JP2004093802A - Electrophotographic photoreceptor, process cartridge and electrophotographic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which has an excellent potential characteristic and electrophotographic characteristic even under a low-temperature and low-humidity environment, and to provide a process cartridge and an electrophotographic device having the electrophotographicphotoreceptor. <P>SOLUTION: The electrophotographic photoreceptor has an intermediate layer and a photosensitive layer on a substrate in the order thereof. Therein, the intermediate layer contains an imide resin having electron transportability and the photosensitive layer contains a product obtained by polymerizing hole transport material which has two or more chain polymerizable functional groups in the same molecule. <P>COPYRIGHT: (C)2004,JPO

Description

【００４２】
（式（１）中、Ｙ^１１は２価の有機基を示し、Ａ^１１は下記式（２）で示される構造を有する２価の基を示す。
【外１０】

【００４３】
（式（２）中、Ｒ^２１〜Ｒ^２４は、それぞれ独立に、水素原子、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシ基、または、シアノ基を示す。））
【００４４】
また、上記電子輸送能を有するイミド樹脂は、下記式（３）で示される繰り返し構造単位を有する樹脂であることが好ましい。
【外１１】

【００４５】
（式（３）中、Ｙ^３１は３価の有機基を示し、Ａ^３１は下記式（４）で示される構造を有する基を示す。
【外１２】

【００４６】
（式（４）中、Ｒ^４１〜Ｒ^４４は、それぞれ独立に、水素原子、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシ基、または、シアノ基を示し、Ｙ^４１は、アルキレン基、エーテル基、チオエーテル基、または、−ＣＯ−Ｏ−基を示す。））
【００４７】
また、上記電子輸送能を有するイミド樹脂は、下記式（５）で示される繰り返し構造単位を有する樹脂であることが好ましい。
【外１３】

【００４８】
（式（５）中、Ｒ^５１は、水素原子またはアルキル基を示し、Ａ^５１は、下記式（４）で示される構造を有する基を示す。
【外１４】

【００４９】
（式（４）中、Ｒ^４１〜Ｒ^４４は、それぞれ独立に、水素原子、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシ基、または、シアノ基を示し、Ｙ^４１は、アルキレン基、エーテル基、チオエーテル基、または、−ＣＯ−Ｏ−基を示す。））
【００５０】
また、上記電子輸送能を有するイミド樹脂は、下記式（６）で示される繰り返し構造単位を有する樹脂であることが好ましい。
【外１５】

【００５１】
（式（６）中、Ａ^６１は、下記式（４）で示される構造を有する基を示す。
【外１６】

【００５２】
（式（４）中、Ｒ^４１〜Ｒ^４４は、それぞれ独立に、水素原子、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシ基、または、シアノ基を示し、Ｙ^４１は、アルキレン基、エーテル基、チオエーテル基、または、−ＣＯ−Ｏ−基を示す。））
【００５３】
また、上記表現の２価の有機基としては、アルキレン基、アリーレン基が挙げられ、３価の有機基としては、置換基を有するアルキル基、アリーレン基が挙げられる。
【００５４】
また、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子などが挙げられ、アルキル基としては、メチル基、エチル基、プロピル基などが挙げられ、アルコキシ基としては、メトキシ基、エトキシ基などが挙げられる。
【００５５】
また、アルキレン基としては、メチレン基、エチレン基が挙げられる。
【００５６】
上記各基が有してもよい置換基としては、ハロゲン原子や、メチル基、エチル基、プロピル基などのアルキル基、メトキシ基、エトキシ基などのアルコキシ基などが挙げられる。
【００５７】
上記電子輸送能を有するイミド樹脂の繰り返し構造単位の具体例を表１〜４に示す。
【００５８】
【表１】

【００５９】
【表２】

【００６０】
【表３】

【００６１】
【表４】

【００６２】
中間層の膜厚は、０．１〜１０μｍが好ましく、さらには０．３〜５μｍがより好ましい。
【００６３】
中間層中に含有される電子輸送能を有するイミド樹脂の量は、中間層全質量に対して、２０〜１００質量％が好ましく、３０〜１００質量％がより好ましい。
【００６４】
中間層の上には、感光層が設けられる。本発明で用いる電子写真感光体の感光層は、上述のとおり、支持体（中間層）側から電荷発生層、電荷輸送層の順に積層した積層型が好ましく、以下、その型の感光層について説明する。
【００６５】
本発明において電荷発生物質としては一般的な材料を用いることが可能である。
【００６６】
電荷発生物質としては、一般的に、セレン−テルル、ピリリウム、チアピリリウム系染料、また各種の中心金属および結晶型、具体的には、例えば、α、β、γ、εおよびＸ型などの結晶型を有するフタロシアニン化合物、アントアントロン顔料、ジベンズピレンキノン顔料、ピラントロン顔料、トリスアゾ顔料、ジスアゾ顔料、モノアゾ顔料、インジゴ顔料、キナクリドン顔料、非対称キノシアニン顔料、キノシアニン、および、特開昭５４−１４３６４５号公報に記載のアモルファスシリコンなどが挙げられる。
【００６７】
また、電荷発生物質以外に、結着樹脂を用いることも可能である。
【００６８】
結着樹脂の具体例としては、ポリエステル、ポリウレタン、ポリアクリレート、ポリエチレン、ポリスチレン、ポリブタジエン、ポリカーボネート、ポリアミド、ポリプロピレン、ポリイミド、フェノール樹脂、アクリル樹脂、シリコーン樹脂、エポキシ樹脂、ユリア樹脂、アリル樹脂、アルキッド樹脂、ポリアミド−イミド、ナイロン、ポリサルフォン、ポリアリルエーテル、ポリアセタール、ブチラール樹脂、ベンザール樹脂などが挙げられる。
【００６９】
電荷発生層中に含まれる電荷発生物質の量は、電荷発生層全質量に対して、１０〜９０質量％が好ましく、３０〜７０質量％がより好ましい。
【００７０】
電荷発生層の膜厚は、０．００１〜６μｍが好ましく、さらには０．０１〜２μｍがより好ましい。
【００７１】
本発明の電子写真感光体は、感光層が、好ましくは積層型の感光層における電荷輸送層が、同一分子内に２つ以上の連鎖重合性官能基を有する正孔輸送物質を重合したものを含有する。
【００７２】
連鎖重合性官能基としては、ラジカルあるいはイオンなどの中間体を経由して反応が進行する不飽和重合性官能基あるいは開環重合性官能基が挙げられる。これら官能基の例を以下に示す。
【００７３】
【外１７】

（７）
【００７４】
【外１８】

（８）
【００７５】
【外１９】

（９）
【００７６】
【外２０】

（１０）
【００７７】
【外２１】

（１１）
【００７８】
【外２２】

（ｎは１から３の整数）　（１２）
【００７９】
【外２３】

（ｎは１から３の整数）　（１３）
【００８０】
これらの中でも特に式（７）（８）に示されるアクリロイルオキシ基及びメタクリロイルオキシ基が、重合特性において好ましい。
【００８１】
上記同一分子内に２つ以上の連鎖重合性官能基を有する正孔輸送物質の具体例を以下に示す。
【００８２】
【表５】

