JP2004018566A - Epoxy compound having charge transporting ability - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new epoxy compound remarkably improving mechanical durability such as abrasion or scuff resistance and having a charge transporting ability satisfying even electrophotographic characteristics and to provide a mixture thereof. <P>SOLUTION: The epoxy compound having the charge transporting ability is represented by general formula (1) (wherein, R<SP>1</SP>denotes a hydrogen atom, a substituted or an unsubstituted alkyl group or a substituted or an unsubstituted aryl group; Ar<SP>1</SP>denotes an aryl group having at least one tertiary amino group; Ar<SP>2</SP>and Ar<SP>3</SP>denote each a substituted or an unsubstituted arylene group, with the proviso that Ar<SP>2</SP>and Ar<SP>3</SP>may be the same or different; and n denotes an integer of 0-5,000). <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０〜５０００の整数を表す。）
【化９】

（式中、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０〜５０００の整数を表す。）
【化１０】

（式中、Ｒ^２、Ｒ^３は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^２〜Ａｒ^４は置換もしくは無置換のアリレン基を表す。但し、Ｒ^２とＲ^３、Ａｒ^２〜Ａｒ^４は、それぞれ同一でも異なっていてもよい。ｎは０〜５０００の整数を表す。）
【化１１】

（式中、Ｒ^２、Ｒ^３は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。Ｒ^４〜Ｒ^１１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す。Ａｒ^４は置換もしくは無置換のアリレン基を表す。但し、Ｒ^２とＲ^３、Ｒ^４〜Ｒ^１１はそれぞれ同一でも異なっていてもよい。ｎは０〜５０００の整数を表す。）
【化１２】

（式中、Ｒ^２、Ｒ^３は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。Ｒ^４〜Ｒ^１５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す。但し、Ｒ^２とＲ^３、Ｒ^４〜Ｒ^１５はそれぞれ同一でも異なっていてもよい。ｎは０〜５０００の整数を表す。）
【化１３】

（式中、Ｒ^４〜Ｒ^１５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。Ｒ^１６〜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、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアリール基、置換もしくは無置換のアリールオキシ基を表し、それぞれ同一でも異なっていてもよい。ｎは０〜５０００の整数を表す。）
【化１４】

（式中、Ｒ^４〜Ｒ^１５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。Ｒ^１６〜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、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアリール基、置換もしくは無置換のアリールオキシ基を表し、それぞれ同一でも異なっていてもよい。）
【０００９】
【発明の実施の形態】
以下に本発明をさらに詳細に説明する。
本発明の前記一般式（１）〜（７）で表される電荷輸送能を有するエポキシ化合物は、新規物質であり、測鎖部分に３級アミノ基や芳香環以外の炭素−炭素二重結合を有するため、これらエポキシ化合物を用いて感光体を作製した場合、該感光体は帯電時の静電的ハザードに対して耐久性が高く、耐摩耗性に極めて優れたものとなる。これは、主鎖方向での分子切断等が生起しないことによるものと考えられる。
一方、主鎖部分に３級アミノ基や芳香環以外の炭素−炭素二重結合を有する化合物では、帯電時の静電的ハザードに対して該アミノ基や該二重結合部位は切れやすいため、分子量が下がり耐摩耗性が低くなる傾向にある。
また、エポキシ基の硬化反応に光重合を利用する場合、感光体のような大面積の均一架橋膜を得ることは難しく、感光体特性や摩耗特性に不具合を生じやすいため、本発明の電荷輸送能を有するエポキシ化合物は、活性水素基を利用した熱硬化方法を利用することが好ましく、該方法により均一な膜質の大面積の架橋膜を得ることができる。
さらに本発明のようなエポキシ化合物（エポキシ樹脂）を用いて作製した感光体は、従来の熱可塑性樹脂から作製した感光体と異なり、３次元架橋された硬化性樹脂から構成されているために、機械的、静電的ハザードに対して飛躍的に強い。特に、エポキシ樹脂の３次元架橋膜は、他の堅くてもろい３次元架橋膜と異なり、靭性に優れていることから、耐摩耗性にも優れている。
【００１０】
本発明の電荷輸送能を有するエポキシ化合物の、前記一般式（１）、（２）、（３）、（４）、（５）、（６）及び（７）で表される電荷輸送能を有するエポキシ化合物において、Ｒ^１〜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。
【００１１】
また、Ｒ^１〜Ｒ^２５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（８）で表される基も挙げることができる。
【化１５】

