents an integer of 0 to 100. )
[0019]
In the epoxy group-containing amine compounds represented by the general formulas (1) and (2), ¹ , R ⁴ ~ R ²⁵ The substituted or unsubstituted alkyl group is a linear or branched alkyl group having 1 to 5 carbon atoms, which may be substituted with a halogen atom or a phenyl group. It may be substituted by an alkyl group having 1 to 5 carbon atoms. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl, n-pentyl, trifluoromethyl, Examples include a benzyl group, a 4-chlorobenzyl group, and a 4-methylbenzyl group.
[0020]
Also, R ¹ As a substituted or unsubstituted aryl group, phenyl, naphthyl, biphenylyl, terphenylyl, pyrenyl, fluorenyl, 9,9-dimethyl-2-fluorenyl, azulenyl, anthryl, triphenylenyl, chrysenyl These aryl groups may be substituted with a halogen atom, the above-mentioned alkyl group, phenyl group and the like. Further, a group represented by the following general formula (5) can also be mentioned.
Embedded image

[Wherein X is -O-, -S-, -SO-, -SO ₂ -, -CO- and the following divalent groups.
Embedded image

Embedded image

(Where R ²⁶ , R ²⁷ Represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, a represents an integer of 1 to 12, and b represents an integer of 1 to 3. )]
Incidentally, R in the general formula (5) ²⁶ , R ²⁷ Is a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group ¹ , R ⁴ ~ R ²⁵ And its definitions and specific examples are the same.
[0021]
In the epoxy group-containing amine compound represented by the general formula (1), Ar ¹ The aryl group of the aryl group having at least one tertiary amino group represented by ¹ And the same as those described in the description.
Further, as the tertiary amino group, the aforementioned R ¹⁶ ~ R ²⁵ And a group having a nitrogen atom to which two phenyls having the group represented by are bonded.
[0022]
In the epoxy group-containing amine compound represented by the general formula (1), Ar ² , Ar ³ As the substituted or unsubstituted arylene group of ¹ Description (ie, R ¹ ), And a divalent group derived from the aryl group mentioned above.
Further, as the substituent of the arylene group, the aforementioned R ⁴ ~ R ¹¹ And the same as those described in the description.
[0023]
Ar ¹ Is a substituted or unsubstituted heterocyclic group having at least one tertiary amino group, such as pyrrole, pyrazole, imidazole, triazole, dioxazole, indole, isoindole, benzimidazole, benzotriazole, benzotriazole, Isoxazine, carbazole, phenoxazine and the like, and these heterocyclic groups are represented by the aforementioned R ¹ May be substituted with a substituted or unsubstituted alkyl group, a halogen atom, or a substituted or unsubstituted aryl group defined in the above.
Further, as the tertiary amino group, the aforementioned Ar ¹ And the same as those mentioned in the description.
[0024]
Furthermore, specific examples of the halogen atom in each of the above groups include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0025]
Examples of the alkoxysilane compound used in the present invention include a compound represented by the following general formula (3).
Embedded image
(R) _n -Si- (X) _4-n (3)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to a silicon atom, X represents a hydrolyzable group, at least one is an alkoxy group, and n represents an integer of 0 to 3. )
[0026]
In the general formula (3), examples of the organic group in which a carbon atom is directly bonded to a silicon atom represented by R include alkyl groups such as methyl, ethyl, propyl, and butyl; and phenyl, tolyl, naphthyl, and biphenyl. Examples include an aryl group, a halogen-containing group such as γ-chloropropyl, 1,1,1-trifluoropropyl, nonafluorohexyl, and perfluorooctylethyl, a nitro group, and a cyano-substituted alkyl group. Examples of the hydrolyzable group for X include an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy, a halogen group, and an acyloxy group. Particularly, an alkoxy group having 6 or less carbon atoms is preferable.
The compound represented by the general formula (3) may be used alone or in combination of two or more.
[0027]
Examples of the silanol compound used in the present invention include a compound represented by the following general formula (4).
Embedded image
(R) _n -Si- (Y) _4-n (4)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to a silicon atom, n represents an integer of 0 to 3, when n is 3, Y represents a hydroxyl group, and when n is 0 to 2, Y represents one hydroxyl group and the remainder represents a hydroxyl group or a hydrolyzable group.)
[0028]
In the general formula (4), examples of the organic group in which a carbon atom is directly bonded to a silicon atom represented by R include the same organic groups as those described in the description of the general formula (3). Examples of the hydrolyzable group for Y include the same groups as those described in the description of X in the general formula (3).
[0029]
When n is 2 or more in the specific compounds of the organosilicon compounds represented by the general formulas (3) and (4), a plurality of Rs may be the same or different. Similarly, when n is 2 or less, a plurality of Xs and Ys may be the same or different. When two or more organosilicon compounds represented by the general formula (3) and / or the general formula (4) are used, R, X and Y may be the same or different between the respective compounds. .
[0030]
In order to increase the compatibility with the epoxy group-containing amine compound and obtain a uniform transparent film, it is preferable to use an alkoxysilane compound and / or a silanol compound having at least one aromatic group for R. Is more preferably used in a mixture with an alkoxysilane compound and / or a silanol compound having no.
[0031]
In the general formulas (3) and (4), when the number of hydrolyzable groups and / or hydroxyl groups is 2 or more (n = 2 or less), the silane compound is condensed to obtain an organopolysiloxane resin. However, when the number is 3 (n = 1), a crosslinkable organopolysiloxane resin capable of three-dimensionally cross-linking is obtained. Therefore, it is preferable to include a trifunctional silane monomer with n = 1 as a raw material. The properties (stability, coating strength, etc.) of the resin are adjusted by appropriately adding another bifunctional silane monomer (n = 2) component or a tetrafunctional silane monomer (n = 0) component to the trifunctional silane monomer. be able to.
[0032]
The reaction product of the epoxy group-containing amine compound and the alkoxysilane compound in the present invention is a condensation reaction between silanol groups formed by hydrolysis of the alkoxy group or the alkoxy group of the alkoxysilane compound, and the reaction of the epoxy group-containing amine compound. It refers to a resin product that is integrally and three-dimensionally cross-linked by a condensation reaction between an epoxy group and the silanol group and a condensation reaction between a hydroxy group generated after the epoxy group undergoes a ring-opening addition reaction with the silanol group and the silanol group.
[0033]
Further, the reaction product of the epoxy group-containing amine compound and the silanol compound in the present invention includes a condensation reaction with a silanol group generated by further hydrolyzing a silanol group and / or an alkoxy group of the silanol compound, and an epoxy group-containing amine. An addition reaction between the epoxy group of the compound and the silanol group, and a three-dimensionally cross-linked resin material integrally formed by a condensation reaction of the hydroxyl group formed after the epoxy group undergoes a ring-opening addition reaction with the silanol group and the silanol group. To tell.