【００８３】
【表６】

【００８４】
層の形成方法としては、上記正孔輸送物質を含有する溶液を塗布後、重合／架橋反応させるのが好ましいが、前もって正孔輸送物質を含む溶液を反応させて硬化物を得た後に、再度溶剤中に分散あるいは溶解させたものなどを用いて形成することも可能である。
【００８５】
同一分子内に２つ以上の連鎖重合性官能基を有する正孔輸送物質を重合したものを電荷発生層上の電荷輸送層に使用する場合、硬化後の電荷輸送層全質量に対して、３０質量％以上が好ましく、さらには５０質量％以上がより好ましい。１０質量％未満であると、電荷輸送能が低下し、感度の低下および残留電位の上昇などの問題点が生じる場合がある。
【００８６】
電荷輸送層の膜厚は、１〜５０μｍが好ましく、さらには３〜３０μｍがより好ましい。
【００８７】
また、積層型感光層を有する電子写真感光体においては、電子写真感光体表面の機械的強度向上を目的として、表面層にあたる電荷輸送層を、支持体側の第１電荷輸送層と表面側の第２電荷輸送層とに機能分離してもよい。この第２電荷輸送層は、保護層と呼ばれることもある。
【００８８】
同一分子内に２つ以上の連鎖重合性官能基を有する正孔輸送物質を重合したものを第２電荷輸送層に使用する場合は、その下層に当たる第１電荷輸送層は、適当な電荷輸送物質、例えば、ポリ−Ｎ−ビニルカルバゾールおよびポリスチリルアントラセンなどの複素環や縮合多環芳香族を有する高分子化合物や、ピラゾリン、イミダゾール、オキサゾール、トリアゾールおよびカルバゾールなどの複素環化合物、トリフェニルメタンなどのトリアリールアルカン誘導体、トリフェニルアミンなどのトリアリールアミン誘導体、フェニレンジアミン誘導体、Ｎ−フェニルカルバゾール誘導体、スチルベン誘導体およびヒドラジン誘導体などの低分子化合物などを、適当な結着樹脂（上述の電荷発生層用樹脂の中から選択できる）と共に溶剤に分散／溶解した溶液を塗布し、乾燥することによって形成する従来の電荷輸送層としてもよい。
【００８９】
第１電荷輸送層における電荷輸送物質と結着樹脂の比率は、両者の全質量を１００とした場合に電荷輸送物質の重量が３０〜１００であることが好ましく、さらには５０〜１００であることがより好ましい。電荷輸送物質の量が３０に満たないと、電荷輸送能が低下し、感度の低下および残留電位の上昇などの問題点が生じやすくなる。
【００９０】
一方、第２電荷輸送層においては、同一分子内に２つ以上の連鎖重合性官能基を有する正孔輸送物質を重合したものは、硬化後の第２電荷輸送層全質量に対して、３０質量％以上が好ましく、さらには５０質量％以上がより好ましい。１０質量％未満であると、電荷輸送能が低下し、感度の低下および残留電位の上昇などの問題点が生じる場合がある。
【００９１】
機能分離した電荷輸送層を採用する場合は、電荷輸送層の膜厚は、第１電荷輸送層と第２電荷輸送層との合計膜厚が１〜５０μｍとなることが好ましく、さらには５〜３０μｍであることがより好ましい。
【００９２】
なお、上記単層型感光層を有する電子写真感光体においても、上記第２電荷輸送層と同様の層を最表面に設けることができる。
【００９３】
本発明の電子写真感光体の製造方法としては、蒸着、塗布などの方法が用いられる。塗布による方法は、薄膜から厚膜まで広い範囲で、しかもさまざまな組成の膜が形成可能である。具体的には、バーコーター、ナイフコーター、浸漬塗布、スプレー塗布、ビーム塗布、静電塗布、ロールコーター、アトライター、粉体塗布などで塗布される。
【００９４】
また、本発明の電子写真感光体の感光層には、各種添加剤を添加することができる。添加剤とは酸化防止剤および紫外線吸収剤などの劣化防止剤や、フッ素原子含有樹脂微粒子などの潤滑剤その他である。
【００９５】
本発明においては、同一分子内に２つ以上の連鎖重合性官能基を有する正孔輸送物質の重合（そして架橋）は、放射線により行うことが好ましい。
【００９６】
放射線による重合の最大の利点は、重合開始剤を必要としない点であり、これにより非常に高純度な三次元感光層マトリックスの作製が可能となり、良好な電子写真特性を確保することができる。また、短時間で、かつ効率的な重合反応であるがゆえに生産性も高い。さらに、放射線は透過性に優れるので、添加剤などの遮蔽物質が層中に存在する場合や、厚い層を形成する場合の硬化阻害の影響が非常に小さいことなども挙げられる。
【００９７】
ただし、連鎖重合性官能基の種類や中心骨格の種類によっては、重合反応が進行しにくい場合があり、その際には影響のない範囲内で重合開始剤を添加することは可能である。
【００９８】
使用する放射線としては、電子線およびγ線などが挙げられるが、効率の点では電子線が好ましい。
【００９９】
電子線照射をする場合、加速器としてはスキャニング型、エレクトロカーテン型、ブロードビーム型、パルス型およびラミナー型などいずれの形式も使用することができる。
【０１００】
また、電子線を照射する場合に、本発明においては、電気特性および耐久性能を発現させる上で照射条件が非常に重要である。
【０１０１】
加速電圧は、３００ｋＶ以下が好ましく、さらには１５０ｋＶ以下がより好ましい。
【０１０２】
線量は、１Ｍｒａｄ〜１０Ｍｒａｄの範囲が好ましく、さらには３Ｍｒａｄ〜５０Ｍｒａｄの範囲がより好ましい。
【０１０３】
加速電圧が３００ｋＶを超えると、電子写真感光体特性に対する電子線照射のダメージが増加する傾向にある。また、線量が１Ｍｒａｄよりも少ない場合には架橋が不十分となりやすく、１００Ｍｒａｄを超えると電子写真感光体の劣化が起こりやすいので注意が必要である。
【０１０４】
図１に、本発明の電子写真感光体を有するプロセスカートリッジを有する電子写真装置の概略構成例を示す。
【０１０５】
図１において、１は像担持体としての本発明のドラム型電子写真感光体であり軸２を中心に矢印方向に所定の周速度で回転駆動される。
【０１０６】
該電子写真感光体１は回転過程で帯電手段３によりその周面に正または負の所定電位の均一帯電を受け、次いで露光手段により露光光４（スリット露光・レーザービーム走査露光など）を受ける。これにより電子写真感光体周面に露光像に対応した静電潜像が順次形成されていく。
【０１０７】
その静電潜像は、次いで現像手段５でトナー現像され、そのトナー現像像は転写手段６により不図示の給紙部から電子写真感光体１と転写手段６との間に電子写真感光体１の回転と同期取り出されて給紙された転写材７の面に順次転写されていく。
【０１０８】
像転写を受けた転写材７は、電子写真感光体面から分離されて、定着手段８へ導入されて像定着を受けて複写物（コピー）として機外へ出力される。
【０１０９】
像転写後の電子写真感光体１の表面は、クリーニング手段９にて転写残りトナーの除去を受けて清浄面化され、さらに前露光手段１０により除電処理されて繰り返して像形成に使用される。
【０１１０】
帯電手段３が図のように接触帯電手段である場合は、前露光手段は必ずしも必要ではない。
【０１１１】
上述の電子写真感光体や現像手段、クリーニング手段などの構成要素のうち、複数のものを装置ユニットとして一体に結合して構成し、このユニットを装置本体に対して着脱自在に構成してもよい。
【０１１２】
例えば、電子写真感光体１とクリーニング手段９とを一体化して１つの装置ユニット（プロセスカートリッジ１１）とし、装置本体のレール１２などの案内手段を用いて着脱自在の構成にしてもよい。このとき、上記の装置ユニットの方に帯電手段および／または現像手段を伴って構成してもよい。
【０１１３】
露光光４は、電子写真装置を複写機やプリンターとして使用する場合には、原稿からの反射光や透過光、あるいは原稿を読取り信号化し、この信号によりレーザービームの走査、ＬＥＤアレイの駆動、または液晶シャッターアレイの駆動などにより行われる。ファクシミリのプリンターとして使用する場合には、露光光４は受信データをプリントするための露光になる。
【０１１４】
本発明の電子写真感光体は、電子写真複写機に利用するのみならず、レーザービームプリンター、ＣＲＴプリンター、ＬＥＤプリンター、液晶プリンター、レーザー製版など電子写真応用分野にも広く用いることができる。
【０１１５】
【実施例】
以下、実施例にしたがい、本発明をより一層詳細に説明する。
【０１１６】
なお、「部」は「質量部」を意味する。
【０１１７】
［実施例１］
本実施例における電子写真感光体は以下のとおりである。
【０１１８】
まず、導電層用の塗料を以下の手順で調製した。
【０１１９】
１０％の酸化アンチモンを含有する酸化スズで被覆した導電性酸化チタン粉体５０部、レゾール型フェノール樹脂２５部、メチセロソルブ２０部、メタノール５部およびシリコーンオイル（ポリジメチルシロキサンポリオキシアルキレン共重合体、平均分子量３０００）０．００２部を直径１ｍｍのガラスビーズを用いたサンドミル装置で２時間分散して調製した。上記塗料を直径３０ｍｍのアルミニウムシリンダー上に浸漬コーティング法で塗布し、１４０℃で３０分乾燥して、膜厚２０μｍの導電層を形成した。
【０１２０】
次に、表１中の化合物例１で示される繰り返し構造単位を有するポリアミド酸１０部を、Ｎ，Ｎ−ジメチルアセトアミド９０部に溶解した液を浸漬塗布し、１８０℃で１時間加熱硬化することによって、膜厚が１μｍの中間層を形成した。
【０１２１】
次に、ＣｕＫαのＸ線回折におけるブラッグ角２θ±０．２°の９．０°、１４．２°、２３．９°および２７．１°に強いピークを有するオキシチタニウムフタロシアニンを２部、ポリビニルブチラール（商品名エスレックＢＭ−２、積水化学（株）製）１部、およびシクロヘキサノン３５部を、直径１ｍｍのガラスビーズを用いたサンドミル装置で２時間分散し、その後に酢酸エチル６０部を加えて電荷発生層用塗料を調製した。この塗料を上記中間層上に浸漬塗布方法で塗布して５０℃１０分間乾燥し、膜厚０．２μｍの電荷発生層を形成した。
【０１２２】
次に、下記式（８）で示される繰り返し構造単位を有するポリカーボネート樹脂（粘度平均分子量２２０００）１０部と、
【外２４】