〔式中、Ｘは−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−及び以下の２価基を表す。
【化１６】

【化１７】

（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（８）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^３、Ｒ^１６〜Ｒ^２５と、その定義及び具体例は同様である。
【００１２】
また前記一般式（６）及び（７）で表される電荷輸送能を有するエポキシ化合物において、Ｒ^１６〜Ｒ^２５の置換もしくは無置換のアルコキシ基、置換もしくは無置換のアリールオキシ基は、それぞれ、前記Ｒ^１〜Ｒ^２５の説明において挙げた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からそれぞれ誘導される基が挙げられる。
【００１３】
また前記一般式（１）及び（２）で表される電荷輸送能を有するエポキシ化合物において、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〜Ｒ^３、Ｒ^１６〜Ｒ^２５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、−ＮＲ^２Ｒ^３基で表される基が挙げられ、該Ｒ^２、Ｒ^３の定義及び具体例は前記したものと同様である。
【００１４】
また前記一般式（１）、（２）、（３）及び（４）で表される電荷輸送能を有するエポキシ化合物において、Ａｒ^２、Ａｒ^３及びＡｒ^４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〜Ｒ^３、Ｒ^１６〜Ｒ^２５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^１５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。
【００１５】
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。
【００１６】
また本発明の前記一般式（１）〜（７）のいずれかで表される電荷輸送能を有するエポキシ化合物は、それらと他のエポキシ化合物との混合物、またはそれらの混合物、或いはそれらの混合物とさらに他のエポキシ化合物との混合物として用いることも好ましい。
このように混合物として用いることにより、感光体設計（例えば、静電特性、電荷移動度、機械的耐久性、ガラス転移温度など）を容易に、かつ自由に行なうことができる。また市販のエポキシ化合物と組み合わせることにより、感光体を安価に製造できるという利点も有する。
【００１７】
さらに本発明の前記一般式（１）〜（６）のいずれかで表される電荷輸送能を有するエポキシ化合物の混合物の数平均分子量は、６００〜５０００００が好ましい。
該数平均分子量が６００〜５０００００の範囲の場合、感光体製造において溶液系塗工が容易であるとともに感光体特性の制御も容易である。
一方、該数平均分子量が５０００００を越えた場合、溶剤に不溶であったり、溶液に不溶部を有する等の不具合などが生じ、溶液系塗工による均一な感光層の形成が困難となる。
【００１８】
本発明の電荷輸送能を有するエポキシ化合物は新規物質であり、以下に一般的な製造方法の例を示すが、これに限定されるものではない。
例えば前記一般式（３）で表される化合物は、下記一般式（９）で表されるヒドロキシ化合物のグリシジル化により合成される。
【化１８】

（式中、Ｒ^２、Ｒ^３、Ａｒ^２、Ａｒ^３、Ａｒ^４は、前記した定義と同一のものを表す。）
【００１９】
ヒドロキシル化合物のグリシジル化による基本反応は、例えば、日刊工業新聞社　新保正樹著の「エポキシ樹脂ハンドブック」Ｐ２１〜２３に記載されている。
このときの反応は、従来公知の方法でよく、例えばトルエン、ジクロロメタン、テトラヒドロフランなどの溶媒もしくは無溶媒下で、ヒドロキシル化合物とエピクロルヒドリンなどのグリシジル化剤を溶解もしくは分散させた後、水酸化カリウム水溶液、水酸化ナトリウム水溶液などのアルカリ物質を少しずつ加え、室温〜１５０℃付近で反応させることにより容易に合成することができる。また、このときエポキシ基の加水分解を防ぐために反応系内の余分な水分は、エステル菅などを用いて反応系外へ排出する方が望ましい。
【００２０】
本発明の電荷輸送能を有するエポキシ化合物は、電子写真感光体に於ける光導電性素材、とくに光導電性を有する硬化型保護層として極めて有用であり、染料やルイス酸などの増感剤によって光学的あるいは化学的に増感される。更にこのものは、有機顔料あるいは無機材料を電荷発生物質とする、いわゆる機能分離型に於ける電荷輸送物質としても有用である。
【００２１】
上記増感剤としては、例えば、メチルバイオレット、クリスタルバイオレット等のトリアリールメタン染料、ローズベンガル、エリスロシン、ローダミン等のキサンテン染料、メチレンブルー等のチアジン染料、２，４，７−トリニトロ−９−フルオレノン、２，４−ジニトロ−９−フルオレノン等が挙げられる。
【００２２】
また、有機顔料としてはシーアイピグメントブルー２５（ＣＩ　Ｎｏ．２１１８０）、シーアイピグメントレッド４１（ＣＩ　Ｎｏ．２１２００）、シーアイピグメントレッド３（ＣＩ　Ｎｏ．４５２１０）等のアゾ顔料、シーアイピグメントブルー１６（ＣＩ　Ｎｏ．７４１００）等のフタロシアニン系顔料、シーアイバットブラウン５（ＣＩ　Ｎｏ．７３４１０）、シーアイバットダイ（ＣＩＮｏ．７３０３０）等のインジゴ系顔料、アルゴスカーレットＢ、インダンスレンスカーレッドＲ等のペリレン系顔料が挙げられる。また、セレン、セレン−テルル、硫化カドミウム、α−シリコン等の無機材料も使用できる。
【００２３】
本発明の電荷輸送能を有するエポキシ化合物の具体例を下記の表１及び表２に示す。
尚、表１には前記一般式（１）においてＡｒ^１が−Ａｒ^４ＮＲ^２Ｒ^３基である場合の具体例を示す。また表２には表１中の化合物Ｎｏ．１〜１０においてｎ＝０の場合の具体例を示す。
【００２４】
【表１】