[0034]
Further, the coating liquid for an electrophotographic photoreceptor of the present invention is prepared by adding water necessary for hydrolyzing a silicon-containing monomer such as a compound represented by the general formula (3) and / or the general formula (4). It may be used after being hydrolyzed under acidic to basic conditions.
[0035]
The hydrolysis can be performed with pure water or an acidic aqueous solution such as hydrochloric acid, sulfuric acid, or acetic acid, and is performed by using alkoxysilane alone or by diluting with a solvent. When a plurality of alkoxysilanes are used, they can be separately hydrolyzed and mixed, or the mixed alkoxysilanes can be co-hydrolyzed, or one of the alkoxysilanes can be hydrolyzed to another alkoxysilane. A sequential hydrolysis method in which a silane body is added and hydrolysis is continued can be applied.
[0036]
The solvent used in the electrophotographic photoreceptor coating solution is preferably a mixed solvent of at least one solvent selected from ketone, ester, ether and aromatic solvents and an alcohol solvent.
Examples of ketone solvents include methyl ethyl ketone, methyl isobutyl ketone, acetone, and cyclohexanone; examples of ester solvents include ethyl acetate and t-butyl acetate; examples of ether solvents include methyl cellosolve, ethyl cellosolve, diethyl ether, and dibutyl ether. , Dipropyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and the like, and aromatic solvents such as toluene and xylene. Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and t-butanol.
[0037]
Although various solvents can be used in this way, in order to achieve the solubility of each composition and uniform film properties at the time of crosslinking and curing, it is necessary to consider a solubility and mix a solvent having a relatively high boiling point. Is preferred.
Preferred solvents include butanol, benzyl alcohol, cyclohexanone, 2-methoxyethyl acetate, tetrahydrofuran, and acetylacetone. Among them, benzyl alcohol and cyclohexanone are preferably used as solvents having a relatively high boiling point. When these solvents are not used, it is difficult to prepare a uniform coating liquid and a uniform cured film.
Among these, those that dissolve an epoxy group-containing amine compound, an alkoxysilane compound, and a silanol compound are used.
[0038]
The concentration of the solid content in the coating solution for the electrophotographic photoreceptor is optimally selected depending on the structure of the alkoxysilane compound, the silanol compound, the epoxy group-containing amine compound, the coating method, and the like, but is usually preferably 2 to 50% by weight. .
[0039]
The coating solution for the electrophotographic photoreceptor includes, as a catalyst for promoting a crosslinking reaction, alkali metal salts of organic carboxylic acids, nitrous acid, sulfurous acid, aluminate, carbonic acid and thiocyanic acid, and organic amine salts (tetramethylammonium hydroxide, Tetramethylammonium acetate), tin organic acid salts (stannas octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin malate), aluminum, zinc octenoic acid, naphthenic acid Salts, acetylacetone complex compounds and the like may be used.
The amount of the catalyst is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the alkoxysilane compound and the silanol compound.
[0040]
As the catalyst, in particular, the general formula: AlX _n Y _3-n The aluminum chelate compound represented by is preferred.
(Where X is a lower alkoxyl group, Y is M ¹ COCH ₂ COM ² , And M ³ COCH ₂ COOM ⁴ A ligand derived from a compound selected from the group consisting of ¹ , M ² , M ³ And M ⁴ Is a lower alkyl group, and n is 0, 1 or 2. )
By using this aluminum chelate compound, the cross-linking hardly progresses when not heated and the cross-linking progresses rapidly when heated, so that the pot life of the coating liquid is long and the coating condition management during production is easy. Become.
Among the aluminum chelate compounds, the following examples are given as specific compounds from the viewpoint of catalytic activity, solubility and stability.
Aluminum acetylacetonate, aluminum ethyl acetoacetate bisacetylacetonate, aluminum bisacetoacetate acetylacetonate, aluminum di-n-butoxide monoethylacetoacetate, aluminum di-i-propoxide monomethylacetoacetate, and mixtures thereof.
[0041]
Further, the coating liquid for an electrophotographic photoreceptor may be prepared by further adding a colloid of a metal oxide such as colloidal silica or colloidal alumina. Colloidal silica is an aqueous or alcoholic sol having a particle size of preferably 100 nm or less, particularly preferably 50 nm or less.
Component D fine silica having an average particle size of 1 to 100 nm is also used as the colloidal silica.
The addition of colloidal silica improves the film-forming properties and eliminates the occurrence of cracks during thermosetting. In addition, hardness is increased and scratch resistance is increased.
The amount of colloidal silica to be added is not particularly limited, but it is preferable that the amount of colloidal silica is 1 to 30% by weight in the curable resin layer after drying.
[0042]
In addition, the coating solution for the electrophotographic photoreceptor includes various other materials known as materials for electrophotography, for example, antioxidants such as hindered amine and hindered phenol, leveling agents such as silicone oil, amine compounds and the like. And a hole transporting agent such as quinones.
[0043]
Although the drying temperature of the coating film varies depending on the type of solvent used and the presence or absence of a catalyst, heating is preferably performed for about 10 minutes to 5 hours in a range of about 60 to 160 ° C, and further for 20 minutes to 3 hours in a range of 80 to 150 ° C. It is preferable to heat and cure at a temperature of 100 to 150 ° C. for 30 minutes to 2 hours. If the temperature is lower than 80 ° C., the crosslinking reaction may not proceed sufficiently. If the temperature is higher than 150 ° C., the electrophotographic characteristics tend to deteriorate due to deterioration of the material in the photoconductor.
[0044]
The layer constitution of the photoreceptor to which the outermost layer of the present invention is applied is not particularly limited. However, a preferred embodiment is a configuration in which the outermost surface layer of the present invention is provided as a protective layer on a conventionally known photoreceptor.
In this case, the thickness of the protective layer is usually 0.1 to 15 μm, preferably 1 to 15 μm, and more preferably 1 to 5 μm. When the thickness is less than 1 μm, sufficient abrasion resistance cannot be obtained, and when the thickness is more than 15 μm, cracks and detachment are likely to occur in the protective layer.
[0045]
As described above, the composition used in the present invention and the method for producing the composition have been described. A more preferable composition configuration will be described.
One is that it contains the following components A, B and C, and the mixing ratio of components A and B is (component B) / (component A + component B) = 0.1 to 0.7 in terms of solid content weight ratio. , A cured coating composition.
A: A silane compound having a hydroxyl group bonded to a silicon atom in the molecule
B: an epoxy compound represented by the following general formula (1)
Embedded image

