JP2004093806A - Electrophotographic photoreceptor body, process cartridge having the same and electrophotographic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor body which exhibits a stable and excellent potential characteristic and continuously forms the initial excellent image under the whole environment from low temperature and low humidity to high temperature and high humidity, and to provide a process cartridge and an electrophotographic device having the electrophotographic photoreceptor body. <P>SOLUTION: The electrophotographic photoreceptor body has a photoreceptive layer and an intermediate layer on a conductive substrate. Therein, the intermediate layer comprises a polymer compound having a specified repeated structural unit. <P>COPYRIGHT: (C)2004,JPO

Description

（１）
また、本発明は、上記電子写真感光体を有するプロセスカートリッジ及び電子写真装置である。
【００１１】
【発明の実施の形態】
好ましくは、導電性支持体上に中間層を介して感光層を有する電子写真感光体において、該中間層が下記式（１）の構造単位を有する電子輸送性高分子化合物からなり、且つ、該電子輸送性高分子化合物の電子移動度が１×１０^−８乃至１×１０^−５ｃｍ^２／Ｖ　ｓｅｃの範囲であること特徴とする電子写真感光体である。
【外８】

（１）
【００１２】
式（１）中のＲ１が式（２）に示す構造から水素原子１個を除いた構造であることが好ましい。式（２）中のＸおよびＹは置換基を有してもよいアルキル基、アリール基、アラルキル基、複素環基を示し、同一であってもよい。また、Ｒ_２乃至Ｒ_５は水素原子、置換基を有してもよいアルキル基、アリール基、アラルキル基、複素環基、ハロゲン原子、ニトロ基、またはシアノ基を示す。
【外９】

（２）
【００１３】
また、式（１）中の電子輸送能を有する構造単位Ｒ_１が、式（３）に示す構造から水素原子１個を除いた構造であることを特徴とする電子写真感光体である。式（３）中のＲ_６およびＲ_７は、水素原子、置換基を有してもよいアルキル基、アリール基、アラルキル基、複素環基、またはシアノ基を示し、Ｒ_８およびＲ_９は水素原子、置換基を有してもよいアルキル基、アルコキシ基、またはハロゲン原子、ニトロ基、シアノ基、エステル基を示す。ａおよびｂは０、１または２を示す。
【外１０】

（３）
【００１４】
また、式（１）中の電子輸送能を有する構造単位Ｒ_１が、式（４）に示す構造から水素原子１個を除いた構造であることを特徴とする電子写真感光体である。式（４）中のＲ_８およびＲ_９は水素原子、置換基を有してもよいアルキル基、アルコキシ基、またはハロゲン原子、ニトロ基、シアノ基、エステル基を示し、Ｒ_１０は、置換基を有してもよいアルキル基、アリール基、アラルキル基、複素環基、またはシアノ基を示し、ａおよびｂは０、１または２を示す。
【外１１】

（４）
【００１５】
また、式（１）中の電子輸送能を有する構造単位Ｒ_１が、式（５）に示す構造から水素原子１個を除いた構造であることを特徴とする電子写真感光体である。式（５）中のＺは酸素原子、硫黄原子またはジシアノメチレン基を示し、Ｒ_８およびＲ_９は水素原子、置換基を有してもよいアルキル基、アルコキシ基、ハロゲン原子、ニトロ基、シアノ基、またはエステル基を示す。ａおよびｂは０、１または２を示す。
【外１２】

（５）
【００１６】
また、式（１）中の電子輸送能を有する構造単位Ｒ_１が、式（６）に示す構造から水素原子１個を除いた構造であることを特徴とする電子写真感光体である。式（６）中のＰは酸素原子、硫黄原子またはジシアノメチレン基を示し、Ｒ_１１およびＲ_１２は水素原子、置換基を有してもよいアルキル基、アルコキシ基、またはハロゲン原子、ニトロ基、シアノ基を示す。ａおよびｂは０、１または２を示す。
【外１３】

