JPH07295276A - Electrophotographic photoreceptor and electrophotographic device having the electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE:To lower the coefft. of friction of a surface layer, to improve cleanability and durability and to prevent image deterioration by repetitive use by containing a fluorine comb-type graft polymerized resin which is passed through a narrow nozzle under a high pressure and is then refined again by settling into the surface layer. CONSTITUTION:The surface layer contains fluororesin particulates and the fluorine comb-type graft polymerized resin. The fluorine comb-type graft polymerized resin which is passed through the narrow nozzle under the high pressure and is then refined again by settlement is incorporated into the surface layer. For example, a resin soln. from a fluorine comb-type graft polymerized resin soln. tank 10 is pressurized by a highpressure pump 11 and is introduced to the narrow nozzle 12. The treated liquid is received in a resin soln. tank 13. Namely, the fluorine comb-type graft polymerized resin forms micelle in the solvent and impurities are taken into the micelle at the time of refining by settlement. Sufficient refining of this resin is thus not possible. However, the resin is passed through the narrow nozzle under the high pressure, by which the formation of the micelle is hindered and the resin is sufficiently refined of the impurities at the time of the refining by the settlement.

Description

【発明の詳細な説明】Detailed Description of the Invention

【産業上の利用分野】本発明は電子写真感光体及び該電
子写真感光体を備えた電子写真装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member and an electrophotographic apparatus equipped with the electrophotographic photosensitive member.

【０００２】[0002]

【従来の技術】電子写真感光体は適用される電子写真プ
ロセスに応じた感度、電気特性、光学特性を備えている
ことが必要であるが、更に繰り返し使用される感光体に
あっては表面層には、帯電、トナ−現像、紙への転写、
クリ−ニング等のプロセスにより電気的、機械的外力が
直接加えられるため、これらに対する耐久性が要求され
る。具体的には摩擦による表面の摩耗、傷の発生、また
高湿下における表面の劣化等に対する耐久性が要求され
る。またトナ−による現像、クリ−ニングの繰り返しに
より表面層へトナ−が付着するという問題があり、これ
に対しては表面層のクリ−ニング性の向上が求められ
る。上記のような表面層に要求される特性を満たすため
種々の方法が検討されている。その中で、フッ素系樹脂
粒子を分散させた樹脂層を表面に設ける手段は、ある程
度効果的である。2. Description of the Related Art An electrophotographic photosensitive member is required to have sensitivity, electrical characteristics and optical characteristics according to an electrophotographic process to be applied. Includes charging, toner development, transfer to paper,
Since external electric and mechanical forces are directly applied by a process such as cleaning, durability against them is required. Specifically, it is required to have durability against abrasion of the surface due to friction, generation of scratches, deterioration of the surface under high humidity and the like. Further, there is a problem that the toner adheres to the surface layer due to repeated development and cleaning by the toner. To this end, improvement of the cleaning property of the surface layer is required. Various methods have been studied in order to satisfy the properties required for the surface layer as described above. Among them, the means of providing the resin layer in which the fluorine-based resin particles are dispersed on the surface is effective to some extent.

