JP3897522B2 - Electrophotographic photosensitive member, process cartridge having the electrophotographic photosensitive member, and electrophotographic apparatus - Google Patents

Description

【外５】

【００２７】
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および電子写真装置である。
【００２８】
【発明の実施の形態】
本発明に係る式（１−１）または（１−２）の反応性基を有するモノマーは、芳香族アミン構造を有する電荷輸送物質を混合する系で使用する場合には、モノマーの反応性が高く、高強度が得られるため、モノマー構造中にフマル酸エステル構造を有していることが必要である。
【００２９】
さらに、機械的強度を高めるという観点から、混合する電荷輸送物質は、式（１−１）または（１−２）の反応性基を有するモノマーと反応可能な反応性基を有し、具体的には、以下の構造から選ばれる反応性基を有していることが好ましい。
【００３０】
【外６】

【００３１】
上記の反応性基を有する電荷輸送物質の基本構造に特に制限はないが、下記構造式（３）〜（４）で示される芳香族アミン構造を有する電荷輸送物質が好ましい。
【００３２】
【外７】

（式中、Ａｒ_１、Ａｒ_２およびＡｒ_３は、それぞれ置換されてもよい芳香環基または複素環基を示す。Ａｒ_１、Ａｒ_２およびＡｒ_３の少なくとも１つは前記式（１−１）または（１−２）で示される反応性基と反応可能な反応性基を有する。）
【００３３】
【外８】

（式中、Ａｒ_４およびＡｒ_５は置換されてもよい芳香環基を示し、Ａｒ_６は置換されてもよい２価の芳香環基または２価の複素環基を示し、Ｒ_１は置換されてもよいアルキル基または芳香環基を示し、Ｒ_２は水素原子、置換されてもよいアルキル基または芳香環基を示す。ｍは１または２であり、Ｒ_１とＲ_２は結合して環を形成してもよい。Ａｒ_４、Ａｒ_５、Ｒ_１およびＲ_２の少なくとも１つは前記式（１−１）または（１−２）で示される反応性基と反応可能な反応性基を有する。）
【００３４】
上記表現のアルキル基としてはメチル、エチル、プロピルなどの基、芳香環基としてはフェニル、ナフチル、アンスリルなどの基、複素環基としてはピリジル、チオニル、チアゾイル、カルバゾイル、ベンゾイミダゾリル、ヘンゾチアゾリルなどの基が挙げられる。
【００３５】
以下に、本発明に用いられるモノマー例を示す。
【００３６】
【表１】