【０１２３】
電荷輸送物質として下記式（９）で示される構造を有するトリールアミン化合物１０部を
【外２５】

【０１２４】
モノクロロベンゼン３０部およびジクロロメタン３０部の混合溶媒中に溶解し、第１電荷輸送層用塗料を調製した。
【０１２５】
この塗料を、上記電荷発生層上に浸漬コーティング法によって塗布し、１２０℃で６０分間熱風乾燥して、膜厚１５μｍの第１電荷輸送層を形成した。
【０１２６】
次に、化合物例（Ｈ−１）６０部を、モノクロロベンゼン１００部およびジクロロメタン１００部の混合溶媒中に溶解し、第２電荷輸送層用塗料を調製した。
【０１２７】
この塗料を上記第１電荷輸送層上にスプレーコーティングし、加速電圧１５０ｋＶ、照射線量３０Ｍｒａｄの条件で電子線を照射し、上記化合物を含有する塗料を硬化し、膜厚５μｍの正孔輸送能を有する第２電荷輸送層を形成し、電子写真感光体を得た。
【０１２８】
このようにして得られた電子写真感光体を、１５℃、１０％ＲＨ環境下に２日放置後、キヤノン（株）製ＧＰ４０５を用いて、１０００枚通紙前後での露光時電位、非露光時電位を評価した。
【０１２９】
評価結果を表７に示す。
【０１３０】
［実施例２〜５］
実施例１において、化合物例（Ｈ−１）を、化合物例（Ｈ−２）〜（Ｈ−５）にそれぞれ変更した以外は、実施例１と同様に電子写真感光体を作製し、評価した。
【０１３１】
評価結果を表７に示す。
【０１３２】
［実施例６］
実施例１において、表１中の化合物例１で示される繰り返し構造単位を有するポリアミド酸を、表１中の化合物例３で示される繰り返し構造単位を有するポリアミド酸に変更した以外は、実施例１と同様に電子写真感光体を作製し、評価した。
【０１３３】
評価結果を表７に示す。
【０１３４】
［実施例７］
実施例１において、中間層を表２の中の化合物例１に変更した以外は、実施例１と同様に電子写真感光体を作成し、評価した。評価結果を表７に示す。
【０１３５】
［実施例８］
実施例１において、中間層を表３の中の化合物例１に変更した以外は、実施例１と同様に電子写真感光体を作成し、評価した。評価結果を表７に示す。
【０１３６】
［実施例９］
実施例１において、中間層を表４の中の化合物例１に変更した以外は、実施例１と同様に電子写真感光体を作成し、評価した。評価結果を表７に示す。
【０１３７】
［比較例１〜５］
実施例１〜５の中間層を、メトキシメチル化ナイロン（重量平均分子量３２，０００）５部とアルコール可溶性共重合ナイロン（重量平均分子量２９，０００）１０部をメタノール９５部に溶解した液を浸漬塗布し、１００℃２０分乾燥して形成した膜厚１μｍの中間層に変更した以外は、それぞれ実施例１〜５と同様に電子写真感光体を作製し、評価を行った。
【０１３８】
評価結果を表７に示す。
【０１３９】
【表７】