（６）
【００１７】
本発明の電子輸送性高分子化合物は、マレイミドの繰り返し構造単位の側鎖部分、即ち、式（１）中のＲ_１に電子輸送機能を有する化学構造を導入する。Ｒ_１は電子輸送機能を有する化学構造であればその化学構造は限定されるものではないが、式（２）乃至式（６）に示す化学構造は電子輸送機能が高いために特に好ましい。本発明の電子輸送性高分子化合物からなる中間層は、電子移動度として１×１０^−８乃至１×１０^−５ｃｍ^２／Ｖ　ｓｅｃの範囲であることが好ましい。電子移動度の測定は、タイム−オフ−フライト法などの既知の方法で測定することができる。
【００１８】
本発明の電子輸送性高分子化合物からなる中間層を有する電子写真感光体は、帯電極性が負帯電の場合、電荷発生層で発生した正孔は、電界に従って電荷輸送層に注入し、正孔輸送物質により感光層表面へ移動し、また、電荷発生層で発生した電子は、電界に従って中間層に注入し、電子輸送性高分子化合物により効率よく導電性支持体側に移動する。従って、電荷発生層と電荷輸送層の界面、電荷発生層と中間層の界面、または電荷発生層や中間層の内部での電荷の滞留が極めて小さくなり、その結果、残留電位の低減や繰り返し使用における電位変動の抑制などの電子写真特性に対して大きな効果を示す。
【００１９】
本発明の電子輸送性高分子化合物からなる中間層は、体積抵抗率が高く、温度や湿度の変化に対して安定であるために、導電性支持体からの電荷注入に対して効果的で電荷バリア性に優れる。中間層の体積抵抗率は１×１０^１１Ωｃｍ以上であることが好ましい。
【００２０】
従って、本発明の電子輸送性高分子を含有する中間層は、導電性支持体側からの電荷注入を効果的に阻止することができ、帯電能の低下やカブリ、ポチなどの画像欠陥に対して安定である。
【００２１】
本発明の電子輸送性高分子化合物の代表例をそのマレイミド部分について表１に例示する。ただし、本発明の電子輸送性高分子化合物は表１の例示化合物だけに限定されるものではない。
【００２２】
本発明の電子輸送性高分子化合物は、下記式に示すように、例えば無水マレイン酸とアミン化合物の反応によりマレイミドモノマーを合成し、さらにマレイミドモノマーを熱重合開始剤や光重合開始剤などの重合開始剤を用いて高分子量化して合成する。本発明の電子輸送性高分子化合物は、同一のマレイミドモノマーで重合した単一重合体、異なる二種類以上のマレイミドモノマーで重合した共重合体、あるいはマレイミドモノマーとマレイミドモノマー以外のビニルモノマーやアクリルモノマーなどと重合した共重合体が挙げられる。
【００２３】
本発明の電子輸送性高分子化合物の数平均分子量は５００乃至１、０００，０００の範囲であることが好ましく、特には１，０００乃至１００，０００の範囲であることが好ましい。
【００２４】
（マレイミドモノマー合成）
【外１４】