【００３７】
以上の中では、本発明に用いるモノマーとしては電荷輸送物質との相溶性の点で、２０が好ましい。
【００３８】
本発明の電子写真感光体は、特に優れた耐ソルベントクラック性と機械的強度とＡＣ帯電における耐電気特性を合わせ持ち、良好な電子写真特性を持つものである。
【００３９】
本発明のバインダー樹脂は、式（１−１）または（１−２）で示される反応性基を有しているため成膜時の加熱により縮合反応が進行し、硬化することにより結合密度が高まるために、高分子被膜全体の耐久性が上がると同時にソルベントクラックにも強くなるものと考えられる。
【００４０】
本発明の電子写真感光体においては、本発明のバインダー樹脂を形成する上記のモノマーが単一のものであっても、２種類以上の複数のモノマーを有していてもよい。
【００４１】
また、必要に応じて、膜の均一性を高める目的で、本発明の顕著な効果が得られる範囲で、既存の樹脂、オリゴマーを含有してもよい。
【００４２】
その他必要に応じて、光カチオン重合開始剤などの開始剤や、フッ素原子含有樹脂微粒子などの滑剤、酸化防止剤や金属酸化物などの無機フィラーなどを含有してもよい。
【００４３】
以下、本発明に用いる電子写真感光体の構成について説明する。
【００４４】
本発明における電子写真感光体は、感光層が電荷輸送物質と電荷発生物質を同一の層に含有する単層型であっても、電荷輸送物質を含有する電荷輸送層と電荷発生物質を含有する電荷発生層に分離した積層型でもよいが、電子写真特性的には積層型が好ましい。本発明に用いられる重合物は優れた耐久性を有するため、電子写真感光体の表面層に含有されることが好ましい。さらには、電荷輸送層に含有されることが好ましい。
【００４５】
使用する支持体は導電性を有するものであればよく、アルミニウムおよびステンレスなどの金属、あるいは導電層を設けた金属、紙およびプラスチックなどが挙げられ、形状はシート状や円筒状などが挙げられる。
【００４６】
ＬＢＰなど画像入力がレーザー光の場合は、散乱による干渉縞防止、または支持体の傷を被覆することを目的とした導電層を設けてもよい。これはカーボンブラックおよび金属粒子などの導電性粉体をバインダー樹脂に分散させて形成することができる。導電層の膜厚は５〜４０μｍであることが好ましく、１０〜３０μｍであることがより好ましい。
【００４７】
その上に接着機能を有する中間層を設ける。中間層の材料としてはポリアミド、ポリビニルアルコール、ポリエチレンオキシド、エチルセルロース、カゼイン、ポリウレタンおよびポリエーテルウレタンなどが挙げられる。これらは適当な溶剤に溶解して塗布される。中間層の膜厚は０．０５〜５μｍであることが好ましく、０．３〜１μｍであることがより好ましい。
【００４８】
中間層の上には電荷発生層が形成される。本発明に用いられる電荷発生物質としてはセレン−テルル、ピリリウム、チアピリリウム系染料、フタロシアニン、アントアントロン、ジベンズピレンキノン、トリスアゾ、シアニン、ジスアゾ、モノアゾ、インジゴ、キナクリドンおよび非対称キノシアニン系の各顔料が挙げられる。
【００４９】
機能分離型の場合、電荷発生層は前記電荷発生物質を、好ましくは質量で０．３〜４倍量のバインダー樹脂および溶剤と共にホモジナイザー、超音波分散、ボールミル、振動ボールミル、サンドミル、アトライター、ロールミルおよび液衝突型高速分散機などの方法でよく分散し、分散液を塗布し、乾燥させて形成される。電荷発生層の膜厚は５μｍ以下であることが好ましく、０．１〜２μｍであることがより好ましい。
【００５０】
電荷輸送層は主として電荷輸送物質と本発明のバインダー樹脂とを溶剤中に溶解させた塗料を塗工乾燥して形成する。用いられる電荷輸送物質としてはトリアリールアミン系化合物、ヒドラゾン化合物、スチルベン化合物、ピラゾリン系化合物、オキサゾール系化合物、トリアリルメタン系化合物およびチアゾール系化合物などが挙げられる。
【００５１】
これらは、好ましくは質量で０．５〜２倍量のバインダー樹脂と組み合わされ塗工し、乾燥し電荷輸送層を形成する。電荷輸送層の膜厚は５〜４０μｍであることが好ましく、１５〜３０μｍであることがより好ましい。
【００５２】
また、感光層が単層型の場合、前述の電荷発生物質、電荷輸送物質およびバインダー樹脂を含有する。膜厚は１０〜５０μｍであることが好ましく、２０〜４０μｍであることがより好ましい。
【００５３】
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を示す。
【００５４】
図において、１はドラム状の本発明の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。感光体１は、回転過程において、１次帯電手段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、ついで、スリット露光やレーザービーム走査露光などの露光手段（不図示）からの露光光４を受ける。こうして感光体１の周面に静電潜像が順次形成されていく。