【０１４０】
【発明の効果】
以上のように、本発明によれば、低温低湿環境下でも優れた電位特性および電子写真特性を有する電子写真感光体、該電子写真感光体を有するプロセスカートリッジおよび電子写真装置を提供することができる。
【図面の簡単な説明】
【図１】本発明の電子写真感光体を有するプロセスカートリッジを有する電子写真装置の概略構成の例を示す図である。
【符号の説明】
１　電子写真感光体
２　軸
３　帯電手段
４　露光光
５　現像手段
６　転写手段
７　転写材
８　定着手段
９　クリーニング手段
１０　前露光手段
１１　プロセスカートリッジ
１２　レール（案内手段）[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus. More specifically, the present invention relates to an electrophotographic photosensitive member having an intermediate layer and a photosensitive layer on a support in this order, and an electrophotographic photosensitive member. The present invention relates to a process cartridge having the same and an electrophotographic apparatus.
[0002]
[Prior art]
An organic electrophotographic photoreceptor using an organic conductive substance has an advantage of being able to provide an inexpensive electrophotographic photoreceptor with extremely high productivity because it has good film-forming properties and can be produced by coating.
[0003]
In addition, there is an advantage that the photosensitive wavelength range can be freely controlled by selecting a dye or a pigment to be used, and wide studies have been made so far.
[0004]
Recently, with the development of a function-separated electrophotographic photoreceptor in which a charge generation layer containing an organic conductive dye or pigment and a charge transport layer containing a photoconductive polymer or a low-molecular organic photoconductive substance are laminated, Significant improvements have been made in sensitivity and durability, which have been regarded as disadvantages of conventional organic electrophotographic photosensitive members, and these have become the mainstream of organic electrophotographic photosensitive members.
[0005]
However, when the photosensitive layer is formed directly on the support, there are problems such as low charging ability and lack of potential stability upon repeated use.
[0006]
If these potentials are not stable, the image density will not be stable or the image will fog.
[0007]
Therefore, a barrier layer between the photosensitive layer and the support and an adhesive layer are provided between the photosensitive layer and the support because of the barrier property between the photosensitive layer and the support, and the covering property of defects, dirt, deposits, and scratches on the support surface. It has been proposed to provide an intermediate layer having the function of
[0008]
Examples of such an intermediate layer include polyamide (described in JP-A-46-47344 and JP-A-52-25638) and polyester (described in JP-A-52-20836 and JP-A-54-26738). Described), polyurethane (described in JP-A-49-10044 and JP-A-53-89435), casein (described in JP-A-55-103556), polypeptide (described in JP-A-53-48523). ), Polyvinyl alcohol (described in JP-A-52-100240), polyvinylpyrrolidone (described in JP-A-48-30936), vinyl acetate-ethylene copolymer (described in JP-A-48-26141), anhydrous Maleic ester polymer (described in JP-A-52-10138), polyvinyl butyral (JP-A-57-90639, JP-A-58-106549; quaternary ammonium salt-containing polymers (JP-A-51-149149 and JP-A-56-60448); ethyl cellulose (JP-A-55-143564) It is known to use such resins.
[0009]
Also, needless to say, the electrophotographic photoreceptor is required to have sensitivity, electrical characteristics, and optical characteristics according to the applied electrophotographic process.
[0010]
In particular, in the case of an electrophotographic photoreceptor that is repeatedly used, external electric and mechanical forces such as charging, exposure, toner development, transfer to paper, and cleaning of residual toner are applied to the electrophotographic photoreceptor surface. Since they are added directly, durability against them is required.
[0011]
More specifically, durability of the surface due to rubbing and durability against scratching, surface deterioration due to charging, for example, deterioration of transfer efficiency and slipperiness, and further, deterioration of electrical characteristics such as sensitivity deterioration and charging potential reduction. Durability is required.
[0012]
Generally, the configuration of an electrophotographic photoreceptor is formed by laminating thin resin layers, and the characteristics of the resin are very important.
[0013]
In recent years, acrylic resins, polycarbonate resins, and the like have been put to practical use as resins that satisfy the above-mentioned conditions to some extent. However, not all of the above-mentioned characteristics are satisfied by these resins. In order to improve the durability of the body, it is difficult to say that the resin film hardness is sufficiently high. Even when these resins are used as a resin for forming a surface layer, there has been a problem that the surface layer is worn when repeatedly used, and further damage is generated.
[0014]
Furthermore, due to recent demands for higher sensitivity of organic electrophotographic photoreceptors, low molecular weight compounds such as charge transport substances are often added in relatively large amounts. In this case, these low molecular weight substances are used as plasticizers. Due to the action, the film strength is remarkably reduced, and abrasion of the surface layer and generation of scratches at the time of further repeated use are problematic. In addition, when the electrophotographic photoreceptor is stored for a long period of time, there is a problem that the above-mentioned low molecular weight component is precipitated and the layers are separated.
[0015]
As means for solving these problems, an attempt to use a curable resin as a resin for the charge transport layer is disclosed in, for example, Japanese Patent Application Laid-Open No. 2-127652. As described above, by using a curable resin as the resin for the charge transport layer and curing and cross-linking the charge transport layer, the mechanical strength is increased, and the wear resistance and scratch resistance during repeated use are greatly improved.
[0016]
However, even if a curable resin is used, the low molecular weight component acts as a plasticizer in the binder resin to the last, so that the above-described problems of precipitation and layer separation have not been fundamentally solved. Further, in the charge transport layer composed of an organic charge transport material and a binder resin, the charge transport ability is highly dependent on the resin, for example, the charge transport ability is not sufficient in a hardening resin having sufficiently high hardness, Both have not been satisfied, for example, an increase in the residual potential is observed upon repeated use.
[0017]
Further, in JP-A-5-216249 and JP-A-7-72640, a charge transporting layer contains a monomer having a carbon-carbon double bond, and the carbon-carbon double bond of the charge transporting substance is heated or heat-dissipated. An electrophotographic photoreceptor in which a charge transport layer cured film is formed by reacting with light energy has been disclosed, but the charge transport substance is merely fixed in a pendant form to the polymer main skeleton, and the plastic Mechanical action cannot be sufficiently eliminated, and the mechanical strength is not sufficient.
[0018]
Further, when the concentration of the charge transporting substance is increased to improve the charge transporting ability, the crosslink density becomes low, and sufficient mechanical strength cannot be secured. Further, there is a concern that the initiators required at the time of polymerization may affect the electrophotographic properties.
[0019]
As another solution, for example, an electrophotographic photoreceptor in which a charge transporting layer is formed by introducing a group having a charge transporting ability into a thermoplastic polymer main chain in JP-A-8-248649 is disclosed. Although it is disclosed, compared to the conventional molecular dispersion type charge transport layer, it is effective for precipitation and layer separation and improves mechanical strength, but is a thermoplastic resin to the last, The strength is limited, and it is hard to say that it is sufficient in handling including the solubility of the resin and productivity.
[0020]
On the other hand, as shown in JP-A-2000-66425, by using an electrophotographic photoreceptor containing a compound obtained by polymerizing and curing a compound having a chain polymerizable functional group in the same molecule, high mechanical strength is obtained. It has been proposed to achieve a balance between the charge transport ability.
[0021]
However, in this case, due to the effect of electron beam irradiation used when polymerizing and curing the above compound, deterioration of the electrophotographic photoreceptor is contrary to the mechanical strength of the obtained polymerized cured product, specifically, poor charging, light Deterioration of electrophotographic characteristics such as a decrease in sensitivity and an increase in residual potential poses a problem. In particular, electrophotographic characteristics deteriorate in a low-temperature and low-humidity environment, and the obtained electrophotographic photoreceptor does not satisfy both the mechanical strength and the electrophotographic characteristics.
[0022]
[Problems to be solved by the invention]
In a conventional intermediate layer formed by electric conduction, when the resistance is increased to ensure the barrier property from the support, the residual potential increases, and when the resistance is reduced, the barrier property becomes insufficient and fog becomes severe. There is nature.
[0023]
In an electrophotographic photoreceptor having a photosensitive layer formed by polymerization and curing by electron beam irradiation and using a conventional resin as an intermediate layer, the potential is liable to change due to the influence of temperature and humidity environment, especially in low humidity. In an environment, there is a disadvantage that the residual potential caused by the intermediate layer increases, and the density of the copied image decreases.
[0024]
An object of the present invention is to solve the above problems and provide an electrophotographic photosensitive member having excellent potential characteristics and electrophotographic characteristics even under a low-temperature and low-humidity environment, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus. is there.
[0025]
[Means for Solving the Problems]
The present inventors have conducted intensive studies and found that polymerization and curing are performed by electron beam irradiation by using an intermediate layer having a rectifying action of the same polarity with respect to a charged potential, regardless of general electric conduction. It was also found that an electrophotographic photoreceptor using a photosensitive layer exhibited stable electrophotographic characteristics regardless of the use environment, and also exhibited excellent characteristics in durability.
[0026]
That is, the present invention provides an electrophotographic photosensitive member having an intermediate layer and a photosensitive layer on a support in this order,
The intermediate layer contains an imide resin having an electron transporting ability,
An electrophotographic photoconductor, wherein the photosensitive layer contains a polymer obtained by polymerizing a hole transport material having two or more chain-polymerizable functional groups in the same molecule.
[0027]
Further, the present invention is a process cartridge and an electrophotographic apparatus having the above electrophotographic photosensitive member.
[0028]
BEST MODE FOR CARRYING OUT THE INVENTION
The electrophotographic photosensitive member of the present invention will be described in more detail.
[0029]
The imide resin used in the intermediate layer of the electrophotographic photoreceptor of the present invention has an electron transporting ability. Generally, an amide resin having an imide group (-NH-) is referred to as an imide resin.
[0030]
The structure of the electrophotographic photoreceptor of the present invention is such that an intermediate layer and a photosensitive layer are sequentially formed on a support.
[0031]
The photosensitive layer is a single-layer photosensitive layer containing a charge generating substance and a charge transporting substance in a single layer, and a stacked type having a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance. They are roughly classified into photosensitive layers. The laminated photosensitive layer includes a type in which a charge generation layer and a charge transport layer are laminated in this order from the support side, and the reverse type.
[0032]
In terms of electrophotographic characteristics, a laminate type in which a charge generation layer and a charge transport layer are laminated in this order from the support side is preferable. Hereinafter, the term “laminated type” indicates this layer order.
[0033]
The support of the electrophotographic photoreceptor of the present invention includes a metal or alloy such as iron, copper, gold, silver, aluminum, zinc, titanium, lead, nickel, tin, antimony, indium, or an oxide or carbon of the above metal. , A conductive polymer or the like can be used.
[0034]
The shape includes a drum shape such as a cylindrical shape and a column shape, and a belt shape and a sheet shape.
[0035]
The above-mentioned conductive material may be processed by etching, plasma treatment, when it is formed as it is, when it is used as a paint, when it is deposited, or when it is deposited.
[0036]
In the case of a coating material, paper, plastic, and the like can be used for the support as well as the above metals and alloys.
[0037]
It is preferable to provide a conductive layer on the support for covering unevenness and defects of the support and for preventing interference fringes due to scattering when image input is laser light.
[0038]
The conductive layer can be formed by dispersing conductive powder such as carbon black, metal particles, and metal oxide in a binder resin.
[0039]
The thickness of the conductive layer is preferably from 5 to 40 μm, more preferably from 10 to 30 μm.
[0040]
In the case of the electrophotographic photoreceptor of the present invention, an intermediate layer containing an imide resin having an electron transporting ability is provided on the support or the conductive layer. The intermediate layer functions as charge injection control at the interface and as an adhesive layer.
[0041]
The imide resin having an electron transporting ability is preferably a resin having a repeating structural unit represented by the following formula (1).
[Outside 9]