【００２５】
本発明の電子輸送性高分子からなる中間層は、必要に応じて他の高分子化合物、添加剤及び導電性物質などを本発明の効果が得られる範囲の量で含有することができる。他の高分子化合物としては、ポリアミド、ポリエステルおよびフェノール樹脂などが挙げられ、添加剤としては、２，５，７−トリニトロフルオレノンおよびベンゾキノンなどの電子移動機能を有する有機化合物などが挙げられ、また、導電性物質としては酸化インジウム、酸化スズ、酸化チタン、酸化亜鉛などの金属酸化物および金属硫化物が挙げられる。
【００２６】
いずれの場合も、本発明の電子輸送性高分子化合物の含有量は、中間層全重量に対して１０乃至９０重量％であることが好ましく、特には３０乃至７０重量％であることが好ましい。
【００２７】
本発明の中間層の厚さは、電子写真特性および基板上の欠陥などを考慮して適宜設定され得るものであるが、０．１乃至２０μｍの範囲であるのが好ましく、特には０．５乃至５μｍの範囲であることが好ましい。
【００２８】
本発明の電子写真感光体の感光層は、電荷発生物質と電荷輸送物質を同一の層に含有する単層型および電荷発生物質を含有する電荷発生層と電荷輸送物質を含有する電荷輸送層を有する積層型に大別されるが、いずれの場合でも良い。
【００２９】
電荷発生物質としては、モノアゾ、ジスアゾ、トリスアゾなどのアゾ系顔料、金属フタロシアニン、無金属フタロシアニンなどのフタロシアニン系顔料、インジゴ、チオインジゴなどのインジゴ系顔料、ペリレン酸無水物、ペリレン酸イミドなどのペリレン系顔料、アントアントロン、ピレンキノンなどの多環キノン系顔料、スクワリリウム系色素、ピリリウム、チオピリリウム塩類、トリフェニルメタン系色素などが挙げられる。
【００３０】
電荷輸送物質としては、ピレン、アントラセンなどの多環芳香族化合物、カルバゾ−ル、インド−ル、イミダゾ−ル、オキサゾ−ル、チアゾ−ル、オキサジアゾ−ル、ピラゾ−ル、ピラゾリン、チアジアゾ−ル、トリアゾ−ルなどの複素環化合物、ｐ−ジエチルアミノベンズアルデヒド−Ｎ，Ｎ−ジフェニルヒドラゾン、Ｎ，Ｎ−ジフェニルヒドラジノ−３−メチルデン−９−エチルカルバゾ−ルなどのヒドラゾン系化合物、α−フェニル−４’−Ｎ，Ｎ−ジフェニルアミノスチルベン、５−［４−（ジ−ｐ−トリルアミノ）ベンジリデン］−５Ｈ−ジベンゾ［ａ，ｄ］ジクロルヘプテンなどのスチリル系化合物、ベンジジン系化合物、トリアリ−ルメタン系化合物、トリフェニルアミンあるいはこれらの化合物からなる基を主鎖または側鎖に有するポリマ−（例えばポリ−Ｎ−ビニルカルバゾ−ル、ポリビニルアントラセンなど）が挙げられる。
【００３１】
電荷発生層の厚さは５μｍ以下、特には０．０１乃至１μｍの範囲であることが好ましい。また、電荷輸送層の厚さは５乃至４０μｍ範囲、特には１０乃至３０μｍの範囲であることが好ましい。
【００３２】
導電性支持体としては、アルミニウム、アルミニウム合金、銅、亜鉛、ステンレス、チタン、ニッケル、インジウム、金や白金などが用いられる。また、金属または合金を真空蒸着法によって被膜形成したプラスチック（ポリエチレン、ポリプロピレン、ポリ塩化ビニル及びポリエチレンテレフタレ−ト、アクリル樹脂）や導電性粒子（カ−ボンブラック、銀粒子）を適当な結着樹脂とともにプラスチックまたは金属支持体上に被覆した支持体あるいは導電性粒子をプラスチックや紙に含浸した支持体などが挙げられる。
【００３３】
感光層上に保護層として樹脂層や導電性粒子を含有する樹脂層を積層することもできる。
【００３４】
本発明における中間層は、一層のみで構成されてもよく、複数の層で構成されてもよい。中間層が複数の層で構成される場合、本発明の電子輸送性高分子化合物からなる中間層以外に、酸化錫、酸化亜鉛、カーボンブラックなどの導電性物質を含有する導電性中間層であるのが好ましい。
【００３５】
各種の層の塗布は、例えば浸漬コ−テイング法、スプレ−コ−テイング法、スピンナ−コ−テイング法、ビ−ドコ−テイング法、ブレ−ドコ−テイング法、ビ−ムコ−テイング法などの任意の塗布方法で行うことができる。
【００３６】
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−ザ−ビ−ムプリンタ−、ＣＲＴプリンタ−、ＬＥＤプリンタ−、液晶プリンタ−、レ−ザ−製版、ファクシミリなどの電子写真応用分野にも広く用いることができる。
【００３７】
また、本発明は前記本発明の電子写真感光体を備えた電子写真装置から構成される。
【００３８】
【実施例】
実施例１
アルミニウムシリンダー（外径３０ｍｍ×長さ３５７．５ｍｍ）上に、例示化合物Ｎｏ．１で示される例示化合物１の電子輸送性高分子化合物１０部をテトラヒドロフラン９０重量部に溶解した液を浸漬塗布し、１００℃で１０分間加熱することによって、膜厚１．２μｍの中間層を形成した。本実施例の中間層の電子移動度は２×１０^−６ｃｍ^２／Ｖ　ｓｅｃであった。また、本実施例の中間層の体積抵抗率は、５×１０^１２Ω　ｃｍ（２３℃、４０％ＲＨ）であった。
【００３９】
次にヒドロキシガリウムフタロシアニン顔料６重量部、ポリビニルブチラ−ル樹脂（商品名：ＢＸ−１、積水化学工業株式会社製）３重量部およびシクロヘキサノン４０重量部からなる混合液をサンドミルで１５時間分散した後、酢酸エチル６０重量部を加えて電荷発生層用の分散液を調合し、中間層上に浸漬塗布し、さらに１００℃で１０分間乾燥して膜厚約０．１μの電荷発生層を形成した。
【００４０】
次に下記構造式で示されるトリアリ−ルアミン化合物４０重量部およびビスフェノ−ルＺ型ポリカ−ボネ−ト樹脂６０重量部をモノクロルベンゼン２００重量部およびジメトキシメタン２００部に溶解した溶液を電荷発生層上に浸漬塗布し、１１０℃の雰囲気中で１時間加熱乾燥して膜厚２３μｍの電荷輸送層を形成し、電子写真感光体を作製した。
【外１５】