【０００３】フッ素系樹脂粒子の分散により表面層の摩
擦係数が減少し、クリ−ニング性の向上、摩耗や傷に対
する耐久性が向上する作用がある。しかしながら、フッ
素系樹脂粒子の分散において、その分散性、凝集性に問
題があり、均一で平滑な膜を形成することが困難であ
り、形成された表面層は画像ムラやピンホ−ル等の画像
欠陥を有することが避けられなかった。また、分散性の
良好なバインダ−樹脂、分散助剤等は殆どの場合、その
使用は電子写真特性の劣化を生じており、効果的なもの
は見いだせなかった。分散助剤の例としてフッ素系クシ
型グラフト重合樹脂が挙げられるが、この場合、フッ素
系樹脂粒子の分散は良好となるが、高湿下における繰り
返し使用による画質劣化が生じるという問題が生じた。
即ち、繰り返し使用により残留電位が上昇し、画像カブ
リを生じた。原因としては、フッ素系樹脂粒子に含まれ
る界面活性剤やフッ素系クシ型グラフト重合樹脂、フッ
素系樹脂粒子に不純物として含まれる有機塩類、モノマ
−等と水分が作用して残留電位が上昇することにある。
そのため、再沈、洗浄等の種々の精製方法が試みられた
が十分な結果は得られていなかった。Dispersion of the fluorine resin particles has the effect of reducing the friction coefficient of the surface layer, improving the cleanability, and improving the durability against abrasion and scratches. However, in the dispersion of the fluorine-based resin particles, there is a problem in the dispersibility and cohesiveness, it is difficult to form a uniform and smooth film, and the formed surface layer has an image unevenness or an image such as pinholes. It was unavoidable to have defects. In most cases, binder resins, dispersion aids, etc. having good dispersibility have been found to cause deterioration of electrophotographic characteristics, and effective ones have not been found. An example of the dispersion aid is a fluorine-type comb-type graft polymerization resin. In this case, although the dispersion of the fluorine-based resin particles is good, there is a problem that image quality is deteriorated due to repeated use under high humidity.
That is, the residual potential increased due to repeated use, and image fog occurred. The cause is that the residual potential rises due to water acting on the surfactant and the fluorine-type graft-polymerized resin contained in the fluorine-based resin particles, the organic salts contained as impurities in the fluorine-based resin particles, monomers and the like. It is in.
Therefore, various purification methods such as reprecipitation and washing have been tried, but sufficient results have not been obtained.

【０００４】[0004]

【発明が解決しようとする課題】本発明の目的は、表面
層の摩擦係数を減少させ、クリ−ニング性、摩耗や傷に
対する耐久性を有し、かつ、繰り返しの電子写真プロセ
スにおいて残留電位の上昇がなく、常に高品位の画像が
得られる電子写真感光体及び該電子写真感光体を備えた
電子写真装置を提供することである。SUMMARY OF THE INVENTION The object of the present invention is to reduce the coefficient of friction of the surface layer, to provide cleaning properties, durability against abrasion and scratches, and to reduce residual potential in repeated electrophotographic processes. An object of the present invention is to provide an electrophotographic photosensitive member that does not rise and can always obtain a high-quality image, and an electrophotographic apparatus including the electrophotographic photosensitive member.

【０００５】[0005]

【課題を解決するための手段】本発明は表面層にフッ素
系樹脂粒子及びフッ素系クシ型グラフト重合樹脂を含有
する電子写真感光体において、該表面層に高圧で狭いノ
ズルを通過させた後再沈精製されたフッ素系クシ型グラ
フト重合樹脂を含有することを特徴とする電子写真感光
体から構成される。The present invention relates to an electrophotographic photoreceptor containing fluorine-based resin particles and a fluorine-type comb-type graft-polymerized resin in a surface layer, which is re-exposed after passing through a narrow nozzle at high pressure. It is composed of an electrophotographic photoconductor characterized by containing a precipitated and purified fluorine-type comb-type graft polymerization resin.

【０００６】本発明の原理については、フッ素系クシ型
グラフト重合樹脂は溶媒中においてミセルを形成してお
り、再沈精製時に不純物がミセルに取り込まれ十分精製
ができない。しかし、高圧で狭いノズルを通過させるこ
とにより、ミセルの形成が阻害され、再沈精製時に不純
物が十分精製されるようになる。According to the principle of the present invention, the fluorine-type comb-type graft-polymerized resin forms micelles in a solvent, and impurities are incorporated into the micelles during purification by reprecipitation, so that sufficient purification cannot be performed. However, by passing through a narrow nozzle at high pressure, formation of micelles is hindered, and impurities are sufficiently purified during reprecipitation purification.

【０００７】本発明において用いるフッ素系クシ型グラ
フト重合樹脂を精製する場合には、フッ素系クシ型グラ
フト重合樹脂を良溶媒で溶解しその溶液を高圧で狭いノ
ズルに通過させる。In the case of purifying the fluorine-type comb-type graft polymer resin used in the present invention, the fluorine-type comb-type graft polymer resin is dissolved in a good solvent and the solution is passed under high pressure through a narrow nozzle.