[0042]
(In the formula (1), Y ¹¹ Represents a divalent organic group; ¹¹ Represents a divalent group having a structure represented by the following formula (2).
[Outside 10]

[0043]
(In the formula (2), R ²¹ ~ R ²⁴ Each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a cyano group. ))
[0044]
The imide resin having an electron transporting ability is preferably a resin having a repeating structural unit represented by the following formula (3).
[Outside 11]

[0045]
(In the formula (3), Y ³¹ Represents a trivalent organic group; ³¹ Represents a group having a structure represented by the following formula (4).
[Outside 12]

[0046]
(In the formula (4), R ⁴¹ ~ R ⁴⁴ Each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a cyano group; ⁴¹ Represents an alkylene group, an ether group, a thioether group, or a -CO-O- group. ))
[0047]
The imide resin having an electron transporting ability is preferably a resin having a repeating structural unit represented by the following formula (5).
[Outside 13]

[0048]
(In the formula (5), R ⁵¹ Represents a hydrogen atom or an alkyl group; ⁵¹ Represents a group having a structure represented by the following formula (4).
[Outside 14]

[0049]
(In the formula (4), R ⁴¹ ~ R ⁴⁴ Each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a cyano group; ⁴¹ Represents an alkylene group, an ether group, a thioether group, or a -CO-O- group. ))
[0050]
Further, the imide resin having an electron transporting ability is preferably a resin having a repeating structural unit represented by the following formula (6).
[Outside 15]