【００４１】
得られた電子写真感光体を帯電−露光−現像−転写−クリーニングプロセスを有する反転現像方式の複写機（ＧＰ−４０改造機。キヤノン製；露光量を０．２５μＪ／ｃｍ^２に調整）に装着し、低温低湿（１５℃、１０％ＲＨ）、常温常湿（２５℃、４０％ＲＨ）及び高温高湿（３０℃、８５％ＲＨ）の各環境下での電位（暗部電位Ｖ_Ｄ、明部電位Ｖ_Ｌ）評価及び低温低湿環境下での連続１時間の帯電−露光を繰り返した前後の電位変動量（ΔＶ）を求めた。評価結果を表２および表３に示す。低温低湿から高温高湿に至る環境下において電位が安定しており、また、繰り返し使用による電位変動量も小さかった。
【００４２】
実施例２〜１１
樹脂例２〜１１の本発明の電子輸送性高分子化合物を中間層に用いた他は、実施例１と同様にして電子写真感光体を作製し、実施例１と同様の方法により電子写真特性を評価した。評価結果を表２および表３に示す。また、電子移動度の評価結果も表２に示す。低温低湿から高温高湿に至る環境下において電位が安定しており、また、繰り返し使用による電位変動量も小さかった。
【００４３】
比較例１
実施例１の電子輸送性高分子化合物に代えて式（７）の繰り返し構造単位を有するポリマレイミドを用いた他は、実施例１と同様にして電子写真感光体を作製し、実施例１と同様の方法によって電子写真特性を評価した。評価結果を表２および表３に示す。式（７）の繰り返し構造単位を有するポリマレイミドを用いた場合、電子写真感度が悪く、特に繰り返し使用による電位上昇が顕著であった。
【外１６】

（７）
【００４４】
比較例２
中間層を、アルコール可溶性共重合ナイロン（アミランＣＭ−８０００、東レ（株）製）５部をメタノール４５部及びブタノール３０部に溶解した溶液を用いて形成した以外は、実施例１と同様にして電子写真感光体を作成し、評価した。中間層の厚さは１μｍである。評価結果を第２表および第３表に示す。アミランＣＭ−８０００を用いた場合、電子写真感度が悪く、特に繰り返し使用による電位上昇が顕著であった。
【００４５】
【表１】

【００４６】
【表２】

【００４７】
【表３】

【００４８】
【発明の効果】
以上のように、本発明によれば、低温低湿から高温高湿に至る全環境下において、環境安定性や繰り返し使用による安定性に対して優れた電位特性および画像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。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electrophotographic photoreceptor and an electrophotographic apparatus provided with the electrophotographic photoreceptor, and more particularly, to an electrophotographic photoreceptor having an intermediate layer made of a polymer compound having a specific chemical structure, and containing the electrophotographic photoreceptor. The present invention relates to a process cartridge and an electrophotographic apparatus.
[0002]
[Prior art]
Electrophotographic photoreceptors are required to have sensitivity, electrical characteristics, optical characteristics, and high-quality image quality free from image defects according to the applied electrophotographic process, and in any environment from low temperature and low humidity to high temperature and high humidity. It is required to have environmental stability so that the characteristics can be sufficiently exhibited.
[0003]
Typical image defects include image streaks, black spots on white background, white spots on black, white fog on white background, and exposure using laser diodes such as digital copiers and laser beam printers as light sources. Examples include interference fringes generated by factors such as the surface shape of the support and the unevenness of the thickness of the photoreceptor.
[0004]
As a method for preventing the above-described image defects, an intermediate layer is used as necessary. The intermediate layer is required to have an electric blocking function so that charge injection from the support does not occur when a voltage is applied to the electrophotographic photosensitive member. When charge is injected from the support, the chargeability is reduced, the image contrast is reduced, and in the case of the reversal development system, black spots and fog on a white background are caused, and the image quality is significantly reduced.
[0005]
On the other hand, if the electrical resistance of the intermediate layer is too high, it is difficult for the charges generated in the photosensitive layer to move to the support via the intermediate layer, and stay inside the photosensitive layer, resulting in an increase in the residual potential. And potential fluctuation due to repeated use. Therefore, in addition to the electrical blocking function, it is necessary to reduce the electrical resistance of the intermediate layer to some extent, and the blocking function and the electrical resistance characteristics are not significantly changed in any environment from low temperature and low humidity to high temperature and high humidity. No.
[0006]
Examples of the intermediate layer having a blocking function and an electric resistance characteristic in an appropriate range include, for example, JP-A-46-47344 and JP-A-52-100240 as an intermediate layer made of an organic polymer. JP-A-54-151843 and JP-A-1-118848 propose an intermediate layer in which a substance or a metal nitride is dispersed in an organic polymer.
[0007]
[Problems to be solved by the invention]
However, the electrophotographic photoreceptor using the above-mentioned material as an intermediate layer has a large change in electric resistance of the intermediate layer due to a change in temperature and humidity, and has a stable electric potential in all environments from low temperature and low humidity to high temperature and high humidity. It has been difficult to produce an electrophotographic photosensitive member having characteristics and capable of forming an excellent image.
[0008]
SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photoreceptor that can stably exhibit excellent potential characteristics and continuously form an excellent initial image in all environments from low temperature and low humidity to high temperature and high humidity. It is in.
[0009]
Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the above-described electrophotographic photosensitive member.
[0010]
[Means for Solving the Problems]
The present invention relates to an electrophotographic photosensitive member having a photosensitive layer and an intermediate layer on a conductive support, wherein the intermediate layer is represented by the following formula (1) (R ₁ represents a structural unit having an electron transporting ability). An electrophotographic photoreceptor comprising a polymer compound having a repeating structural unit.
[Outside 7]