【００２５】
【表２】

【００２６】
【実施例】
以下に実施例を示し、本発明を更に具体的に説明する。しかしながら、本発明はこれら実施例に限定されるものではない。
【００２７】
実施例１
＜化合物Ｎｏ．１の合成＞
かき混ぜ装置、温度計、滴下漏斗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９．６７ｇ（２０．０ｍｍｏｌ）とエピクロルヒドリン１８．５１ｇ（２００．０ｍｍｏｌ）、トルエン２０ｍｌを入れ、窒素気流下、２０ｗｔ％水酸化ナトリウム水溶液９．６０ｇ（４８．０ｍｍｏｌ）を５分間かけて滴下し、８５℃で４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、ジクロロメタンを加えて有機層を水洗浄した後、無水硫酸マグネシウムで乾燥し、減圧下で濃縮した。これをメタノール中で再沈し、濾過して、黄色粉末８．９８ｇ（収率７５．４％）を得た。融点は非晶質であった。
赤外線吸収スペクトル（ＮａＣｌ液膜法）を図１に示す。
【００２８】
実施例２
＜化合物Ｎｏ．１１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２に示す。
元素分析結果を以下に示す。
元素分析値（ｗｔ％）

【００２９】
応用例１
＜電子写真感光体の作製＞
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１、電荷輸送層用塗工液２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、３０±１μｍの電荷輸送層１、５±１μｍの電荷輸送層２を形成して、電子写真感光体を得た。
〔下引き層用塗工液〕
アルキッド樹脂（ベッコゾール１３０７−６０−ＥＬ
大日本インキ化学工業製）　　　　　　　　　　　　　　　　　６部
メラミン樹脂（スーパーベッカミンＧ−８２１−６０
大日本インキ化学工業製）　　　　　　　　　　　　　　　　　４部
酸化チタン　　　　　　　　　　　　　　　　　　　　　　　　４０部
メチルエチルケトン　　　　　　　　　　　　　　　　　　　　５０部
〔電荷発生層用塗工液〕
オキシチタニウムフタロシアニン顔料　　　　　　　　　　　　　３部
ポリビニルブチラール（ＵＣＣ製：ＸＹＨＬ）　　　　　　　　　２部
テトラヒドロフラン　　　　　　　　　　　　　　　　　　　　９５部
〔電荷輸送層用塗工液１〕
ビスフェノールＺ型ポリカーボネート
（帝人化成製：ＰＣＸ−５）　　　　　　　　　　　　　　　１０部
下記構造式で表される低分子電荷輸送材料　　　　　　　　　　　７部
【化１９】

ジクロロメタン　　　　　　　　　　　　　　　　　　　　　１５０部
〔電荷輸送層用塗工液２〕
２，２−ビスグリシジルオキシフェニルプロパン　　　　　　　２０部
実施例１で得られたエポキシ化合物　Ｎｏ．１　　　　　　　　１４部
イソホロンジアミン　　　　　　　　　　　　　　　　　　　　　７部
ジクロロメタン　　　　　　　　　　　　　　　　　　　　　３７０部
【００３０】
比較例１
応用例１において、電荷輸送層用塗工液２を塗布しない以外は、応用例１と全く同様にして電子写真感光体を作製した。
【００３１】
各種評価試験
応用例１および比較例１で作製した電子写真感光体を実装用にした後、（株）リコー製複写機イマジオＭＦ２２００に装着し、６０Ｋ枚（Ａ４用紙）の連続通紙試験を行い、感光体の膜厚減少量と耐傷性およびトナー画像の評価を行った。結果を下記表３に示す。
【表３】