[0051]
(In the formula (6), A ⁶¹ Represents a group having a structure represented by the following formula (4).
[Outside 16]

[0052]
(In the formula (4), R ⁴¹ ~ R ⁴⁴ Each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a cyano group; ⁴¹ Represents an alkylene group, an ether group, a thioether group, or a -CO-O- group. ))
[0053]
The divalent organic group in the above expression includes an alkylene group and an arylene group, and the trivalent organic group includes an alkyl group having a substituent and an arylene group.
[0054]
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.Examples of the alkyl group include a methyl group, an ethyl group and a propyl group.Examples of the alkoxy group include a methoxy group and an ethoxy group. No.
[0055]
Examples of the alkylene group include a methylene group and an ethylene group.
[0056]
Examples of the substituent which each of the above groups may have include a halogen atom, an alkyl group such as a methyl group, an ethyl group and a propyl group, and an alkoxy group such as a methoxy group and an ethoxy group.
[0057]
Tables 1 to 4 show specific examples of the repeating structural units of the imide resin having an electron transporting ability.
[0058]
[Table 1]

[0059]
[Table 2]

[0060]
[Table 3]

[0061]
[Table 4]

[0062]
The thickness of the intermediate layer is preferably from 0.1 to 10 μm, more preferably from 0.3 to 5 μm.
[0063]
The amount of the imide resin having an electron transporting ability contained in the intermediate layer is preferably from 20 to 100% by mass, more preferably from 30 to 100% by mass, based on the total mass of the intermediate layer.
[0064]
A photosensitive layer is provided on the intermediate layer. As described above, the photosensitive layer of the electrophotographic photosensitive member used in the present invention is preferably a laminated type in which a charge generation layer and a charge transport layer are laminated in this order from the support (intermediate layer) side. I do.
[0065]
In the present invention, a general material can be used as the charge generating substance.
[0066]
As the charge generating substance, generally, selenium-tellurium, pyrylium, thiapyrylium-based dyes, various center metals and crystal forms, specifically, for example, crystal forms such as α, β, γ, ε and X forms A phthalocyanine compound having an anthrone pigment, a dibenzopyrene quinone pigment, a pyranthrone pigment, a trisazo pigment, a disazo pigment, a monoazo pigment, an indigo pigment, a quinacridone pigment, an asymmetric quinocyanine pigment, a quinocyanine, and JP-A No. 54-143645. The described amorphous silicon is exemplified.
[0067]
In addition, it is also possible to use a binder resin other than the charge generation material.
[0068]
Specific examples of the binder resin include polyester, polyurethane, polyacrylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, phenol resin, acrylic resin, silicone resin, epoxy resin, urea resin, allyl resin, and alkyd resin. , Polyamide-imide, nylon, polysulfone, polyallyl ether, polyacetal, butyral resin, benzal resin and the like.
[0069]
The amount of the charge generation substance contained in the charge generation layer is preferably from 10 to 90% by mass, more preferably from 30 to 70% by mass, based on the total mass of the charge generation layer.
[0070]
The thickness of the charge generation layer is preferably from 0.001 to 6 μm, and more preferably from 0.01 to 2 μm.
[0071]
The electrophotographic photoreceptor of the present invention has a photosensitive layer, preferably a charge transport layer in a laminated photosensitive layer, obtained by polymerizing a hole transport material having two or more chain-polymerizable functional groups in the same molecule. contains.
[0072]
Examples of the chain polymerizable functional group include an unsaturated polymerizable functional group or a ring-opening polymerizable functional group in which a reaction proceeds via an intermediate such as a radical or an ion. Examples of these functional groups are shown below.
[0073]
[Outside 17]

(7)
[0074]
[Outside 18]

(8)
[0075]
[Outside 19]

(9)
[0076]
[Outside 20]

(10)
[0077]
[Outside 21]

(11)
[0078]
[Outside 22]

(N is an integer from 1 to 3) (12)
[0079]
[Outside 23]

(N is an integer from 1 to 3) (13)
[0080]
Among these, acryloyloxy groups and methacryloyloxy groups represented by the formulas (7) and (8) are particularly preferable in terms of polymerization characteristics.
[0081]
Specific examples of the hole transporting substance having two or more chain-polymerizable functional groups in the same molecule are shown below.
[0082]
[Table 5]

[0083]
[Table 6]