(1)
Further, the present invention is a process cartridge and an electrophotographic apparatus having the above electrophotographic photosensitive member.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
Preferably, in an electrophotographic photoreceptor having a photosensitive layer on a conductive support via an intermediate layer, the intermediate layer comprises an electron transporting polymer compound having a structural unit represented by the following formula (1); An electrophotographic photoconductor, wherein the electron transporting polymer compound has an electron mobility in a range of 1 × 10 ^{−8 to} 1 × 10 ⁻⁵ cm ² / V sec.
[Outside 8]

(1)
[0012]
It is preferable that R1 in the formula (1) has a structure obtained by removing one hydrogen atom from the structure shown in the formula (2). X and Y in the formula (2) represent an alkyl group, an aryl group, an aralkyl group, and a heterocyclic group which may have a substituent, and may be the same. R _{2 to} R _{5 each} represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group, an aralkyl group, a heterocyclic group, a halogen atom, a nitro group, or a cyano group.
[Outside 9]

(2)
[0013]
Further, the structural unit R ₁ having an electron transporting ability in the formula (1) is an electrophotographic photosensitive member, which is a structure obtained by removing one hydrogen atom from the structure represented by the formula (3). R ₆ and R ₇ in the formula (3) represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group, an aralkyl group, a heterocyclic group, or a cyano group, and R ₈ and R ₉ represent hydrogen An atom, an alkyl group which may have a substituent, an alkoxy group, or a halogen atom, a nitro group, a cyano group, or an ester group. a and b represent 0, 1 or 2.
[Outside 10]

(3)
[0014]
Further, the structural unit R ₁ having an electron transporting ability in the formula (1) is an electrophotographic photosensitive member, which is a structure obtained by removing one hydrogen atom from the structure represented by the formula (4). R ₈ and R ₉ in the formula (4) represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, or a halogen atom, a nitro group, a cyano group, or an ester group, and R ₁₀ represents a substituent Represents an alkyl group, an aryl group, an aralkyl group, a heterocyclic group, or a cyano group, and a and b each represent 0, 1 or 2.
[Outside 11]

(4)
[0015]
Further, the structural unit R ₁ having an electron transporting ability in the formula (1) is an electrophotographic photosensitive member, which is a structure obtained by removing one hydrogen atom from the structure represented by the formula (5). Z in the formula (5) represents an oxygen atom, a sulfur atom or a dicyanomethylene group, and R ₈ and R ₉ are a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a halogen atom, a nitro group, a cyano group. Group or ester group. a and b represent 0, 1 or 2.
[Outside 12]

(5)
[0016]
Further, the structural unit R ₁ having an electron transporting ability in the formula (1) is an electrophotographic photosensitive member, which is a structure obtained by removing one hydrogen atom from the structure represented by the formula (6). P in the formula (6) represents an oxygen atom, a sulfur atom or a dicyanomethylene group, and R ₁₁ and R ₁₂ represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, which may have a substituent, a halogen atom, a nitro group, Shows a cyano group. a and b represent 0, 1 or 2.
[Outside 13]