【００３２】
評価方法及び評価基準
（１）膜厚減少量
評価方法：ＦＩＳＣＨＥＲ社製　フィッシャースコープ　ＭＭＳ　渦電流式膜厚測定器で感光体上の任意の２０点について、それぞれ１０回測定し、それらの平均値をとって膜厚とした。
（２）耐傷性
評価方法：感光体の外観を目視により観察した。
評価基準：未発生を○、局所的に発生を△、全面に発生を×、とした。
（３）トナー画像評価
評価方法：白画像（全面露光画像）の地肌汚れについて、目視により評価した。
評価基準：未発生を○、局所的に発生を△、全面に発生を×、とした。
【００３３】
この結果から電子写真感光体の最表面層として、本発明の電荷輸送能を有するエポキシ化合物を三次元架橋することにより形成することで、機械的耐久性（耐摩耗性、耐傷性）を飛躍的に向上させ、かつトナー画像も良好な電子写真感光体を提供できた。
【００３４】
【発明の効果】
本発明によれば、従来の電子写真感光体の機械的耐久性（耐摩耗性、耐傷性）を飛躍的に向上させ、かつ電子写真特性をも満足する新規な電荷輸送能を有するエポキシ化合物、及びそれらの混合物を提供することができる。
【図面の簡単な説明】
【図１】化合物Ｎｏ．１の赤外線吸収スペクトル図（ＮａＣｌ液膜法）。
【図２】化合物Ｎｏ．１１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 provides a three-dimensional crosslinked film that dramatically improves the mechanical durability (abrasion resistance, scratch resistance, etc.) of an electrophotographic photoreceptor, suppresses the deposition of a charge transport material, and does not impair the electrostatic properties. The present invention relates to an epoxy compound having charge transportability that can be prepared, and a mixture thereof.
[0002]
[Prior art]
Conventionally, as a photoconductive material used for an electrophotographic photoreceptor, inorganic materials such as selenium, cadmium sulfide, and zinc oxide, and poly-N-vinylcarbazole and triphenylamine compounds (US Pat. No. 3,180,730) ), Benzidine compounds (U.S. Pat. No. 3,265,496, JP-B-39-11546, JP-A-53-27033) and the like.
Inorganic photoreceptors have good sensitivity and durability, but have high production costs and have problems such as toxicity, disposability, and flexibility. ing. However, organic photoreceptors tend to be inferior in sensitivity and mechanical durability as compared with inorganic photoreceptors, and in particular, improvements in mechanical durability are strongly demanded.
[0003]
At present, many organic photoconductors are of a function-separated type having a charge generation layer and a charge transport layer, and the use of a function-separated type achieves both electrostatic characteristics and mechanical durability.
In addition to the sensitivity, electrostatic characteristics, and optical characteristics according to each electrophotographic process, the organic photoreceptor has durability against electrical and mechanical hazards (such as charging, exposure, development, transfer, and cleaning). Is also required.
[0004]
Specifically, electrostatic deterioration (sensitivity decrease, potential decrease, residual potential increase, etc.) of the photoreceptor due to charging or oxidizing gas (ozone, NOx) during the electrophotographic process, and physical deterioration due to rubbing ( It is required to improve durability against abrasion, scratches, increase in friction coefficient, and the like.
[0005]
In general, the surface layer of an organic photoreceptor comprises a resin photosensitive layer in which a charge transporting substance is molecularly dispersed in a binder resin. Since this charge transporting substance acts as a plasticizer and lowers the film strength, the mechanical durability of the photoreceptor greatly depends on the type of binder resin. At present, polycarbonate resins, acrylic resins, and the like have been put to practical use as resins satisfying the above requirements, but in reality, they do not satisfy all characteristics. Further, the organic photoreceptor also has a problem that a charge transport substance is deposited during storage.
[0006]
As means for solving these problems, use of a curable resin as a binder resin is disclosed in Japanese Patent Application Laid-Open No. 2-127652. However, when a curable resin is used as a binder resin, abrasion resistance and scratch resistance are greatly improved, but if the hardness is simply too high, the charge transport ability tends to be low, and the residual potential in repeated use tends to increase. is there. In addition, since the molecule-dispersed charge transport substance acts as a plasticizer to the last, problems such as precipitation are not fundamentally solved, so it is required that the curable resin and electrophotographic characteristics be compatible at a high level. I have.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to solve the problems of the conventional electrophotographic photoreceptor, in particular, to dramatically improve the mechanical durability (abrasion resistance, scratch resistance, etc.) and to prevent the photosensitive layer from depositing a charge transport material. It is an object of the present invention to provide a novel epoxy compound having a charge transport ability useful for forming a compound, and a mixture thereof.
[0008]
[Means for Solving the Problems]
According to the present invention, an epoxy compound having charge transport ability represented by the following general formulas (1), (2), (3), (4), (5), (6) and (7), and a number Mixtures thereof having an average molecular weight of 600 to 500,000 are provided.
Embedded image