(Where R ¹ Represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹ Represents an aryl group having at least one tertiary amino group and a heterocyclic group having at least one tertiary amino group. Ar ² , Ar ³ Represents a substituted or unsubstituted arylene group. Where Ar ² And Ar ³ May be the same or different. n represents an integer of 0 to 100. )
C: General formula, AlX _n Y _3-n Aluminum chelate compound represented by
(Wherein X is a lower alkoxyl group, Y is M ¹ COCH ₂ COM ² , And M ³ COCH ₂ COOM ⁴ A ligand derived from a compound selected from the group consisting of ¹ , M ² , M ³ And M ⁴ Is a lower alkyl group, and n is 0, 1 or 2. )
[0046]
The silane compound having a hydroxyl group bonded to a silicon atom in the molecule of the component A is a hydrolyzate of the alkoxysilane compound.
Component B is a structure in which the epoxy group-containing amine compound is preferable.
The mixing ratio of the component A and the component B is 0.1 to 0.7 as the solid content weight ratio of the component B (component B) / (component A + component B). If the ratio is smaller than 0.1, the charge transporting property is hardly obtained, resulting in deterioration of characteristics such as an increase in the residual potential of the photoreceptor and a decrease in sensitivity. On the other hand, when it exceeds 0.7, the film strength is greatly reduced due to the decrease in the silanol condensation crosslinked portion, and the durability of the photoreceptor cannot be maintained.
As the aluminum chelate compound of the component C, the same one as described above is used, but about 0.01 to 30 parts by weight is added to 100 parts by weight of the total amount of the components A and B. If the amount is less than this, curing is incomplete, and if it is too large, the film becomes brittle.
[0047]
Another preferred example includes the following components A, B, C, and D, and the mixing ratio of components A, B, and D is (component B) / (component A + component B + component D) in terms of solids weight ratio. ) = 0.1 to 0.6, and (Component D) / (Component A + Component B + Component D) = 0.01 to 0.3.
The components A, B and C are the same as described above.
Component D is finely divided silica having an average particle size of 1 to 100 nm.
The mixing ratio (solid content weight ratio) of components A, B, and D is 0.1 to 0.6 for component B and 0.01 to 0.3 for component D. When the component B is smaller than 0.1, the charge transporting property is hardly obtained, resulting in deterioration of characteristics such as an increase in the residual potential of the photoreceptor and a decrease in sensitivity. On the other hand, when it exceeds 0.6, the film strength is greatly reduced due to the decrease in the silanol condensation crosslinked portion, and the durability of the photoreceptor cannot be maintained.
When the component D is less than 0.01, improvement in film-forming properties and improvement in coating film hardness cannot be expected. Conversely, when component D exceeds 0.3, coating film defects such as cracking may occur or resolution may be reduced. Or lowering problems.
As the aluminum chelate compound of the component C, the same one as described above is used, but it is preferable to add about 0.01 to 30 parts by weight based on 100 parts by weight of the total amount of the components A, B and D. If the amount is less than this, curing is incomplete, and if it is too large, the film becomes brittle.
[0048]
The layer constitution of the photoreceptor to which the outermost layer of the present invention is applied is not particularly limited. However, a preferred embodiment is a configuration in which the outermost surface layer of the present invention is provided as a protective layer on a conventionally known photoreceptor.
As a typical configuration, an undercoat layer, a charge generation layer, a charge transport layer, and a protective layer are sequentially formed on a conductive support such as aluminum.
[0049]
As the charge generating substance used in the photosensitive layer of the electrophotographic photosensitive member of the present invention, any known charge generating substance can be used.
For example, A-type, B-type and Y-type titanyl phthalocyanines, X-type and τ-type metal-free phthalocyanines, metal phthalocyanines such as copper phthalocyanine, naphthalocyanines, and mixed crystals of these two types of phthalocyanines, azo compounds, pyrylium Examples include compounds, perylene compounds, cyanine compounds, squarium compounds, polycyclic quinone compounds, and the like. These charge generating substances are used alone or dispersed in an appropriate binder resin to form a layer.
[0050]
As the charge transporting substance used in the photosensitive layer of the electrophotographic photosensitive member of the present invention, any known substances can be used.
For example, typical examples of hole transporting substances include oxazole, oxadiazole, thiazole, thiadiazole, a nitrogen-containing heterocyclic nucleus represented by imidazole, and a compound having a condensed ring nucleus thereof, a compound having a polyarylalkane type, Hydrazone compounds, pyrazoline compounds, triarylamine compounds, styryl compounds, poly (bis) styryl compounds, styryltriphenylamine compounds, β-phenylstyryltriphenylamine compounds, butadiene compounds, hexatriene compounds And carbazole-based compounds, condensed polycyclic compounds, and the like. Representative electron-transporting substances include benzoquinone, naphthoquinone, anthraquinone, thiopyranone, fluorenone, indenone, and indandione-based compounds. These charge transporting substances are usually dissolved in a suitable binder resin to form a layer.