【００５５】
形成された静電潜像は、ついで現像手段５によりトナー現像され、現像されたトナー現像像は、不図示の給紙部から感光体１と転写手段６との間に感光体１の回転と同期取り出されて給紙された転写材７に、転写手段６により順次転写されていく。
【００５６】
像転写を受けた転写材７は、感光体面から分離されて像定着手段８へ導入されて像定着を受けることによりコピーとして装置外へプリントアウトされる。
【００５７】
像転写後の感光体１の表面は、クリーニング手段９によっ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（不図示）からの前露光光１０により除電処理された後、繰り返し画像形成に使用される。なお、図１のように１次帯電手段３が帯電ローラーなどに用いた接触帯電手段である場合は、前露光は必ずしも必要ではない。
【００５８】
接触帯電手段の帯電部材には、ローラー形状、ブラシ形状、ベルト形状およびブレード形状など、いずれの形態でも使用できるが、ローラー形状で用いられることが好ましい。図２は、ローラー形状の本発明に用いられる帯電部材１３の層構成の例を示す。
【００５９】
接触帯電方式においては、帯電部材１３と感光体表面との均一な当接状態を確保するために、帯電部材１３に適度な弾性が必要である。そのため、帯電部材１３は、電圧を印加する、ステンレスなどの導電性支持体１３ａとその周囲にゴムや発泡体等を含有する導電性弾性層１３ｂ、さらに、必要に応じて、導電性弾性層１３ｂ上に摩耗性向上や感光体表面の汚染防止のために設けられる導電性被覆層１３ｃを有することが好ましい。
【００６０】
本発明においては、上述の電子写真感光体１、１次帯電手段３、現像手段５およびクリーニング手段９などの構成要素のうち、複数のものをプロセスカートリッジとして一体に結合して構成し、このプロセスカートリッジを複写機やレーザービームプリンターなどの電子写真装置本体に対して着脱自在に構成しても良い。例えば、１次帯電手段３、現像手段５およびクリーニング手段９の少なくとも１つを感光体１と共に一体に支持してカートリッジ化して、装置本体のレール１２などの案内手段を用いて装置本体に着脱自在なプロセスカートリッジ１１とすることができる。
【００６１】
また、露光光４は、電子写真装置が複写機やプリンターである場合には、原稿からの反射光や透過光、あるいは、センサーで原稿を読取り、信号化し、この信号に従って行われるレーザービームの走査、ＬＥＤアレイの駆動および液晶シャッターアレイの駆動などにより照射される光である。
【００６２】
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、液晶プリンターおよび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。
【００６３】
以下、実施例に従って説明する。実施例中、「部」は質量部を示す。
【００６４】
実施例１〜３
直径３０ｍｍ×２５４ｍｍのアルミニウムシリンダーを支持体とし、それに、以下の材料より構成される塗料を支持体上に浸漬コーティング法で塗布し、１４０℃で３０分熱硬化して、膜厚が１８μｍの導電層を形成した。
【００６５】
導電性顔料：ＳｎＯ_２ コート処理硫酸バリウム １０部
抵抗調節用顔料：酸化チタン ２部
バインダー樹脂：フェノール樹脂 ６部
レベリング材：シリコーンオイル ０．００１部
溶剤：メタノール、メトキシプロパノール０．２／０．８ ２０部
【００６６】
次に、この上にＮ−メトキシメチル化ナイロン３部および共重合ナイロン３部をメタノール６５部およびｎブタノール３０部の混合溶媒に溶解した溶液を浸漬コーティング法で塗布して、膜厚が０．７μｍの中間層を形成した。
【００６７】
その上に、ＣｕＫα特性Ｘ線回折のブラック角２θ±０．２°の７．４°および２８．２°に強いピークを有するヒドロキシガリウムフタロシアニン４部、ポリビニルブチラール（商品名：エスレックＢＸ−１、積水化学製）２部およびシクロヘキサノン８０部を直径１ｍｍガラスビーズを用いたサンドミル装置で４時間分散した後、エチルアセテート８０部を加えて電荷発生層用分散液を調製した。これを浸漬コーティング法で塗布して、膜厚が０．２μｍの電荷発生層を形成した。
【００６８】
さらに、第２表の電荷輸送物質を１０部、および第３表のモノマー１２部をモノクロロベンゼン６０部およびジクロロメタン４０部の混合溶媒に溶解して電荷輸送層用塗料を作成し、電荷発生層上に浸漬コーティング法で塗布し、１５０℃で１時間乾燥して、膜厚が２３μｍの電荷輸送層を形成した。
なお、モノマー例３４は下記に示す構造を有する。
【外９】