【０００８】本発明において用いるフッ素系クシ型グラ
フト重合樹脂を溶解する良溶媒としては、フッ素系クシ
型グラフト重合樹脂に対する溶解性が特に良好なものを
選定した方が効果が大きい。特に良好な例としては、メ
チルエチルケトン、アセトン、メチルイソブチルケト
ン、シクロヘキサノン等のケトン類、ジエチルエ−テ
ル、テトラヒドロフラン等のエ−テル類、酢酸エチル、
酢酸ブチル等のエステル類、トルエン、ベンゼン等の炭
化水素類、クロロベンゼン等のハロゲン化炭化水素類な
どが挙げられる。As a good solvent for dissolving the fluorine-type comb-type graft-polymerized resin used in the present invention, it is more effective to select one having a particularly good solubility in the fluorine-type comb-type graft-polymerized resin. Particularly preferable examples include ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone, diethyl ether, ethers such as tetrahydrofuran, ethyl acetate,
Examples thereof include esters such as butyl acetate, hydrocarbons such as toluene and benzene, and halogenated hydrocarbons such as chlorobenzene.

【０００９】本発明で用いるフッ素系クシ型グラフト重
合樹脂溶液を処理するための高圧で狭いノズルを通過さ
せる装置の構成の例を図２に示した。フッ素系クシ型グ
ラフト重合樹脂溶液タンク１０より高圧ポンプ１１で樹
脂溶液を加圧し、これを狭いノズル１２に導く、処理さ
れた液は樹脂溶液タンク（処理済）１３で受ける。FIG. 2 shows an example of the constitution of an apparatus for treating the fluorine-type comb-type graft polymerization resin solution used in the present invention, which is passed through a narrow nozzle at high pressure. The high pressure pump 11 pressurizes the resin solution from the fluorine-type comb-type graft polymerization resin solution tank 10 and guides it to the narrow nozzle 12, and the processed solution is received by the resin solution tank (processed) 13.

【００１０】ノズルの形状の例としては、直線状でもよ
いが、図３の（ａ）のノズルの途中にクランク状の曲が
りがあるもの、図３の（ｂ）の溶液の流れを一旦２つに
分割し衝突させる構造のもの等、乱流の発生しやすいも
のが良好である。As an example of the shape of the nozzle, a linear shape may be used, but there is a crank-shaped bend in the middle of the nozzle of FIG. 3 (a), and there are two solution flows once in FIG. 3 (b). It is preferable to use a structure in which turbulent flow is easily generated, such as a structure in which the structure is divided into two and collided.

【００１１】ノズルの大きさはポンプの容量を必要とす
る圧力によるが１０００μｍ以下が好ましい。The size of the nozzle depends on the pressure required for the capacity of the pump, but is preferably 1000 μm or less.

【００１２】溶液に加える圧力は、ノズルの形状、フッ
素系クシ型グラフト重合樹脂の種類、溶媒の種類によっ
て決定されるが、一般には５０ｋｇ／ｃｍ² 以上、特に
２００ｋｇ／ｃｍ² 以上で良好な結果が得られる。圧力
の上限に関しては装置の構成及びフッ素系クシ型グラフ
ト重合樹脂が分解しない範囲で決めるが２０００ｋｇ／
ｃｍ² 以上では樹脂が分解しやすい。The pressure applied to the solution is determined by the shape of the nozzle, the type of fluorine-type comb-type graft-polymerized resin, and the type of solvent. Generally, 50 kg / cm ² or more, particularly 200 kg / cm ² or more, gives good results. Is obtained. The upper limit of the pressure is determined within the range of the equipment configuration and the range in which the fluorine-based comb-type graft polymerization resin does not decompose, but 2000 kg /
If it is cm ² or more, the resin is easily decomposed.