[0051]
Solvents used for dispersing and dissolving the charge generating material and the charge transporting material include hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane; ketones such as methyl ethyl ketone and cyclohexanone. Esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol, methyl cellosolve and ethyl cellosolve and derivatives thereof; ethers such as tetrahydrofuran, 1,4-dioxane and 1,3-dioxolane; Amines such as diethylamine; amides such as N, N-dimethylformamide; other fatty acids and phenols; one or more of sulfur and phosphorus compounds such as carbon disulfide and triethyl phosphate;
[0052]
Among the photosensitive layers of the electrophotographic photosensitive member of the present invention, the photosensitive layer other than the surface layer includes polystyrene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin, and phenol resin. And polyester resins, alkyd resins, polycarbonate resins, silicone resins, melamine resins, and copolymer resins containing two or more of the repeating units of these resins. In addition to these insulating resins, polymer organic semiconductors such as poly-N-vinylcarbazole can be used.
[0053]
The ratio of the binder resin to the charge generating substance in the photosensitive layer of the electrophotographic photoreceptor of the present invention is preferably 50 to 600 parts by weight of the charge generating substance with respect to 100 parts by weight of the binder resin. The ratio of the charge transport material to the binder resin is preferably 10 to 100 parts by weight of the charge transport material with respect to 100 parts by weight of the binder resin.
[0054]
The thickness of the photosensitive layer of the electrophotographic photoreceptor of the present invention is preferably 0.1 to 10 μm for the charge generation layer and 5 to 30 μm for the charge transport layer. When the photosensitive layer has a single-layer structure, the thickness is preferably 5 to 40 μm.
[0055]
In the electrophotographic photoreceptor of the present invention, as the conductive support for supporting the photosensitive layer, a metal plate or metal drum of aluminum, nickel, or the like, or a plastic film on which aluminum, tin oxide, indium oxide, or the like is deposited, or a conductive material Paper, plastic film and drum coated with
[0056]
Examples of the material used for the undercoat layer of the electrophotographic photoreceptor of the present invention include polyamide resins, vinyl chloride resins, vinyl acetate resins, and copolymer resins containing two or more of repeating units of these resins. Can be Further, a curable metal resin compound obtained by thermally curing an organic metal compound such as a silane coupling agent or a titanium coupling agent may be used.
The thickness of the undercoat layer is preferably 0.01 to 15 μm.
[0057]
In addition, the electrophotographic photoreceptor of the present invention may further contain an additive such as an antioxidant or the like for the dye for color sensitivity correction or the photosensitive layer.
[0058]
As a coating method for producing the electrophotographic photoreceptor of the present invention, dip coating, spray coating, circular amount control type coating, or the like of a coating solution for forming each layer can be used. In particular, in the coating process on the protective layer side of the photosensitive layer, spray coating and circular amount control type coating (a circular slide hopper is a typical example) are used in order to minimize dissolution of the lower layer film and to achieve uniform coating process. Is preferred. The spray coating is described in JP-A-3-90250 and JP-A-3-269238, and the details of the circular amount control type coating are described in JP-A-58-189061. .
[0059]
【Example】
Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited by the examples. All parts are parts by weight.
[0060]
Synthesis example
<Synthesis of epoxy group-containing amine compound>
A reaction vessel equipped with a stirring device, a thermometer, a dropping funnel, and a device for condensing and separating an azeotrope of epichlorohydrin and water and returning a lower epichlorohydrin layer was placed in a reaction vessel equipped with 4- [2,2-bis (4-hydroxy). 19.34 g (40.0 mmol) of phenyl) vinyl] phenyl-bis (4-methylphenyl) amine and 37.01 g (400.0 mmol) of epichlorohydrin were added, and the mixture was heated and stirred at 110 ° C. under a nitrogen stream. To this, 19.20 g (96.0 mmol) of a 20 wt% aqueous sodium hydroxide solution was added dropwise over 3 hours such that the temperature in the reaction system was maintained at 100 ° C to 120 ° C. Only water and epichlorohydrin distilled off during the reaction were returned to the reaction vessel, and after the completion of the dropwise addition of the aqueous sodium hydroxide solution, the reaction was further carried out at 110 ° C. for 1 hour. This was allowed to cool to room temperature, and excess epichlorohydrin was recovered under reduced pressure. Toluene was added, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and the toluene solvent was distilled off under reduced pressure to give a yellow crude product. 20.75 g (yield: 87.1%) of a compound having a melting point of 111.0 to 116.0 ° C was obtained. This was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 20/1 vol.), And then recrystallized from ethyl acetate and ethanol to obtain 15.85 g of pale yellow needle crystals (yield: 66.5%). Got. The melting point was 128.0-129.0 ° C.
FIG. 1 shows an infrared absorption spectrum (NaCl liquid film method).
The results of elemental analysis are shown below.