(Wherein, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, .Ar 2 .Ar ¹ representing a substituted or unsubstituted aryl group of an aryl group having at least one tertiary amino ^group, Ar ³ represents a substituted or unsubstituted arylene group, provided that Ar ² and Ar ³ may be the same or different, and n represents an integer of 0 to 5000.)
Embedded image

(Wherein, ^.Ar 2, Ar ³ Ar ¹ is representative of the aryl group having at least one tertiary amino group is a substituted or unsubstituted arylene group. However, Ar ² and Ar ³ are either the same or different And n represents an integer of 0 to 5000.)
Embedded image

(In the formula, R ² and R ³ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Ar ^{2 to} Ar ⁴ represent a substituted or unsubstituted arylene group, provided that R ² and R 3 represent ³ , and Ar ^{2 to} Ar ⁴ may be the same or different, and n represents an integer of 0 to 5000.)
Embedded image

(In the formula, R ² and R ³ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ^{4 to} R ¹¹ represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group. Ar ⁴ represents a substituted or unsubstituted arylene group, provided that R ² and R ³ , and R ^{4 to} R ¹¹ may be the same or different, and n represents an integer of 0 to 5000.
Embedded image

(In the formula, R ² and R ³ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ^{4 to} R ¹⁵ represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group. However, R ² and R ³ , and R ^{4 to} R ¹⁵ may be the same or different, and n represents an integer of 0 to 5000.)
Embedded image

(In the formula, R ^{4 to} R ¹⁵ represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group, and may be the same or different. R ^{16 to} R ²⁵ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group. Represents a substituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, which may be the same or different, and n represents an integer of 0 to 5000 .)
Embedded image

(In the formula, R ^{4 to} R ¹⁵ represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group, and may be the same or different. R ^{16 to} R ²⁵ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group. Represents a substituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group, which may be the same or different.)
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in more detail.
The epoxy compound having a charge transporting ability represented by the general formulas (1) to (7) of the present invention is a novel substance, and has a carbon-carbon double bond other than a tertiary amino group or an aromatic ring in a chain measurement portion. Therefore, when a photoreceptor is prepared using these epoxy compounds, the photoreceptor has high durability against electrostatic hazards during charging and extremely excellent abrasion resistance. This is considered to be due to the fact that molecular breakage or the like in the main chain direction does not occur.
On the other hand, in a compound having a carbon-carbon double bond other than a tertiary amino group or an aromatic ring in the main chain portion, the amino group or the double bond site is easily cut by an electrostatic hazard at the time of charging. The molecular weight tends to decrease and the wear resistance tends to decrease.
In addition, when photopolymerization is used for the curing reaction of the epoxy group, it is difficult to obtain a large-area uniform crosslinked film such as a photoreceptor, and the characteristics of the photoreceptor and the abrasion characteristics are likely to be deteriorated. It is preferable to use a thermosetting method using an active hydrogen group for the epoxy compound having the function, and a large-area cross-linked film having uniform film quality can be obtained by the method.
Furthermore, unlike a photoreceptor made from a conventional thermoplastic resin, a photoreceptor made using an epoxy compound (epoxy resin) as in the present invention is composed of a three-dimensionally cross-linked curable resin. Dramatically strong against mechanical and electrostatic hazards. In particular, the three-dimensional crosslinked film of epoxy resin is different from other hard and brittle three-dimensional crosslinked films in that it has excellent toughness, and therefore has excellent wear resistance.
[0010]
The charge transport ability of the epoxy compound having charge transport ability of the present invention represented by the general formulas (1), (2), (3), (4), (5), (6) and (7) is as follows. In the epoxy compound having, the substituted or unsubstituted alkyl group of R ^{1 to} R ²⁵ 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. The phenyl group may be further substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, or the like. 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.
[0011]
Examples of the substituted or unsubstituted aryl group for R ^{1 to} R ²⁵ include a phenyl group, a naphthyl group, a biphenylyl group, a terphenylyl group, a pyrenyl group, a fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, and an anthryl group. Group, triphenylenyl group, chrysenyl group and the like. These aryl groups may be substituted by a halogen atom, the above-mentioned alkyl group, phenyl group and the like. Further, a group represented by the following general formula (8) can also be mentioned.
Embedded image