【００６９】
【表２】

【００７０】
【表３】

【００７１】
次に、評価について説明する。
【００７２】
装置はヒューレットパッカード製ＬＢＰ「レーザージェット４０００」（プロセススピード９４．２ｍｍ／ｓ）を改造して用いた。改造は１次帯電のピーク間電圧を２０％ｕｐとした。作成した電子写真感光体をこの装置で２８℃、９０％ＲＨ下で通紙耐久試験を行った。シーケンスはプリント１枚ごとに１回停止する間欠モードとした。
【００７３】
トナーがなくなったならば補給し画像に問題がでるまで耐久した。
【００７４】
また、ＪＩＳのＫ７２０４に準じて、研磨テープを用いたテーパー摩耗試験機を用い２０分摩耗させ、そのときの質量減少分を測定した。
【００７５】
さらに、電子写真感光体の一部に２５００ｌｘ、１５分間の白色蛍光灯の光を当て５分間放置後、明部電位を測定し、光を当てる前の明部電位との差をフォトメモリー値とした。
【００７６】
さらに、感光体表面に指脂を付着させ４８時間放置し、４００倍の顕微鏡観察によりソルベントクラックの有無を観察し、耐ソルベントクラック性を評価した。なお、ソルベントクラックがないものを○、あるものを×として示す。
【００７７】
その結果を第４表に示す。
【００７８】
【表４】

【００７９】
比較例１〜２
直径３０ｍｍ×２５４ｍｍのアルミニウムシリンダーを支持体として、実施例１と同様にして、導電層および中間層を形成した。
【００８０】
次に、ＣｕＫα特性Ｘ線回折のブラッグ角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（ＴｉＯＰｃ）４部、ポリビニルブチラール（商品名：エスレックＢＭ２、積水化学製）２部およびシクロヘキサノン６０部を直径１ｍｍガラスビーズを用いたサンドミル装置で４時間分散した後、エチルアセテート１００部を加えて電荷発生層用分散液を調製した。これを浸漬コーティング法で塗布して、膜厚が０．３μｍの電荷発生層を形成した。
【００８１】
次に、下記構造式のアミン化合物９部、
【００８２】
【外１０】