[0061]
Example 1
An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following compositions were successively applied on an aluminum cylinder by dip coating, dried, and dried to a thickness of 3.5 μm. A 2 μm charge generation layer and a 26 μm charge transport layer were formed.
<Coating solution for undercoat layer>
Titanium dioxide powder: 400 parts
Melamine resin: 40 parts
Alkyd resin: 60 parts
2-butanone: 500 parts
<Coating solution for charge generation layer>
Bisazo pigment represented by the following structural formula: 12 parts
Embedded image

Polyvinyl butyral: 5 parts
2-butanone: 200 parts
Cyclohexanone: 400 parts
<Coating solution for charge transport layer>
Polycarbonate (Z Polyka, Teijin Chemicals): 10 parts
Charge transport material represented by the following structural formula: 10 parts
Embedded image

Tetrahydrofuran: 100 parts
1% silicone oil (KF50-100CS,
Shin-Etsu Chemical Co., Ltd.) Tetrahydrofuran solution: 1 part
Next, a protective layer coating solution having the following composition was further formed on the charge transport layer by spray coating to form a protective layer of about 3 μm, and then dried by heating at 120 ° C. for 2 hours. Was prepared.
<Protective layer coating liquid>
Obtained by synthesis example
Epoxy group-containing amino compound represented by the following structural formula: 4.2 parts
Embedded image