Wherein, X is -O -, - S -, - SO -, - SO 2 -, - CO- and represent a divalent group of the following.
Embedded image

Embedded image

(Where R ²⁶ and R ²⁷ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, a is an integer of 1 to 12, and b is an integer of 1 to 3 Represents.)]
In the general formula (8), the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group represented by R ²⁶ and R ²⁷ are defined as R ^{1 to} R ³ and R ^{16 to} R ²⁵ , respectively, as defined above. Specific examples are the same.
[0012]
In the epoxy compounds having a charge transporting ability represented by the general formulas (6) and (7), a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryloxy group of R ^{16 to} R ²⁵ is, respectively, Examples thereof include groups each derived from a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group described in the description of R ^{1 to} R ²⁵ .
[0013]
Further, in the epoxy compound having a charge transporting ability represented by the general formulas (1) and (2), the aryl group of the aryl group having at least one tertiary amino group of Ar ¹ includes the above-described R ¹ to The same as those described in the description of R ³ and R ^{16 to} R ²⁵ can be given.
Yet the tertiary amino group, include groups represented by -NR ² R ³ group, definition and specific examples of the R ^2, R ³ are the same as those described above.
[0014]
In the epoxy compounds having a charge transporting ability represented by the general formulas (1), (2), (3) and (4), the substituted or unsubstituted arylene groups of Ar ² , Ar ³ and Ar ⁴ are preferably And the divalent group derived from the aryl group described in the description of Ar ¹ (that is, the description of R ^{1 to} R ³ and R ^{16 to} R ²⁵ ).
Further, as the substituent for the arylene group, the same substituents as those described in the description of R ^{4 to} R ¹⁵ can be given.
[0015]
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.
[0016]
Further, the epoxy compound having a charge transporting ability represented by any of the general formulas (1) to (7) of the present invention is a mixture of the epoxy compound with another epoxy compound, a mixture thereof, or a mixture thereof. It is also preferable to use it as a mixture with another epoxy compound.
By using such a mixture, the photoconductor design (eg, electrostatic characteristics, charge mobility, mechanical durability, glass transition temperature, etc.) can be easily and freely performed. There is also an advantage that the photoreceptor can be manufactured at low cost by combining with a commercially available epoxy compound.
[0017]
Further, the number average molecular weight of the mixture of the epoxy compounds having a charge transporting ability represented by any of the general formulas (1) to (6) of the present invention is preferably from 600 to 500,000.
When the number average molecular weight is in the range of 600 to 500,000, solution-based coating is easy in the production of the photoreceptor, and the control of the photoreceptor characteristics is also easy.
On the other hand, when the number average molecular weight exceeds 500,000, inconveniences such as insolubility in a solvent and an insoluble portion in a solution occur, and it is difficult to form a uniform photosensitive layer by solution coating.
[0018]
The epoxy compound having a charge transport ability of the present invention is a novel substance, and examples of a general production method are shown below, but the invention is not limited thereto.
For example, the compound represented by the general formula (3) is synthesized by glycidylation of a hydroxy compound represented by the following general formula (9).
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(In the formula, R ² , R ³ , Ar ² , Ar ³ , and Ar ⁴ represent the same as defined above.)
[0019]
The basic reaction by glycidylation of a hydroxyl compound is described in, for example, “Epoxy Resin Handbook”, pages 21 to 23, written by Masaki Shinbo, Nikkan Kogyo Shimbun.
The reaction at this time may be a conventionally known method, for example, in a solvent or no solvent such as toluene, dichloromethane, and tetrahydrofuran, after dissolving or dispersing the glycidylating agent such as a hydroxyl compound and epichlorohydrin, and then adding an aqueous potassium hydroxide solution. It can be easily synthesized by adding an alkali substance such as an aqueous solution of sodium hydroxide little by little and reacting at room temperature to about 150 ° C. At this time, in order to prevent hydrolysis of the epoxy group, it is preferable that excess water in the reaction system is discharged out of the reaction system using an ester tube or the like.
[0020]
The charge-transporting epoxy compound of the present invention is extremely useful as a photoconductive material in an electrophotographic photoreceptor, in particular, as a curable protective layer having photoconductivity, and is provided by a sensitizer such as a dye or a Lewis acid. Sensitized optically or chemically. Further, this is also useful as a charge transport material in a so-called function separation type in which an organic pigment or an inorganic material is used as a charge generating material.
[0021]
Examples of the sensitizer include triarylmethane dyes such as methyl violet and crystal violet, xanthene dyes such as rose bengal, erythrosine and rhodamine, thiazine dyes such as methylene blue, 2,4,7-trinitro-9-fluorenone, 2,4-dinitro-9-fluorenone and the like.
[0022]
Examples of organic pigments include azo pigments such as C.I. Pigment Blue 25 (CI No. 21180), C.I. Pigment Red 41 (CI. No. 21200), C.I. Pigment Red 3 (CI. No. 45210), and C.I. Phthalocyanine pigments, such as C.I. Brown 100 (CI No. 73410), C.I. No. In addition, inorganic materials such as selenium, selenium-tellurium, cadmium sulfide, and α-silicon can also be used.
[0023]
Specific examples of the epoxy compound having a charge transport ability of the present invention are shown in Tables 1 and 2 below.
Table 1 shows a specific example in the case where Ar ¹ in the general formula (1) is a group of —Ar ⁴ NR ² R ³ . Table 2 shows the compound No. in Table 1. Specific examples when n = 0 in 1 to 10 are shown.
[0024]
[Table 1]