下記構造式のスチリル化合物１部、
【００８３】
【外１１】

および第５表に記載するポリマー１２部をモノクロロベンゼン６０部およびジクロロメタン４０部の混合溶媒に溶解した。
【００８４】
この塗料を浸漬コーティング法で塗布し、１２０℃で２時間乾燥して、膜厚が２２μｍの電荷輸送層を形成した。
【００８５】
感光体の評価は、実施例１と同様の方法で行った。その結果を第７表に示す。
【００８６】
【表５】

【００８７】
比較例３〜５
比較例１の電荷輸送層のポリマーに代えて第６表のモノマーを用いた以外は、比較例１と同様に電子写真感光体を作成し評価した。その結果を第７表に示す。
【００８８】
【表６】

【００８９】
【表７】

【００９０】
【発明の効果】
発明によれば、機械的強度を損なうことなく優れた耐ソルベントクラック性を有し、さらに、機械的強度が強く、かつ接触帯電による放電に対する耐電気特性が良好であり製造が容易な接触帯電に適した、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可能となった。
【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。
【図２】 本発明に用いられるローラー形状の帯電部材の層構成の例を示す図である。[0001]
BACKGROUND 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 containing a specific resin, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus. .
[0002]
[Prior art]
In the electrophotographic method, as shown in U.S. Pat. No. 2,297,691, a photoconductive material consisting of a support coated with an insulating substance changes in electrical resistance in accordance with the dose received during exposure and in the dark. Use. The basic characteristics required for an electrophotographic photosensitive member using this photoconductive material are (1) that it can be charged to an appropriate potential in a dark place, (2) there is little potential dissipation in the dark place, And (3) Dissipating charges rapidly by light irradiation.
[0003]
Conventionally, as an electrophotographic photoreceptor, an inorganic photoreceptor having a photosensitive layer mainly composed of an inorganic photoconductive compound such as selenium, zinc oxide and cadmium sulfide has been widely used. However, these satisfy the above conditions (1) to (3) but are not necessarily satisfactory in terms of thermal stability, moisture resistance, durability and productivity.
[0004]
In order to overcome the disadvantages of inorganic photoreceptors, electrophotographic photoreceptors based on various organic photoconductive compounds as main components have been actively developed in recent years. For example, US Pat. No. 3,378,851 discloses a photoreceptor having a charge transport layer containing triallyl pyrazoline, and US Pat. No. 3,871,880 discloses a charge generation layer comprising a derivative of perylene pigment, and a condensate of 3-propylene and formaldehyde. A photoreceptor composed of a charge transport layer made of is known.
[0005]
Further, the organic photoconductive compound can freely select the photosensitive wavelength range of the electrophotographic photosensitive member depending on the compound. For example, for azo pigments, JP-A 61-272754 and JP-A 56-167759. JP-A 57-19576 and JP-A 61-228453 disclose compounds having sensitivity up to the infrared region.
[0006]
Among these materials, those showing sensitivity in the infrared region are used in laser beam printers (hereinafter abbreviated as LBP) and LED printers that have made remarkable progress in recent years, and the frequency of demand thereof has increased.
[0007]
Electrophotographic photoreceptors using these organic photoconductive compounds are used as functionally separated photoreceptors in which a charge transport layer and a charge generation layer are laminated in order to satisfy both electrical and mechanical characteristics. There are many cases.
[0008]
On the other hand, as a matter of course, the electrophotographic photosensitive member is required to have sensitivity, electrical characteristics, and optical characteristics according to the applied electrophotographic process.
[0009]
In particular, in an electrophotographic photoreceptor to be used repeatedly, electrical and mechanical external forces such as corona or contact charging, exposure, toner development, transfer process and surface cleaning are directly applied to the surface of the electrophotographic photoreceptor. Durability against them is also required.
[0010]
Specifically, electrical degradation due to ozone and nitrogen oxides during charging, electrical degradation due to discharge during charging, and mechanical degradation and scratches caused by rubbing of the cleaning member and durability against electrical degradation Is required.
[0011]
The electrical deterioration is particularly a phenomenon in which a carrier is accumulated in a portion irradiated with light and a potential difference is generated from a portion not irradiated with light, which occurs as a photo memory.
[0012]
The mechanical deterioration is particularly eagerly desired to improve the durability because organic photoreceptors, which are often soft materials unlike inorganic photoreceptors, have poor durability against mechanical deterioration.
[0013]
Various attempts have been made to satisfy the durability characteristics required for the photoreceptor as described above.
[0014]
A polycarbonate resin having a bisphenol A skeleton as a resin that is often used for the surface layer and has good wear and electrical properties has attracted attention. However, it cannot solve all the above-mentioned problems, and the following Has a problem.
[0015]
(1) It has poor solubility and exhibits good solubility only in a part of halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane, and these solvents have low boiling points. When a photoreceptor is manufactured using the prepared coating solution, the coated surface is likely to be whitened. It also takes time to manage the solid content of the coating liquid.
[0016]
(2) Solvents other than halogenated aliphatic hydrocarbons are partially soluble in tetrahydrafuran, dioxane, cyclohexane, or mixed solvents thereof, but the solution gels in several days. It is not suitable for photoconductor production due to poor properties.
[0017]
(3) Furthermore, even if the above (1) and (2) are improved, a solvent crack is likely to occur in the polycarbonate resin having bisphenol A as a skeleton.
[0018]
(4) In addition, with the conventional polycarbonate resin, the coating formed with the resin is not lubricious, so the photoconductor is easily scratched, and the cleaning setting that reduces the wear amount of the electrophotographic photoconductor causes image defects. Or cleaning failure due to early deterioration of the cleaning blade or toner fusion may occur.
[0019]
The solution stability mentioned in the above (1) and (2) has been solved by using a polycarbonate Z resin or copolymerizing with bisphenol Z, bisphenol C, or the like.
[0020]
Solvent cracks can also be solved by using silicon-modified polycarbonate or ether-modified polycarbonate as disclosed in JP-A-6-51544 and JP-A-6-75415. However, these modified polycarbonates have a structure that is more flexible against internal stress in the polymer to prevent solvent cracks than conventional polycarbonate resins, resulting in the mechanical strength of the polymer body. There was a drawback that it decreased.
[0021]
In recent years, contact charging systems such as those disclosed in Japanese Patent Application Laid-Open Nos. 57-17826 and 58-40566, which apply a voltage directly to a charging member and apply an electric charge to an electrophotographic photosensitive member, are becoming mainstream. is there. This is a method in which a roller-shaped charging member made of conductive rubber or the like is directly brought into contact with the electrophotographic photosensitive member to apply a charge. Compared with a scorotron or the like, the amount of ozone generated is significantly smaller. About 80% of the current that flows is wasted because it flows to the shield, whereas contact charging has the merit of being very economical since there is no wasted amount.
[0022]
However, the contact charging has a drawback that the charging stability for charging by discharging according to Paschen's law is very poor. As a countermeasure, a so-called AC / DC charging system in which an AC voltage is superimposed on a DC voltage has been devised (Japanese Patent Laid-Open No. 63-149668).
[0023]
Although this charging system improves the stability during charging, the amount of discharge on the surface of the electrophotographic photosensitive member increases significantly due to the superposition of AC, so that the amount of abrasion of the electrophotographic photosensitive member increases. As a result, not only mechanical strength but also electrical strength has been required.
[0024]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of having a conventional polycarbonate resin as a surface layer, an electrophotographic photosensitive member that has a high mechanical strength while being resistant to solvent cracking and is also resistant to electrical deterioration due to contact charging. Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.
[0025]
[Means for Solving the Problems]
That is, the present invention provides an electrophotographic photosensitive member having a photosensitive layer on a support, the photosensitive layer having a reactive group represented by the following formula (1-1) or formula (1-2), and Copolymerization of a monomer having a fumarate ester structure selected from the following formulas (20) to (24) and formulas (28) to (32) with a charge transport material having a reactive group capable of reacting with the monomer An electrophotographic photoreceptor characterized by containing a product.
[0026]
[Outside 4]