【００１３】本発明においてはフッ素系クシ型グラフト
重合樹脂溶液が高速で狭いノズルを通過する際の強い乱
流によりミセルが解消されるものであるからノズルを通
過する速度を速くする必要がある。好ましくは３０ｍ／
ｓｅｃ以上、特に好ましくは５０ｍ／ｓｅｃ以上であ
る。In the present invention, micelles are eliminated by strong turbulent flow when the fluorine-based comb-type graft polymerized resin solution passes through a narrow nozzle at high speed, and therefore the speed of passing through the nozzle must be increased. Preferably 30 m /
sec or more, particularly preferably 50 m / sec or more.

【００１４】再沈精製の方法に関しては、高圧で狭いノ
ズルを通過させたフッ素系クシ型グラフト重合樹脂溶液
を貧溶媒と混合する。本発明において用いるフッ素系ク
シ型グラフト重合樹脂を溶解する貧溶媒としては、フッ
素系クシ型グラフト重合樹脂に対して溶解性の低いもの
が適しており、特に良好な例としてはメタノ−ル、エタ
ノ−ル、ブタノ−ル、イソプロピルアルコ−ル等のアル
コ−ル類、ノルマルヘキサン、石油エ−テル、シクロヘ
キサン等の炭化水素類等、更に水等が挙げられる。Regarding the method of reprecipitation purification, the fluorine-type comb-type graft polymerized resin solution passed through a narrow nozzle at high pressure is mixed with a poor solvent. As the poor solvent for dissolving the fluorine-type comb-type graft polymerization resin used in the present invention, those having a low solubility with respect to the fluorine-type comb-type graft polymerization resin are suitable, and particularly preferable examples include methanol and ethanol. Alcohol, butanol, butanol, isopropyl alcohol and the like, hydrocarbons such as normal hexane, petroleum ether and cyclohexane, and water.

【００１５】本発明で適用される樹脂精製方法とその他
の一般の精製方法、例えば抽出、通常の再沈精製等と組
み合わせることが可能である。It is possible to combine the resin purification method applied in the present invention with other general purification methods such as extraction and ordinary reprecipitation purification.

【００１６】本発明で用いられるフッ素系クシ型グラフ
ト重合樹脂は、各分子鎖の片末端に重合性の官能基を有
する分子量が１０００から１００００程度の比較的低分
子量のオリゴマ−からなるマクロモノマ−とフッ素系重
合性モノマ−を共重合して得られるものであり、フッ素
系重合体の幹にマクロモノマ−の重合体が板状にぶらさ
がった構造を有している。マクロモノマ−にはグラフト
重合樹脂を添加する樹脂に親和性のあるものが選択さ
れ、例えばアクリル酸エステル類、メタクリル酸エステ
ルあるいはスチレン化合物等の重合体や共重合体等が用
いられる。The fluorine-type comb-type graft polymerization resin used in the present invention is a macromonomer composed of a relatively low molecular weight oligomer having a polymerizable functional group at one end of each molecular chain and having a molecular weight of about 1,000 to 10,000. It is obtained by copolymerizing a fluorine-based polymerizable monomer, and has a structure in which a macromonomer polymer is hung in a plate shape on the trunk of the fluorine-based polymer. As the macromonomer, one having an affinity for the resin to which the graft-polymerized resin is added is selected, and for example, polymers or copolymers of acrylic acid esters, methacrylic acid esters or styrene compounds are used.

【００１７】一方、フッ素系重合性モノマ−としては、
下記（１）〜（６）に示すような側鎖にフッ素原子を有
する重合性モノマ−の１種あるいは２種以上を用いるこ
とができるが、これに限定されるものではない。On the other hand, as the fluorine-based polymerizable monomer,
One or more polymerizable monomers having a fluorine atom in the side chain as shown in the following (1) to (6) can be used, but the present invention is not limited thereto.