[0025]
[Table 2]

[0026]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to these examples.
[0027]
Example 1
<Compound No. Synthesis of 1>
9.67 g (20.0 mmol) of 4- [2,2-bis (4-hydroxyphenyl) vinyl] phenyl-bis (4-methylphenyl) amine was added to a reaction vessel equipped with a stirring device, a thermometer, and a dropping funnel. 18.51 g (200.0 mmol) of epichlorohydrin and 20 ml of toluene were added, and 9.60 g (48.0 mmol) of a 20 wt% aqueous sodium hydroxide solution was added dropwise over 5 minutes under a nitrogen stream, followed by reaction at 85 ° C. for 4 hours. This was allowed to cool to room temperature, excess epichlorohydrin was recovered under reduced pressure, dichloromethane was added, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. This was reprecipitated in methanol and filtered to obtain 8.98 g (yield 75.4%) of a yellow powder. The melting point was amorphous.
FIG. 1 shows an infrared absorption spectrum (NaCl liquid film method).
[0028]
Example 2
<Compound No. Synthesis of 11>
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. 2 shows the infrared absorption spectrum (NaCl liquid film method).
The results of elemental analysis are shown below.
Elemental analysis value (wt%)

[0029]
Application example 1
<Preparation of electrophotographic photoreceptor>
A coating liquid for an undercoat layer, a coating liquid for a charge generation layer, a coating liquid 1 for a charge transport layer, and a coating liquid 2 for a charge transport layer are sequentially coated and dried on an aluminum drum having a diameter of 30 mm. Thus, an undercoat layer of 3.5 μm, a charge generation layer of 0.2 μm, a charge transport layer 1 of 30 ± 1 μm, and a charge transport layer 2 of 5 ± 1 μm were obtained to obtain an electrophotographic photosensitive member.
(Coating liquid for undercoat layer)
Alkyd resin (Veccosol 1307-60-EL
6 parts melamine resin (Super Beckamine G-821-60)
4 parts Titanium oxide 40 parts Methyl ethyl ketone 50 parts [Coating solution for charge generating layer]
Oxytitanium phthalocyanine pigment 3 parts Polyvinyl butyral (UCC: XYHL) 2 parts Tetrahydrofuran 95 parts [Coating liquid 1 for charge transport layer]
Bisphenol Z-type polycarbonate (PCX-5 manufactured by Teijin Chemicals) 10 parts Low molecular charge transporting material represented by the following structural formula 7 parts