(6)
[0017]
The electron transporting polymer compound of the present invention introduces a chemical structure having an electron transporting function into the side chain portion of the maleimide repeating structural unit, ie, R ₁ in the formula (1). R ₁ is not particularly limited as long as it has a chemical structure having an electron transport function, but the chemical structures represented by Formulas (2) to (6) are particularly preferable because of their high electron transport function. The intermediate layer composed of the electron transporting polymer compound of the present invention preferably has an electron mobility in the range of 1 × 10 ^{−8 to} 1 × 10 ⁻⁵ cm ² / V sec. The electron mobility can be measured by a known method such as a time-off-flight method.
[0018]
The electrophotographic photoreceptor having an intermediate layer comprising the electron transporting polymer compound of the present invention is such that, when the charge polarity is negatively charged, holes generated in the charge generation layer are injected into the charge transport layer according to an electric field, and The electrons move to the surface of the photosensitive layer by the transport material, and the electrons generated in the charge generation layer are injected into the intermediate layer according to the electric field, and move to the conductive support side efficiently by the electron transporting polymer compound. Accordingly, the retention of charges at the interface between the charge generation layer and the charge transport layer, the interface between the charge generation layer and the intermediate layer, or inside the charge generation layer or the intermediate layer is extremely small, and as a result, the residual potential is reduced or the charge is repeatedly used. It has a great effect on electrophotographic characteristics such as suppression of potential fluctuations in.
[0019]
The intermediate layer made of the electron transporting polymer compound of the present invention has a high volume resistivity and is stable against changes in temperature and humidity, so that it is effective for charge injection from the conductive support and has a high charge Excellent barrier properties. The volume resistivity of the intermediate layer is preferably 1 × 10 ¹¹ Ωcm or more.
[0020]
Therefore, the intermediate layer containing the electron transporting polymer of the present invention can effectively prevent charge injection from the conductive support side, and reduces image quality such as a decrease in charging ability and fog and spots. It is stable.
[0021]
Table 1 shows typical examples of the electron transporting polymer compound of the present invention with respect to the maleimide moiety. However, the electron transporting polymer compound of the present invention is not limited to the exemplified compounds in Table 1.
[0022]
As shown in the following formula, the electron transporting polymer compound of the present invention synthesizes a maleimide monomer, for example, by reacting maleic anhydride with an amine compound, and further polymerizes the maleimide monomer with a thermal polymerization initiator or a photopolymerization initiator. It is synthesized by increasing the molecular weight using an initiator. The electron transporting polymer compound of the present invention may be a homopolymer polymerized with the same maleimide monomer, a copolymer polymerized with two or more different maleimide monomers, or a vinyl monomer or an acrylic monomer other than the maleimide monomer and the maleimide monomer. And a copolymer obtained by polymerization.
[0023]
The number average molecular weight of the electron transporting polymer compound of the present invention is preferably in the range of 500 to 1,000,000, and particularly preferably in the range of 1,000 to 100,000.
[0024]
(Synthesis of maleimide monomer)
[Outside 14]