Methyltrimethoxysilane: 5 parts
Phenyltriethoxysilane: 5 parts
1% acetic acid aqueous solution: 5.57 parts
Tetrahydrofuran: 30.7 parts
n-butanol: 3.67 parts
[0062]
Example 2
An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the coating of the protective layer was performed as described below.
A prescription liquid having the following composition was prepared in advance and stirred at 60 ° C. for 2 hours to silanol alkoxysilane.
<Pre-formulation liquid for protective layer coating liquid>
Methyltrimethoxysilane: 5 parts
Phenyltriethoxysilane: 5 parts
1% acetic acid aqueous solution: 5.57 parts
Tetrahydrofuran: 30.7 parts
n-butanol: 3.67 parts
Thereafter, 4.2 parts of the epoxy group-containing amino compound used in Example 1 was added to prepare a coating liquid. Using this coating liquid, a protective layer was formed in the same manner as in Example 1, and an electrophotographic photosensitive member of Example 2 was produced.
[0063]
Example 3
An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the coating of the protective layer was performed as described below.
To 21 parts of methyltrimethoxysilane and 21 parts of phenyltriethoxysilane, 8.16 parts of a 1% aqueous acetic acid solution was added dropwise over 25 minutes under ice-cooling, followed by stirring at 5 ° C. for 30 minutes, and then stirring at room temperature 24 ° C. for 2 minutes. Stirred for hours and hydrolyzed.
Thereafter, a coating liquid having the following composition was prepared.
<Protective layer coating liquid>
Hydrolysis solution: 3 parts
Epoxy group-containing amino compound used in Example 1: 0.98 parts
2-methoxyethyl acetate: 2.62 parts
Cyclohexanone: 2.42 parts
Tetrahydrofuran: 0.98 parts
Acetylacetone: 0.12 parts
Aluminum acetylacetonate: 0.12 parts
An electrophotographic photosensitive member of Example 3 having a protective layer of 3 μm was prepared in the same manner as in Example 1 except that a ring coating method was used using this coating solution.
[0064]
Example 4
An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the coating of the protective layer was performed as described below.
To 21 parts of methyltrimethoxysilane and 21 parts of phenyltriethoxysilane, 8.16 parts of a 1% aqueous acetic acid solution was added dropwise over 25 minutes under ice-cooling, followed by stirring at 5 ° C. for 30 minutes, and then stirring at room temperature 24 ° C. for 2 minutes. Stirred for hours and hydrolyzed.
Thereafter, a coating liquid having the following composition was prepared.

Example having a 2 μm protective layer in the same manner as in Example 1 except that the setting time after coating was set to 30 minutes and the curing time was set to 130 ° C. for 1 hour by using a ring coating method using this coating liquid. 4 was prepared.
[0065]
Comparative Example 1
An electrophotographic photoreceptor of Comparative Example 1 was prepared in the same manner as in Example 1, except that a hydroxy group-containing amine compound represented by the following structural formula was used instead of the epoxy group-containing amino compound.
Embedded image

[0066]
Comparative Example 2
An electrophotographic photosensitive member of Comparative Example 2 was produced in the same manner as in Example 1 except that the protective layer was not provided in Example 1.
[0067]
The obtained electrophotographic photoreceptor was set on a Ricoh imagioMF2200 (a modified machine using a 655 nm LD light source), and after running 10,000 sheets of paper running, the amount of wear (change in film thickness) was measured, and the surface of the photoreceptor was observed with a microscope. The potential fluctuations of the dark potential (VD) and the light potential (VL) of the internal potential were measured. Further, the image quality was evaluated visually from the output image of the test chart. In the surface observation, it was evaluated as ○ when only fine linear flaws were present, Δ when some granular dents were generated, and × when granular dents appeared on the entire surface or the film fell off. The image quality was evaluated as ○ when there was no noticeable decrease in image quality, 、 when an abnormal image such as background contamination, white spots, or reduced resolution was generated, △ when the density was reduced or an abnormal image occurred over the entire surface. The results are shown below. Further, a fingerprint was adhered to the surface of the photoreceptor, and the presence or absence of cracks after standing for 48 hours was examined. When no crack was generated, it was evaluated as ○, when it was partially generated, and when it was generated over the entire surface, it was evaluated as ×. The results are shown in Table 1 below.
[0068]
[Table 1]