[Outside 5]

[0027]
The present invention also provides a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.
[0028]
DETAILED DESCRIPTION OF THE INVENTION
When the monomer having a reactive group of formula (1-1) or (1-2) according to the present invention is used in a system in which a charge transport material having an aromatic amine structure is used, the monomer has a reactivity. In order to obtain high strength and high strength, it is necessary that the monomer structure has a fumaric acid ester structure .
[0029]
Furthermore, from the viewpoint of increasing mechanical strength, the charge transport material to be mixed has a reactive group capable of reacting with the monomer having a reactive group of formula (1-1) or (1-2), It preferably has a reactive group selected from the following structures.
[0030]
[Outside 6]

[0031]
The basic structure of the charge transport material having a reactive group is not particularly limited, but charge transport materials having an aromatic amine structure represented by the following structural formulas (3) to (4) are preferable.
[0032]
[Outside 7]

(In the formula, Ar ₁ , Ar ₂ and Ar ₃ each represent an optionally substituted aromatic group or heterocyclic group. At least one of Ar ₁ , Ar ₂ and Ar ₃ represents the above formula (1-1). Or a reactive group capable of reacting with the reactive group represented by (1-2).
[0033]
[Outside 8]

(In the formula, Ar ₄ and Ar ₅ represent an aromatic ring group which may be substituted, Ar ₆ represents a divalent aromatic ring group or a divalent heterocyclic group which may be substituted, and R ₁ is substituted. R ₂ represents a hydrogen atom, an optionally substituted alkyl group or an aromatic ring group, m is 1 or 2, and R ₁ and R ₂ are bonded to form a ring. At least one of Ar ₄ , Ar ₅ , R ₁ and R _{2 represents} a reactive group capable of reacting with the reactive group represented by the formula (1-1) or (1-2). Have)
[0034]
The alkyl group in the above expression is a group such as methyl, ethyl, propyl, the aromatic ring group is a group such as phenyl, naphthyl, anthryl, the heterocyclic group is a group such as pyridyl, thionyl, thiazoyl, thiazoyl, carbazoyl, benzoimidazolyl, henzothiazolyl, etc. Can be mentioned.
[0035]
Examples of monomers used in the present invention are shown below.
[0036]
[Table 1]