[0025]
The intermediate layer made of the electron transporting polymer of the present invention may contain other polymer compounds, additives, conductive substances, and the like, if necessary, in an amount within the range that the effects of the present invention can be obtained. Other polymer compounds include polyamides, polyesters and phenolic resins, and additives include organic compounds having an electron transfer function such as 2,5,7-trinitrofluorenone and benzoquinone. Examples of the conductive substance include metal oxides and metal sulfides such as indium oxide, tin oxide, titanium oxide, and zinc oxide.
[0026]
In any case, the content of the electron transporting polymer compound of the present invention is preferably from 10 to 90% by weight, and particularly preferably from 30 to 70% by weight, based on the total weight of the intermediate layer.
[0027]
The thickness of the intermediate layer of the present invention can be appropriately set in consideration of electrophotographic characteristics, defects on a substrate, and the like, but is preferably in the range of 0.1 to 20 μm, and particularly preferably 0.5 to 20 μm. It is preferably in the range of 5 to 5 μm.
[0028]
The photosensitive layer of the electrophotographic photoreceptor of the present invention comprises a single layer containing a charge generating substance and a charge transporting substance in the same layer and a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance. Although it is roughly classified into a stacked type having any of these, any case may be used.
[0029]
Examples of the charge generating substance include azo pigments such as monoazo, disazo and trisazo, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, indigo pigments such as indigo and thioindigo, perylene anhydrides and perylene imides such as perylene imide. Examples include pigments, polycyclic quinone pigments such as anthantrone and pyrenequinone, squarylium pigments, pyrylium, thiopyrylium salts, and triphenylmethane pigments.
[0030]
Examples of the charge transport material include polycyclic aromatic compounds such as pyrene and anthracene, carbazole, indole, imidazole, oxazole, thiazol, oxadiazol, pyrazol, pyrazoline, and thiadiazol. , A heterocyclic compound such as triazole, a hydrazone-based compound such as p-diethylaminobenzaldehyde-N, N-diphenylhydrazone, N, N-diphenylhydrazino-3-methylden-9-ethylcarbazole, α-phenyl-4 Styryl compounds such as' -N, N-diphenylaminostilbene, 5- [4- (di-p-tolylamino) benzylidene] -5H-dibenzo [a, d] dichloroheptene, benzidine compounds, triarylmethane compounds; Triphenylamine or a group consisting of these compounds in the main chain or side chain To the polymer - (for example, poly -N- vinylcarbazole - le, polyvinyl anthracene and the like).
[0031]
The thickness of the charge generation layer is preferably 5 μm or less, particularly preferably in the range of 0.01 to 1 μm. Further, the thickness of the charge transport layer is preferably in the range of 5 to 40 μm, particularly preferably in the range of 10 to 30 μm.
[0032]
As the conductive support, aluminum, aluminum alloy, copper, zinc, stainless steel, titanium, nickel, indium, gold, platinum or the like is used. In addition, a plastic (polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resin) or a conductive particle (carbon black, silver particle) formed by coating a metal or alloy by a vacuum evaporation method is appropriately bonded. Examples of the support include a support coated on a plastic or metal support together with a resin, or a support in which conductive particles are impregnated in plastic or paper.
[0033]
A resin layer or a resin layer containing conductive particles can be laminated as a protective layer on the photosensitive layer.
[0034]
The intermediate layer in the present invention may be composed of only one layer, or may be composed of a plurality of layers. When the intermediate layer is composed of a plurality of layers, it is a conductive intermediate layer containing a conductive substance such as tin oxide, zinc oxide, and carbon black, in addition to the intermediate layer made of the electron transporting polymer compound of the present invention. Is preferred.
[0035]
The coating of various layers may be performed by, for example, a dipping coating method, a spray coating method, a spinner coating method, a bead coating method, a blade coating method, a beam coating method, or the like. It can be performed by any coating method.
[0036]
The electrophotographic photoreceptor of the present invention is used not only for electrophotographic copying machines but also for laser beam printers, CRT printers, LED printers, liquid crystal printers, laser plate making, facsimile machines and the like. It can be widely used in electrophotographic applications.
[0037]
Further, the present invention comprises an electrophotographic apparatus provided with the electrophotographic photoreceptor of the present invention.
[0038]
【Example】
Example 1
An exemplary compound No. was placed on an aluminum cylinder (outer diameter 30 mm x length 357.5 mm). A solution obtained by dissolving 10 parts of the electron transporting polymer compound of Exemplified Compound 1 in 90 parts by weight of tetrahydrofuran by dip coating and heating at 100 ° C. for 10 minutes to form an intermediate layer having a thickness of 1.2 μm. did. The electron mobility of the intermediate layer in this example was 2 × 10 ⁻⁶ cm ² / V sec. The volume resistivity of the intermediate layer in this example was 5 × 10 ¹² Ωcm (23 ° C., 40% RH).
[0039]
Next, a mixed solution consisting of 6 parts by weight of hydroxygallium phthalocyanine pigment, 3 parts by weight of polyvinyl butyral resin (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 40 parts by weight of cyclohexanone was dispersed in a sand mill for 15 hours. Thereafter, 60 parts by weight of ethyl acetate is added to prepare a dispersion for the charge generation layer, dip-coated on the intermediate layer, and further dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.1 μm. did.
[0040]
Next, a solution prepared by dissolving 40 parts by weight of a triarylamine compound represented by the following structural formula and 60 parts by weight of bisphenol Z-type polycarbonate resin in 200 parts by weight of monochlorobenzene and 200 parts by weight of dimethoxymethane was formed on the charge generation layer. Then, it was dried by heating in an atmosphere at 110 ° C. for 1 hour to form a charge transport layer having a thickness of 23 μm, thereby producing an electrophotographic photosensitive member.
[Outside 15]

[0041]
The obtained electrophotographic photoreceptor is mounted on a reversal development type copying machine (GP-40 modified machine, manufactured by Canon; adjusting the exposure amount to 0.25 μJ / cm ² ) having a charging-exposure-development-transfer-cleaning process. And the potential (dark potential V _D , light) under each environment of low temperature and low humidity (15 ° C., 10% RH), normal temperature and normal humidity (25 ° C., 40% RH), and high temperature and high humidity (30 ° C., 85% RH). Partial potential _VL ) and the amount of potential change (ΔV) before and after repeating charge-exposure for one hour in a low-temperature and low-humidity environment were determined. The evaluation results are shown in Tables 2 and 3. The potential was stable in an environment from low temperature and low humidity to high temperature and high humidity, and the amount of potential fluctuation due to repeated use was small.
[0042]
Examples 2 to 11
An electrophotographic photosensitive member was prepared in the same manner as in Example 1, except that the electron transporting polymer compound of the present invention of Resin Examples 2 to 11 was used for the intermediate layer. Was evaluated. The evaluation results are shown in Tables 2 and 3. Table 2 also shows the evaluation results of the electron mobility. The potential was stable in an environment from low temperature and low humidity to high temperature and high humidity, and the amount of potential fluctuation due to repeated use was small.
[0043]
Comparative Example 1
An electrophotographic photoreceptor was prepared in the same manner as in Example 1, except that a polymaleimide having a repeating structural unit of the formula (7) was used instead of the electron transporting polymer compound of Example 1. The electrophotographic properties were evaluated by the same method. The evaluation results are shown in Tables 2 and 3. When a polymaleimide having a repeating structural unit of the formula (7) was used, the electrophotographic sensitivity was poor, and in particular, a potential increase due to repeated use was remarkable.
[Outside 16]