[0084]
As a method of forming a layer, it is preferable to carry out polymerization / crosslinking reaction after applying the solution containing the above-mentioned hole transporting substance, but after reacting the solution containing the hole transporting substance in advance to obtain a cured product, It is also possible to use a material dispersed or dissolved in a solvent.
[0085]
When a material obtained by polymerizing a hole transporting material having two or more chain-polymerizable functional groups in the same molecule is used for the charge transporting layer on the charge generating layer, 30% based on the total mass of the cured charge transporting layer. % By mass or more, more preferably 50% by mass or more. If the amount is less than 10% by mass, the charge transporting ability may decrease, and problems such as a decrease in sensitivity and an increase in residual potential may occur.
[0086]
The thickness of the charge transport layer is preferably from 1 to 50 μm, and more preferably from 3 to 30 μm.
[0087]
Further, in an electrophotographic photoreceptor having a laminated photosensitive layer, the charge transport layer corresponding to the surface layer is provided with the first charge transport layer on the support side and the first charge transport layer on the surface side for the purpose of improving the mechanical strength of the electrophotographic photoreceptor surface. The function may be separated into two charge transport layers. This second charge transport layer is sometimes called a protective layer.
[0088]
When a material obtained by polymerizing a hole transporting material having two or more chain-polymerizable functional groups in the same molecule is used for the second charge transporting layer, the first charge transporting layer below the second charge transporting layer is made of an appropriate charge transporting material. For example, a polymer compound having a heterocyclic or fused polycyclic aromatic such as poly-N-vinylcarbazole and polystyrylanthracene, a heterocyclic compound such as pyrazoline, imidazole, oxazole, triazole and carbazole, and triphenylmethane. A low molecular compound such as a triarylalkane derivative, a triarylamine derivative such as triphenylamine, a phenylenediamine derivative, an N-phenylcarbazole derivative, a stilbene derivative, or a hydrazine derivative may be added to a suitable binder resin (for the charge generation layer described above). Dispersed in solvent together with resin) Dissolved solution was applied, it may be a conventional charge transporting layer formed by drying.
[0089]
The ratio of the charge transport material to the binder resin in the first charge transport layer is preferably 30 to 100, and more preferably 50 to 100, when the total mass of both is 100. Is more preferred. If the amount of the charge transporting substance is less than 30, the charge transporting ability decreases, and problems such as a decrease in sensitivity and an increase in residual potential are likely to occur.
[0090]
On the other hand, in the second charge transport layer, a polymer obtained by polymerizing a hole transport material having two or more chain-polymerizable functional groups in the same molecule is 30% based on the total mass of the cured second charge transport layer. % By mass or more, more preferably 50% by mass or more. If the amount is less than 10% by mass, the charge transporting ability may decrease, and problems such as a decrease in sensitivity and an increase in residual potential may occur.
[0091]
When a charge transport layer having a function separation is employed, the thickness of the charge transport layer is preferably such that the total thickness of the first charge transport layer and the second charge transport layer is 1 to 50 μm, and more preferably 5 to 50 μm. More preferably, it is 30 μm.
[0092]
In the electrophotographic photoreceptor having the single-layer type photosensitive layer, a layer similar to the second charge transport layer can be provided on the outermost surface.
[0093]
As a method for producing the electrophotographic photoreceptor of the present invention, methods such as vapor deposition and coating are used. The coating method can form films of various compositions in a wide range from a thin film to a thick film. Specifically, it is applied by a bar coater, knife coater, dip coating, spray coating, beam coating, electrostatic coating, roll coater, attritor, powder coating, or the like.
[0094]
Further, various additives can be added to the photosensitive layer of the electrophotographic photosensitive member of the present invention. Additives include deterioration inhibitors such as antioxidants and ultraviolet absorbers, and lubricants such as fine particles of fluorine atom-containing resin.
[0095]
In the present invention, the polymerization (and cross-linking) of a hole transport material having two or more chain-polymerizable functional groups in the same molecule is preferably performed by radiation.
[0096]
The greatest advantage of polymerization by radiation is that no polymerization initiator is required, which makes it possible to prepare a very high-purity three-dimensional photosensitive layer matrix, and to ensure good electrophotographic properties. In addition, productivity is high because the polymerization reaction is efficient in a short time. Furthermore, since radiation is excellent in transparency, it is also possible that a shielding substance such as an additive is present in a layer, or that the effect of curing inhibition when a thick layer is formed is very small.
[0097]
However, depending on the type of the chain polymerizable functional group or the type of the central skeleton, the polymerization reaction may not easily proceed, and in that case, it is possible to add a polymerization initiator within a range that does not affect the polymerization reaction.
[0098]
Examples of the radiation to be used include an electron beam and γ-ray, and an electron beam is preferable in terms of efficiency.
[0099]
When irradiating with an electron beam, any type of accelerator such as a scanning type, an electro curtain type, a broad beam type, a pulse type, and a laminar type can be used.
[0100]
Further, in the case of irradiating an electron beam, in the present invention, the irradiation condition is very important for developing electric characteristics and durability.
[0101]
The acceleration voltage is preferably 300 kV or less, more preferably 150 kV or less.
[0102]
The dose is preferably in the range of 1 Mrad to 10 Mrad, and more preferably in the range of 3 Mrad to 50 Mrad.
[0103]
When the acceleration voltage exceeds 300 kV, the damage of the electron beam irradiation on the characteristics of the electrophotographic photosensitive member tends to increase. When the dose is less than 1 Mrad, crosslinking tends to be insufficient, and when the dose exceeds 100 Mrad, the electrophotographic photosensitive member is liable to be deteriorated.
[0104]
FIG. 1 shows a schematic configuration example of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.
[0105]
In FIG. 1, reference numeral 1 denotes a drum-type electrophotographic photosensitive member of the present invention as an image carrier, which is rotated around an axis 2 at a predetermined peripheral speed in a direction indicated by an arrow.
[0106]
The electrophotographic photosensitive member 1 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the charging means 3 during the rotation process, and then receives exposure light 4 (slit exposure, laser beam scanning exposure, etc.) by the exposure means. As a result, an electrostatic latent image corresponding to the exposure image is sequentially formed on the peripheral surface of the electrophotographic photosensitive member.
[0107]
The electrostatic latent image is then developed with toner by developing means 5, and the developed toner image is transferred between the electrophotographic photosensitive member 1 and the transfer means 6 from a paper feeding unit (not shown) by transfer means 6. Are sequentially transferred to the surface of the transfer material 7 which is taken out and fed in synchronization with the rotation of.
[0108]
The transfer material 7 having undergone the image transfer is separated from the electrophotographic photosensitive member surface, introduced into the fixing means 8 and subjected to image fixing, and is output as a copy (copy) outside the machine.
[0109]
The surface of the electrophotographic photoreceptor 1 after image transfer is cleaned and cleaned by removing the untransferred toner by the cleaning unit 9, further subjected to a charge removal process by the pre-exposure unit 10, and is repeatedly used for image formation.
[0110]
When the charging means 3 is a contact charging means as shown in the figure, the pre-exposure means is not always necessary.
[0111]
Of the above-described components such as the electrophotographic photosensitive member, the developing unit, and the cleaning unit, a plurality of components may be integrally connected as an apparatus unit, and this unit may be configured to be detachable from the apparatus main body. .
[0112]
For example, the electrophotographic photosensitive member 1 and the cleaning means 9 may be integrated into one apparatus unit (process cartridge 11), and may be configured to be detachable using a guide means such as a rail 12 of the apparatus body. At this time, the above-described device unit may be provided with a charging unit and / or a developing unit.
[0113]
When the electrophotographic apparatus is used as a copying machine or a printer, the exposure light 4 is reflected light or transmitted light from a document, or a signal is read from the document, and scanning of a laser beam, driving of an LED array, or This is performed by driving a liquid crystal shutter array or the like. When used as a facsimile printer, the exposure light 4 is an exposure for printing received data.
[0114]
The electrophotographic photoreceptor of the present invention can be widely used not only for electrophotographic copying machines but also for electrophotographic applications such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making.
[0115]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples.
[0116]
In addition, "part" means "part by mass".
[0117]
[Example 1]
The electrophotographic photoreceptor in this example is as follows.
[0118]
First, a paint for a conductive layer was prepared by the following procedure.
[0119]
50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of resole type phenol resin, 20 parts of methicellosolve, 5 parts of methanol, and silicone oil (polydimethylsiloxane polyoxyalkylene copolymer , Average molecular weight 3000) was prepared by dispersing for 2 hours in a sand mill using glass beads having a diameter of 1 mm. The coating material was applied on an aluminum cylinder having a diameter of 30 mm by a dip coating method, and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.
[0120]
Next, a solution prepared by dissolving 10 parts of a polyamic acid having a repeating structural unit shown in Compound Example 1 in Table 1 in 90 parts of N, N-dimethylacetamide is applied by dip coating, and heat-cured at 180 ° C. for 1 hour. As a result, an intermediate layer having a thickness of 1 μm was formed.
[0121]
Next, 2 parts of oxytitanium phthalocyanine having strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα, One part of butyral (trade name: SREC BM-2, manufactured by Sekisui Chemical Co., Ltd.) and 35 parts of cyclohexanone were dispersed in a sand mill using glass beads having a diameter of 1 mm for 2 hours, and then 60 parts of ethyl acetate was added. A paint for a charge generation layer was prepared. This paint was applied onto the above-mentioned intermediate layer by a dip coating method and dried at 50 ° C. for 10 minutes to form a 0.2 μm-thick charge generating layer.
[0122]
Next, 10 parts of a polycarbonate resin (viscosity average molecular weight 22,000) having a repeating structural unit represented by the following formula (8):
[Outside 24]