[0069]
As described above, the electrophotographic photoreceptor of the present invention has high abrasion resistance, has the same electrophotographic characteristics as those without a protective layer, has small potential fluctuations during repeated use, and has good crack resistance. It can be seen that a long-life electrophotographic photosensitive member having both high image quality stability and abrasion resistance can be provided.
[0070]
【The invention's effect】
Conventionally, in order to impart charge transporting ability to a polyorganosiloxane crosslinked film, crosslinking is carried out only by a condensation reaction, the film shrinks greatly during the reaction, internal stress in the film increases, internal defects occur, Sufficient mechanical strength was not obtained due to slight peeling of the film or the like. In addition, it was not easy to synthesize a polyfunctional charge transporting compound, and the crosslink density of a film obtained by reacting these compounds was reduced, and it was difficult to produce a sufficiently hard film.
In the present invention, in the electrophotographic photoreceptor, a film having less shrinkage due to the introduction of a charge transporting group by an addition reaction involving ring opening of an epoxy group and a silanol group and having less distortion is obtained, Hydroxy groups generated by ring opening can also contribute to the crosslinking reaction, and can perform the same function as a polyfunctional compound with a small number of functional groups. Therefore, it is possible to produce a film having a high crosslinking density and being hard and resistant to damage.
In the present invention, an amine compound having an epoxy group is used as a raw material for the addition reaction, and the compound represented by the general formulas (1) and (2) having a high hole mobility is used as the amine compound having an epoxy group. In such a case, since the charge transporting compound can be introduced into the crosslinked film, it is possible to provide a highly durable electrophotographic photoreceptor having excellent charge transfer, exhibiting excellent electrophotographic properties, and exhibiting high durability.
Further, since the charge-transporting group of the charge-transporting compound is doubly cross-linked as described above, a free form is not easily generated, and the electrophotographic photosensitive member is resistant to cracks and the like.
[Brief description of the drawings]
FIG. 1 is an infrared absorption spectrum of an epoxy group-containing amine compound obtained in a synthesis example (NaCl liquid membrane method).

Claims (19)

An electrophotographic photoreceptor comprising a layer containing a composition in which a charge transporting group is bonded by a reaction between an epoxy group and a silanol group in a crosslinked product formed by a condensation reaction of a silanol group. An electrophotographic photosensitive member comprising at least a photosensitive layer provided on a conductive support, wherein the outermost surface layer of the electrophotographic photosensitive member mainly comprises a reaction product of an epoxy group-containing amine compound and an alkoxysilane compound. Photoreceptor. An electrophotographic photosensitive member comprising at least a photosensitive layer provided on a conductive support, wherein the outermost surface layer of the electrophotographic photosensitive member mainly comprises a reaction product of an epoxy group-containing amine compound and a silanol compound. Photoconductor. The electrophotographic photoconductor according to claim 3, wherein the silanol compound is a compound generated by hydrolysis of an alkoxysilane compound. In an electrophotographic photosensitive member having at least a photosensitive layer provided on a conductive support, the outermost surface layer of the electrophotographic photosensitive member was coated with a coating liquid comprising at least a mixture of an epoxy group-containing amine compound and an alkoxysilane compound. And an electrophotographic photoreceptor comprising a reaction product obtained by the reaction. In an electrophotographic photoreceptor having at least a photosensitive layer provided on a conductive support, the outermost surface layer of the electrophotographic photoreceptor has at least a silanol compound generated by hydrolysis of an alkoxysilane compound and an epoxy group-containing amine compound. An electrophotographic photoreceptor comprising a reaction product obtained by applying a coating solution comprising a mixture and reacting the same. 7. The electrophotographic photoreceptor according to claim 5, wherein after application of the coating liquid, the coating liquid is cured by heating at 100 [deg.] C. or higher. The electrophotographic photoreceptor according to any one of claims 2 to 7, wherein the epoxy group-containing amine compound is a compound represented by the following general formula (1).

(Wherein, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹ is an aryl group having at least one tertiary amino group, and at least one tertiary amino group. ^.Ar 2, Ar ^3, which represents a heterocyclic group having an amino group or a substituted or unsubstituted arylene group. However, Ar ² and Ar ³ are optionally be the same or different .n represents an integer of 0 to 100 Represents.) The electrophotographic photoconductor according to any one of claims 2 to 8, wherein the epoxy group-containing amine compound is a compound represented by the following general formula (2).

(In the formula, R ^{4 to} R ²⁵ represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group, and may be the same or different. N represents an integer of 0 to 100.) The electrophotographic photoreceptor according to any one of claims 2, 4 to 9, wherein the alkoxysilane compound is a compound represented by the following general formula (3).

(In the formula, R represents an organic group in which a carbon atom is directly bonded to a silicon atom, X represents a hydrolyzable group, at least one is an alkoxy group, and n represents an integer of 0 to 3. ) The electrophotographic photoreceptor according to any one of claims 3, 4, and 6 to 9, wherein the silanol compound is a compound represented by the following general formula (4).

(In the formula, R represents an organic group in which a carbon atom is directly bonded to a silicon atom, n represents an integer of 0 to 3, when n is 3, Y represents a hydroxyl group, and when n is 0 to 2, Y represents one hydroxyl group and the remainder represents a hydroxyl group or a hydrolyzable group.) The electrophotographic photoreceptor according to any one of claims 2 to 11, wherein the alkoxysilane compound and / or the silanol compound comprises a mixture of two or more kinds. The electrophotographic photoreceptor according to any one of claims 2 to 12, wherein the alkoxysilane compound and / or silanol compound is a compound having at least one aromatic group. Curing that includes the following components A, B, and C, and the mixing ratio of the components A and B is (component B) / (component A + component B) = 0.1 to 0.7 in terms of solids weight ratio. An electrophotographic photosensitive member having a coating composition on the surface.
A: a silane compound having a hydroxyl group bonded to a silicon atom in a molecule B: an epoxy compound represented by the following general formula (1)