[0037]
Among the above, 20 is preferable as the monomer used in the present invention in terms of compatibility with the charge transport material.
[0038]
The electrophotographic photosensitive member of the present invention has particularly excellent solvent crack resistance, mechanical strength, and electric resistance in AC charging, and has good electrophotographic characteristics.
[0039]
Since the binder resin of the present invention has a reactive group represented by the formula (1-1) or (1-2), the condensation reaction proceeds by heating at the time of film formation, and the bond density is increased by curing. Therefore, it is considered that the durability of the polymer coating as a whole increases, and at the same time, it is resistant to solvent cracks.
[0040]
In the electrophotographic photosensitive member of the present invention, the monomer forming the binder resin of the present invention may be a single monomer or may have two or more types of monomers.
[0041]
Moreover, you may contain the existing resin and an oligomer in the range which can obtain the remarkable effect of this invention for the purpose of improving the uniformity of a film | membrane as needed.
[0042]
In addition, you may contain initiators, such as a photocationic polymerization initiator, lubricants, such as a fluorine atom containing resin microparticles | fine-particles, inorganic fillers, such as antioxidant and a metal oxide, as needed.
[0043]
Hereinafter, the structure of the electrophotographic photosensitive member used in the present invention will be described.
[0044]
The electrophotographic photoreceptor of the present invention contains a charge transport layer containing a charge transport material and a charge generation material even if the photosensitive layer is a single layer type containing the charge transport material and the charge generation material in the same layer. A laminated type separated into charge generation layers may be used, but a laminated type is preferred in terms of electrophotographic characteristics. Since the polymer used in the present invention has excellent durability, it is preferably contained in the surface layer of the electrophotographic photoreceptor. Further, it is preferably contained in the charge transport layer.
[0045]
The support to be used is not particularly limited as long as it has conductivity, and examples thereof include metals such as aluminum and stainless steel, metals provided with a conductive layer, paper, and plastics, and examples of the shape include a sheet shape and a cylindrical shape.
[0046]
When the image input such as LBP is laser light, a conductive layer may be provided for the purpose of preventing interference fringes due to scattering or covering a scratch on the support. This can be formed by dispersing conductive powder such as carbon black and metal particles in a binder resin. The thickness of the conductive layer is preferably 5 to 40 μm, and more preferably 10 to 30 μm.
[0047]
An intermediate layer having an adhesive function is provided thereon. Examples of the material for the intermediate layer include polyamide, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, casein, polyurethane, and polyether urethane. These are dissolved in an appropriate solvent and applied. The thickness of the intermediate layer is preferably 0.05 to 5 μm, and more preferably 0.3 to 1 μm.
[0048]
A charge generation layer is formed on the intermediate layer. Examples of the charge generating substance used in the present invention include selenium-tellurium, pyrylium, thiapyrylium dyes, phthalocyanine, anthanthrone, dibenzpyrenequinone, trisazo, cyanine, disazo, monoazo, indigo, quinacridone, and asymmetric quinocyanine pigments. It is done.
[0049]
In the case of the functional separation type, the charge generation layer comprises the charge generation material, preferably a homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor, roll mill together with a binder resin and a solvent in an amount of 0.3 to 4 times by mass. Further, it is formed by dispersing well by a method such as a liquid collision type high-speed disperser, applying the dispersion, and drying. The film thickness of the charge generation layer is preferably 5 μm or less, more preferably 0.1 to 2 μm.
[0050]
The charge transport layer is formed by applying and drying a paint in which a charge transport material and the binder resin of the present invention are dissolved in a solvent. Examples of the charge transport material used include triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, triallylmethane compounds, and thiazole compounds.
[0051]
These are preferably combined with a binder resin in an amount of 0.5 to 2 times by mass and dried to form a charge transport layer. The film thickness of the charge transport layer is preferably 5 to 40 μm, and more preferably 15 to 30 μm.
[0052]
Further, when the photosensitive layer is of a single layer type, it contains the aforementioned charge generating substance, charge transporting substance and binder resin. The film thickness is preferably 10 to 50 μm, and more preferably 20 to 40 μm.
[0053]
FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.
[0054]
In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotated about a shaft 2 in the direction of an arrow at a predetermined peripheral speed. In the rotation process, the photosensitive member 1 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the primary charging unit 3, and then from an exposure unit (not shown) such as slit exposure or laser beam scanning exposure. Exposure light 4 is received. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the photoreceptor 1.
[0055]
The formed electrostatic latent image is then developed with toner by the developing unit 5, and the developed toner developed image is rotated between the photosensitive member 1 and the transfer unit 6 from a sheet feeding unit (not shown). The image is sequentially transferred by the transfer means 6 to the transfer material 7 that is synchronously taken out and fed.
[0056]
The transfer material 7 that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means 8, and subjected to image fixing to be printed out as a copy.
[0057]
After the image transfer, the surface of the photoreceptor 1 is cleaned by removing the transfer residual toner by the cleaning unit 9, and is further subjected to a charge removal process by the pre-exposure light 10 from the pre-exposure unit (not shown), and then repeatedly. Used for image formation. As shown in FIG. 1, when the primary charging unit 3 is a contact charging unit used for a charging roller or the like, pre-exposure is not necessarily required.
[0058]
The charging member of the contact charging means can be used in any form such as a roller shape, a brush shape, a belt shape and a blade shape, but is preferably used in a roller shape. FIG. 2 shows an example of the layer structure of the charging member 13 used in the present invention in a roller shape.
[0059]
In the contact charging method, the charging member 13 needs to have appropriate elasticity in order to ensure a uniform contact state between the charging member 13 and the surface of the photoreceptor. Therefore, the charging member 13 includes a conductive support 13a such as stainless steel to which a voltage is applied, a conductive elastic layer 13b containing rubber or foam around the conductive support 13a, and, if necessary, a conductive elastic layer 13b. It is preferable to have a conductive coating layer 13c provided on the top for improving wear and preventing contamination of the photoreceptor surface.
[0060]
In the present invention, a plurality of components such as the electrophotographic photosensitive member 1, the primary charging unit 3, the developing unit 5, and the cleaning unit 9 are integrally combined as a process cartridge, and this process is performed. The cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photosensitive member 1 to form a cartridge, and is detachable from the apparatus main body using guide means such as a rail 12 of the apparatus main body. Process cartridge 11.
[0061]
Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is reflected or transmitted light from the original, or the original is read by a sensor and converted into a signal, and a laser beam scanning performed according to this signal is performed. The light emitted by driving the LED array and the liquid crystal shutter array.
[0062]
The electrophotographic photoreceptor of the present invention can be used not only in electrophotographic copying machines but also widely in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making.
[0063]
Hereinafter, it demonstrates according to an Example. In the examples, “part” means part by mass.
[0064]
Examples 1-3
An aluminum cylinder having a diameter of 30 mm × 254 mm is used as a support, and a paint composed of the following materials is applied on the support by a dip coating method, and is thermally cured at 140 ° C. for 30 minutes, so that the film thickness is 18 μm. A layer was formed.
[0065]
Conductive pigment: SnO ₂ coated barium sulfate 10 parts Resistance adjusting pigment: Titanium oxide 2 parts Binder resin: Phenol resin 6 parts Leveling material: Silicone oil 0.001 part Solvent: Methanol, methoxypropanol 0.2 / 0.8 20 copies
Next, a solution obtained by dissolving 3 parts of N-methoxymethylated nylon and 3 parts of copolymer nylon in a mixed solvent of 65 parts of methanol and 30 parts of n-butanol was applied thereto by a dip coating method. A 7 μm intermediate layer was formed.
[0067]
Furthermore, 4 parts of hydroxygallium phthalocyanine having strong peaks at 7.4 ° and 28.2 ° of black angle 2θ ± 0.2 ° of CuKα characteristic X-ray diffraction, polyvinyl butyral (trade name: ESREC BX-1, 2 parts of Sekisui Chemical Co., Ltd. and 80 parts of cyclohexanone were dispersed in a sand mill apparatus using glass beads having a diameter of 1 mm for 4 hours, and then 80 parts of ethyl acetate was added to prepare a dispersion for charge generation layer. This was applied by a dip coating method to form a charge generation layer having a thickness of 0.2 μm.
[0068]
Further, 10 parts of the charge transport material of Table 2 and 12 parts of the monomer of Table 3 were dissolved in a mixed solvent of 60 parts of monochlorobenzene and 40 parts of dichloromethane to prepare a charge transport layer coating material on the charge generation layer. Was applied by dip coating and dried at 150 ° C. for 1 hour to form a charge transport layer having a thickness of 23 μm.
The monomer example 34 has the following structure.
[Outside 9]