150 parts of dichloromethane [Coating liquid for charge transport layer 2]
2,2-bisglycidyloxyphenylpropane 20 parts Epoxy compound No. 1 obtained in Example 1 1 14 parts Isophorone diamine 7 parts Dichloromethane 370 parts
Comparative Example 1
An electrophotographic photoreceptor was produced in exactly the same manner as in Application Example 1, except that the coating liquid 2 for the charge transport layer was not applied.
[0031]
Various evaluation tests After the electrophotographic photosensitive members produced in Application Example 1 and Comparative Example 1 were mounted, they were mounted on a copier Imagio MF2200 manufactured by Ricoh Co., Ltd., and a continuous paper passing test of 60K sheets (A4 paper) was performed. Then, the amount of reduction in the thickness of the photoreceptor, the scratch resistance, and the toner image were evaluated. The results are shown in Table 3 below.
[Table 3]

[0032]
Evaluation Method and Evaluation Criteria (1) Film Thickness Reduction Evaluation Method: Measured 10 times for each of 20 arbitrary points on the photoreceptor using a Fischerscope MMS eddy current type film thickness meter manufactured by FISCHER, and averaged the average values. This was taken as the film thickness.
(2) Scratch resistance evaluation method: The appearance of the photoreceptor was visually observed.
Evaluation criterion: O was not generated, Δ was locally generated, and X was generated over the entire surface.
(3) Toner image evaluation evaluation method: The background image of a white image (entirely exposed image) was visually evaluated.
Evaluation criteria: O was not generated, Δ was locally generated, and X was generated over the entire surface.
[0033]
From these results, the mechanical durability (abrasion resistance and scratch resistance) is dramatically improved by forming the outermost surface layer of the electrophotographic photosensitive member by three-dimensionally crosslinking the epoxy compound having the charge transport ability of the present invention. And an electrophotographic photoreceptor having a good toner image was provided.
[0034]
【The invention's effect】
According to the present invention, there is provided an epoxy compound having a novel charge transporting ability that dramatically improves the mechanical durability (abrasion resistance and scratch resistance) of a conventional electrophotographic photoreceptor and also satisfies electrophotographic properties. And mixtures thereof.
[Brief description of the drawings]
FIG. 1. Compound No. 1 is an infrared absorption spectrum diagram (NaCl liquid membrane method).
FIG. 2. Compound No. 11 is an infrared absorption spectrum diagram (NaCl liquid membrane method).

Claims (8)

An epoxy compound having a charge transporting ability represented by the following general formula (1).

(Wherein, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, .Ar 2 .Ar ¹ representing a substituted or unsubstituted aryl group of an aryl group having at least one tertiary amino ^group, Ar ³ represents a substituted or unsubstituted arylene group, provided that Ar ² and Ar ³ may be the same or different, and n represents an integer of 0 to 5000.) An epoxy compound having a charge transporting ability represented by the following general formula (2).

(Wherein, ^.Ar 2, Ar ³ Ar ¹ is representative of the aryl group having at least one tertiary amino group is a substituted or unsubstituted arylene group. However, Ar ² and Ar ³ are either the same or different And n represents an integer of 0 to 5000.) An epoxy compound having a charge transporting ability represented by the following general formula (3).

(In the formula, R ² and R ³ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Ar ^{2 to} Ar ⁴ represent a substituted or unsubstituted arylene group, provided that R ² and R 3 represent ³ , and Ar ^{2 to} Ar ⁴ may be the same or different, and n represents an integer of 0 to 5000.) An epoxy compound having a charge transporting ability represented by the following general formula (4).

(In the formula, R ² and R ³ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ^{4 to} R ¹¹ represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group. Ar ⁴ represents a substituted or unsubstituted arylene group, provided that R ² and R ³ , and R ^{4 to} R ¹¹ may be the same or different, and n represents an integer of 0 to 5000. An epoxy compound having a charge transporting ability represented by the following general formula (5).

(In the formula, R ² and R ³ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ^{4 to} R ¹⁵ represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group. However, R ² and R ³ , and R ^{4 to} R ¹⁵ may be the same or different, and n represents an integer of 0 to 5000.) An epoxy compound having a charge transporting ability represented by the following general formula (6).

(In the formula, R ^{4 to} R ¹⁵ represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group, and may be the same or different. R ^{16 to} R ²⁵ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group. Represents a substituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, which may be the same or different, and n represents an integer of 0 to 5000 .) An epoxy compound having a charge transporting ability represented by the following general formula (7).

(In the formula, R ^{4 to} R ¹⁵ represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group, and may be the same or different. R ^{16 to} R ²⁵ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group. Represents a substituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group, which may be the same or different.) The mixture containing the epoxy compound having a charge transport ability according to any one of claims 1 to 7, which has a number average molecular weight of 600 to 500,000.

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