(7)
[0044]
Comparative Example 2
The intermediate layer was formed in the same manner as in Example 1 except that an intermediate layer was formed using a solution in which 5 parts of alcohol-soluble copolymerized nylon (Amilan CM-8000, manufactured by Toray Industries, Inc.) was dissolved in 45 parts of methanol and 30 parts of butanol. An electrophotographic photoreceptor was prepared and evaluated. The thickness of the intermediate layer is 1 μm. The evaluation results are shown in Tables 2 and 3. When Amilan CM-8000 was used, the electrophotographic sensitivity was poor, and the potential increase due to repeated use was remarkable.
[0045]
[Table 1]

[0046]
[Table 2]

[0047]
[Table 3]

[0048]
【The invention's effect】
As described above, according to the present invention, in all environments from low temperature and low humidity to high temperature and high humidity, an electrophotographic photosensitive member having excellent potential characteristics and image characteristics with respect to environmental stability and stability by repeated use, A process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member can be provided.

Claims (11)

In an electrophotographic photosensitive member having a photosensitive layer and an intermediate layer on a conductive support, the intermediate layer has a repeating structural unit represented by the following formula (1) (R ₁ represents a structural unit having an electron transporting ability). An electrophotographic photosensitive member comprising a high molecular compound having the same.
[Outside 1]

(1) 2. The electrophotographic photosensitive member according to claim 1, wherein the ratio of the repeating structural unit of the formula (1) to all the repeating structural units of the polymer compound is 30% or more. 3. The electrophotographic photoreceptor according to claim 1, wherein the high molecular compound has an electron mobility in a range of 1 × 10 ^{−8 to} 1 × 10 ⁻⁵ cm ² / V sec. The electrophotographic photoreceptor according to any one of claims 1 to 3, wherein a volume resistivity of the polymer compound is 1 × 10 ¹¹ Ωcm or more. Structural units R ₁ having an electron transporting ability in the formula (1) is, according to any one of the preceding claims, characterized in that a structure obtained by removing one hydrogen atom from the structure represented by the formula (2) Electrophotographic photoreceptor.
[Outside 2]

(2)
X and Y in the formula (2) represent an alkyl group, an aryl group, an aralkyl group, and a heterocyclic group which may have a substituent, and may be the same. R _{2 to} R _{5 each} represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group, an aralkyl group, a heterocyclic group, a halogen atom, a nitro group, or a cyano group. Structural units R ₁ having an electron transporting ability in the formula (1) is, according to any one of the preceding claims, characterized in that a structure obtained by removing one hydrogen atom from the structure represented by the formula (3) Electrophotographic photoreceptor.
[Outside 3]

(3)
R ₆ and R ₇ in the formula (3) represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group, an aralkyl group, a heterocyclic group, or a cyano group, and R ₈ and R ₉ represent hydrogen Represents an atom, an alkyl group which may have a substituent, an alkoxy group, a halogen atom, a nitro group, a cyano group, or an ester group. a and b represent 0, 1 or 2. Structural units R ₁ having an electron transporting ability in the formula (1) is, according to any one of the preceding claims, characterized in that a structure obtained by removing one hydrogen atom from the structure represented by the formula (4) Electrophotographic photoreceptor.
[Outside 4]

(4)
R ₈ and R ₉ in the formula (4) represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, or a halogen atom, a nitro group, a cyano group, or an ester group, and R ₁₀ represents a substituent Represents an alkyl group, an aryl group, an aralkyl group, a heterocyclic group, or a cyano group which may have a, and a and b represent 0, 1 or 2. Structural units R ₁ having an electron transporting ability in the formula (1) is, according to any one of the preceding claims, characterized in that a structure obtained by removing one hydrogen atom from the structure represented by the formula (5) Electrophotographic photoreceptor.
[Outside 5]

(5)
Z in the formula (5) represents an oxygen atom, a sulfur atom or a dicyanomethylene group, and R ₈ and R ₉ are a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a halogen atom, a nitro group, a cyano group. Group or ester group. a and b represent 0, 1 or 2. Structural units R ₁ having an electron transporting ability in the formula (1) is, according to any one of the preceding claims, characterized in that a structure obtained by removing one hydrogen atom from the structure represented by the formula (6) Electrophotographic photoreceptor.
[Outside 6]

(6)
P in the formula (6) represents an oxygen atom, a sulfur atom or a dicyanomethylene group, and R ₁₁ and R ₁₂ are a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a halogen atom, a nitro group, or Shows a cyano group. a and b represent 0, 1 or 2. An electrophotographic apparatus main body that integrally supports at least one unit selected from the group consisting of the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposing unit, a developing unit, and a cleaning unit. A process cartridge, which is detachably mounted on a process cartridge. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposing unit, a developing unit, and a transferring unit.