[0123]
As a charge transport material, 10 parts of a tolylamine compound having a structure represented by the following formula (9) is used.
[Outside 25]

[0124]
It was dissolved in a mixed solvent of 30 parts of monochlorobenzene and 30 parts of dichloromethane to prepare a first charge transport layer coating.
[0125]
This paint was applied on the charge generation layer by a dip coating method, and was dried with hot air at 120 ° C. for 60 minutes to form a first charge transport layer having a thickness of 15 μm.
[0126]
Next, 60 parts of Compound Example (H-1) was dissolved in a mixed solvent of 100 parts of monochlorobenzene and 100 parts of dichloromethane to prepare a coating for the second charge transport layer.
[0127]
This paint is spray-coated on the first charge transport layer, irradiated with an electron beam under the conditions of an acceleration voltage of 150 kV and an irradiation dose of 30 Mrad, and the paint containing the compound is cured to have a hole transport ability of 5 μm in film thickness. To form an electrophotographic photoreceptor.
[0128]
The electrophotographic photoreceptor thus obtained was left under an environment of 15 ° C. and 10% RH for 2 days, and then, using a GP405 manufactured by Canon Inc., the potential at the time of exposure before and after passing 1,000 sheets, and the non-exposure potential The time potential was evaluated.
[0129]
Table 7 shows the evaluation results.
[0130]
[Examples 2 to 5]
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1, except that Compound Example (H-1) was changed to Compound Examples (H-2) to (H-5) in Example 1. .
[0131]
Table 7 shows the evaluation results.
[0132]
[Example 6]
Example 1 was repeated except that the polyamic acid having a repeating structural unit shown in Compound Example 1 in Table 1 was changed to a polyamic acid having a repeating structural unit shown in Compound Example 3 in Table 1. An electrophotographic photoreceptor was prepared and evaluated in the same manner as described above.
[0133]
Table 7 shows the evaluation results.
[0134]
[Example 7]
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the intermediate layer was changed to Compound Example 1 in Table 2 in Example 1. Table 7 shows the evaluation results.
[0135]
Example 8
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the intermediate layer was changed to Compound Example 1 in Table 3 in Example 1. Table 7 shows the evaluation results.
[0136]
[Example 9]
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that the intermediate layer was changed to Compound Example 1 in Table 4. Table 7 shows the evaluation results.
[0137]
[Comparative Examples 1 to 5]
The intermediate layers of Examples 1 to 5 were immersed in a solution prepared by dissolving 5 parts of methoxymethylated nylon (weight average molecular weight 32,000) and 10 parts of alcohol-soluble copolymerized nylon (weight average molecular weight 29,000) in 95 parts of methanol. Electrophotographic photoreceptors were prepared and evaluated in the same manner as in Examples 1 to 5, except that the intermediate layer having a thickness of 1 μm was formed by coating and drying at 100 ° C. for 20 minutes.
[0138]
Table 7 shows the evaluation results.
[0139]
[Table 7]

[0140]
【The invention's effect】
As described above, according to the present invention, it is possible to provide an electrophotographic photosensitive member having excellent potential characteristics and electrophotographic characteristics even in a low-temperature and low-humidity environment, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus. .
[Brief description of the drawings]
FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member of the present invention.
[Explanation of symbols]
1. Electrophotographic photoreceptor
2 axes
3 Charging means
4 Exposure light
5 Developing means
6 transfer means
7 Transfer material
8 Fixing means
9 Cleaning means
10 Pre-exposure means
11 Process cartridge
12 rails (guide means)

Claims (9)

In an electrophotographic photosensitive member having an intermediate layer and a photosensitive layer in this order on a support,
The intermediate layer contains an imide resin having an electron transporting ability,
An electrophotographic photosensitive member, wherein the photosensitive layer contains a polymerized hole transport material having two or more chain-polymerizable functional groups in the same molecule. The photosensitive layer has a charge generation layer and a charge transport layer, and the charge transport layer contains a material obtained by polymerizing a hole transport material having two or more chain-polymerizable functional groups in the same molecule. Item 2. The electrophotographic photosensitive member according to Item 1. 3. The electrophotographic photoreceptor according to claim 1, wherein the polymerization of the hole transport material having two or more chain-polymerizable functional groups in the same molecule is polymerization by an electron beam. The electrophotographic photoreceptor according to any one of claims 1 to 3, wherein the imide resin having an electron transporting ability is a resin having a repeating structural unit represented by the following formula (1).
[Outside 1]

(In the formula (1), Y ¹¹ represents a divalent organic group, and A ¹¹ represents a divalent group having a structure represented by the following formula (2).
[Outside 2]

(In Formula (2), R ^{21 to} R ²⁴ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a cyano group.) The electrophotographic photosensitive member according to any one of claims 1 to 4, wherein the imide resin having an electron transporting ability is a resin having a repeating structural unit represented by the following formula (3).
[Outside 3]

(In the formula (3), Y ³¹ represents a trivalent organic group, and A ³¹ represents a group having a structure represented by the following formula (4).
[Outside 4]

(In Formula (4), R ^{41 to} R ⁴⁴ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a cyano group, and Y ⁴¹ represents , An alkylene group, an ether group, a thioether group, or a -CO-O- group.)) The electrophotographic photosensitive member according to any one of claims 1 to 5, wherein the imide resin having an electron transporting ability is a resin having a repeating structural unit represented by the following formula (5).
[Outside 5]

(In the formula (5), R ⁵¹ represents a hydrogen atom or an alkyl group, and A ⁵¹ represents a group having a structure represented by the following formula (4).
[Outside 6]

(In Formula (4), R ^{41 to} R ⁴⁴ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a cyano group, and Y ⁴¹ represents , An alkylene group, an ether group, a thioether group, or a -CO-O- group.)) The electrophotographic photosensitive member according to any one of claims 1 to 6, wherein the imide resin having an electron transporting ability is a resin having a repeating structural unit represented by the following formula (6).
[Outside 7]

(In the formula (6), A ⁶¹ represents a group having a structure represented by the following formula (4).
[Outside 8]

(In Formula (4), R ^{41 to} R ⁴⁴ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a cyano group, and Y ⁴¹ represents , An alkylene group, an ether group, a thioether group, or a -CO-O- group.)) An electrophotographic photoreceptor according to any one of claims 1 to 7, and at least one means selected from the group consisting of a charging means, a developing means, and a cleaning means, which are integrally supported and detachably attached to an electrophotographic apparatus main body. A process cartridge, comprising: An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an exposing unit, a developing unit, and a transferring unit.

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