[0069]
[Table 2]

[0070]
[Table 3]

[0071]
Next, evaluation will be described.
[0072]
The apparatus used was modified LBP “Laser Jet 4000” (process speed 94.2 mm / s) manufactured by Hewlett-Packard. In the modification, the peak-to-peak voltage of primary charging was set to 20% up. The prepared electrophotographic photosensitive member was subjected to a paper passing durability test using this apparatus at 28 ° C. and 90% RH. The sequence was an intermittent mode that stopped once for each printed sheet.
[0073]
If the toner runs out, it is replenished and it lasts until there is a problem with the image.
[0074]
Further, according to JIS K7204, a taper wear tester using an abrasive tape was used for 20 minutes, and the mass loss at that time was measured.
[0075]
Furthermore, after irradiating a part of the electrophotographic photosensitive member with 2500 lx, 15 minutes of white fluorescent light for 5 minutes and measuring the light portion potential, the difference from the light portion potential before the light is applied is determined as the photomemory value. did.
[0076]
Furthermore, finger grease was attached to the surface of the photoreceptor and allowed to stand for 48 hours, and the presence or absence of a solvent crack was observed by microscopic observation at 400 times to evaluate the solvent crack resistance. In addition, a thing without a solvent crack is shown as (circle) and a certain thing is shown as x.
[0077]
The results are shown in Table 4.
[0078]
[Table 4]

[0079]
Comparative Examples 1-2
A conductive layer and an intermediate layer were formed in the same manner as in Example 1 using an aluminum cylinder having a diameter of 30 mm × 254 mm as a support.
[0080]
Next, 4 parts of oxytitanium phthalocyanine (TiOPc) having strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° with a Bragg angle 2θ ± 0.2 ° of CuKα characteristic X-ray diffraction , 2 parts of polyvinyl butyral (trade name: ESREC BM2, manufactured by Sekisui Chemical Co., Ltd.) and 60 parts of cyclohexanone were dispersed in a sand mill apparatus using glass beads having a diameter of 1 mm for 4 hours, and then 100 parts of ethyl acetate was added to the dispersion for charge generation layer. Was prepared. This was applied by a dip coating method to form a charge generation layer having a thickness of 0.3 μm.
[0081]
Next, 9 parts of an amine compound of the following structural formula,
[0082]
[Outside 10]

1 part of a styryl compound of the structural formula
[0083]
[Outside 11]

And 12 parts of the polymer listed in Table 5 were dissolved in a mixed solvent of 60 parts of monochlorobenzene and 40 parts of dichloromethane.
[0084]
This paint was applied by a dip coating method and dried at 120 ° C. for 2 hours to form a charge transport layer having a thickness of 22 μm.
[0085]
The evaluation of the photoconductor was performed in the same manner as in Example 1. The results are shown in Table 7.
[0086]
[Table 5]

[0087]
Comparative Examples 3-5
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Comparative Example 1 except that the monomers shown in Table 6 were used instead of the polymer of the charge transport layer of Comparative Example 1. The results are shown in Table 7.
[0088]
[Table 6]

[0089]
[Table 7]

[0090]
【The invention's effect】
According to the invention, it has excellent solvent crack resistance without impairing mechanical strength, and further has high mechanical strength and good electric resistance against electric discharge due to contact charging, making contact charging easy to manufacture. It has become possible to provide a suitable electrophotographic photosensitive member, 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.
FIG. 2 is a diagram illustrating an example of a layer configuration of a roller-shaped charging member used in the present invention.

Claims (6)

In an electrophotographic photosensitive member having a photosensitive layer on a support, the photosensitive layer has a reactive group represented by the following formula (1-1) or formula (1-2), and the following formula (20): Or a copolymer of a monomer having a fumarate structure selected from (24) and formulas (28) to (32) and a charge transport material having a reactive group capable of reacting with the monomer. An electrophotographic photosensitive member.
[Outside 1]

[Outside 2]

The electrophotographic photosensitive member according to claim 1, wherein the reactive group of the charge transport material has a structure selected from the following structures.
[Outside 3]

  3. The electrophotographic photosensitive member according to claim 1 and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means are integrally supported and detachably attached to the main body of the electrophotographic apparatus. A process cartridge characterized by being.   The process cartridge according to claim 3, wherein the charging unit is a contact charging unit.   An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an exposure unit, a developing unit, and a transfer unit.   The electrophotographic apparatus according to claim 5, wherein the charging unit is a contact charging unit.

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