(Wherein, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹ is an aryl group having at least one tertiary amino group, and at least one tertiary amino group. ^.Ar 2, Ar ^3, which represents a heterocyclic group having an amino group or a substituted or unsubstituted arylene group. However, Ar ² and Ar ³ are optionally be the same or different .n represents an integer of 0 to 100 Represents.)
C: _Formula, aluminum chelate compounds represented by AlX _{n Y 3-n} (wherein, X is a lower alkoxy group, Y is selected from the group consisting of ^M 1 COCH ^₂ COM _2, and ^M 3 COCH ₂ COOM ⁴ The ligands arising from the compound, M ¹ , M ² , M ³ and M ⁴ are lower alkyl groups, and n is 0, 1 or 2.) The following components A, B, C, and D are contained, and the mixing ratio of the components A, B, and D is (component B) / (component A + component B + component D) = 0.1 to 0 in terms of the solid content weight ratio. 6. An electrophotographic photoreceptor having on its surface a cured coating composition wherein (Component D) / (Component A + Component B + Component D) = 0.01 to 0.3.
A: a silane compound having a hydroxyl group bonded to a silicon atom in a molecule B: an epoxy compound represented by the following general formula (1)

(Wherein, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹ is an aryl group having at least one tertiary amino group, and at least one tertiary amino group. ^.Ar 2, Ar ^3, which represents a heterocyclic group having an amino group or a substituted or unsubstituted arylene group. However, Ar ² and Ar ³ are optionally be the same or different .n represents an integer of 0 to 100 Represents.)
C: _Formula, aluminum chelate compounds represented by AlX _{n Y 3-n} (wherein, X is a lower alkoxy group, Y is selected from the group consisting of ^M 1 COCH ^₂ COM _2, and ^M 3 COCH ₂ COOM ⁴ The ligands arising from the compound, M ¹ , M ² , M ³ and M ⁴ are lower alkyl groups, and n is 0, 1 or 2.)
D: Fine particle silica having an average particle diameter of 1 to 100 nm The electrophotographic photosensitive member according to claim 14, wherein the cured coating composition has a thickness of 1 to 15 μm. A composition comprising the following components A, B, and C, and the mixing ratio of the components A and B is (component B) / (component A + component B) = 0.1 to 0.7 in terms of solid content weight ratio. Producing a coating solution in which the product is dissolved or dispersed in a solvent, applying the coating solution on the surface of the photoreceptor, and heating and curing at 80 to 150 ° C. Method.
A: a silane compound having a hydroxyl group bonded to a silicon atom in a molecule B: an epoxy compound represented by the following general formula (1)

(Wherein, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹ is an aryl group having at least one tertiary amino group, and at least one tertiary amino group. ^.Ar 2, Ar ^3, which represents a heterocyclic group having an amino group or a substituted or unsubstituted arylene group. However, Ar ² and Ar ³ are optionally be the same or different .n represents an integer of 0 to 100 Represents.)
C: _Formula, aluminum chelate compounds represented by AlX _{n Y 3-n} (wherein, X is a lower alkoxy group, Y is selected from the group consisting of ^M 1 COCH ^₂ COM _2, and ^M 3 COCH ₂ COOM ⁴ The ligands arising from the compound, M ¹ , M ² , M ³ and M ⁴ are lower alkyl groups, and n is 0, 1 or 2.) The following components A, B, C, and D are contained, and the mixing ratio of the components A, B, and D is (component B) / (component A + component B + component D) = 0.1 to 0 in terms of the solid content weight ratio. .6, (Component D) / (Component A + Component B + Component D) = 0.01-0.3 A composition was prepared by dissolving or dispersing the composition in a solvent, and this coating solution was exposed to light. A method for producing an electrophotographic photoreceptor, comprising applying heat to a body surface at 80 to 150 ° C. after coating.
A: a silane compound having a hydroxyl group bonded to a silicon atom in a molecule B: an epoxy compound represented by the following general formula (1)

(Wherein, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹ is an aryl group having at least one tertiary amino group, and at least one tertiary amino group. ^.Ar 2, Ar ^3, which represents a heterocyclic group having an amino group or a substituted or unsubstituted arylene group. However, Ar ² and Ar ³ are optionally be the same or different .n represents an integer of 0 to 100 Represents.)
C: _Formula, aluminum chelate compounds represented by AlX _{n Y 3-n} (wherein, X is a lower alkoxy group, Y is selected from the group consisting of ^M 1 COCH ^₂ COM _2, and ^M 3 COCH ₂ COOM ⁴ The ligands arising from the compound, M ¹ , M ² , M ³ and M ⁴ are lower alkyl groups, and n is 0, 1 or 2.)
D: Fine particle silica having an average particle diameter of 1 to 100 nm 19. The electrophotographic photosensitive member according to claim 17, wherein the solvent contains at least one solvent selected from benzyl alcohol, cyclohexanone, 2-methoxyethyl acetate, tetrahydrofuran, and acetylacetone. Production method.

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