【化１】 [Chemical 1]

【化２】 [Chemical 2]

【化３】 [Chemical 3]

【化４】 [Chemical 4]

【化５】 [Chemical 5]

【化６】 式中、Ｒ₁ は水素原子またはメチル基を表わす。Ｒ₂ は
水素原子、ハロゲン原子、アルキル基、アルコキシ基ま
たはニトリル基を表わし、その数種類の組み合わせでも
よい。ｎは１以上の整数、ｍは１〜５の整数、ｋは１〜
４の整数を表わし、ｍ＋ｋ＝５である。[Chemical 6] In the formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a nitrile group, and may be a combination of several kinds thereof. n is an integer of 1 or more, m is an integer of 1 to 5, k is 1
It represents an integer of 4, and m + k = 5.

【００１８】フッ素系クシ型グラフト重合樹脂中におけ
るフッ素系モノマ−殘基の含量は、フッ素系クシ型グラ
フト重合樹脂中５〜９０重量％が好ましく、１０〜７０
重量％が更に好ましい。フッ素系モノマ−殘基の含量が
５重量％未満では、疎水化の改質効果は十分に発揮でき
ず、また、フッ素系モノマ−殘基の含量が９０重量％を
超えるとマクロモノマ−との溶解性が悪くなる。The content of the fluorine-containing monomer group in the fluorine-type comb-type graft polymerized resin is preferably 5 to 90% by weight, preferably 10-70% by weight in the fluorine-type comb-type graft polymerized resin.
Weight% is more preferred. If the content of the fluorine-containing monomer group is less than 5% by weight, the hydrophobizing effect cannot be sufficiently exerted, and if the content of the fluorine-containing monomer group exceeds 90% by weight, it is dissolved with the macromonomer. The sex becomes worse.

【００１９】本発明において用いるフッ素系クシ型グラ
フト重合樹脂としては、アクリル酸エステル類、メタク
リル酸エステル、スチレン化合物より選ばれたマクロモ
ノマ−及びパ−フルオロアルキルエチルメタクリレ−ト
よりグラフト重合された樹脂が望ましいが、特にメチル
メタクリレ−トを幹としパ−フルオロアルキルエチルメ
タクリレ−トとグラフト重合された樹脂が好ましい。The fluorine-type comb-type graft-polymerized resin used in the present invention is a resin graft-polymerized from a macromonomer selected from acrylic acid esters, methacrylic acid esters, and styrene compounds, and perfluoroalkylethyl methacrylate. However, a resin which is graft-polymerized with perfluoroalkylethyl methacrylate as a backbone of methyl methacrylate is preferable.

【００２０】本発明において用いるフッ素系樹脂粒子群
としては、四フッ化エチレン樹脂、三フッ化塩化エチレ
ン樹脂、六フッ化エチレンプロピレン樹脂、フッ化ビニ
ル樹脂、フッ化ビニリデン樹脂、二フッ化二塩化エチレ
ン樹脂及びこれら共重合体から１種あるいは２種以上を
適宜選択するのが望ましいが、特に四フッ化エチレン樹
脂、フッ化ビニリデン樹脂が好ましい。樹脂の分子量や
粒子の粒径は、適宜選択することができ、特に制限され
るものではない。The fluorine resin particles used in the present invention include tetrafluoroethylene resin, trifluoroethylene chloride resin, hexafluoroethylene propylene resin, vinyl fluoride resin, vinylidene fluoride resin, and difluoride dichloride. It is desirable to appropriately select one kind or two or more kinds from the ethylene resin and the copolymers thereof, and the tetrafluoroethylene resin and the vinylidene fluoride resin are particularly preferable. The molecular weight of the resin and the particle size of the particles can be appropriately selected and are not particularly limited.

【００２１】フッ素系グラフト重合樹脂の存在によりフ
ッ素系樹脂粒子群の分散性が向上し、また塗膜形成時の
凝集が防止されるので、極めて均一で平滑なフッ素系樹
脂粒子分散層が形成される。またフッ素系グラフト重合
樹脂は上述の構造を有しているので、樹脂層形成用のバ
インダ−樹脂を含有する塗布液に対する相溶性が優れて
いるため、表面層上へ移行や滲み出しがない。更に、高
圧で狭いノズルを通過させた後再沈精製されたフッ素系
グラフト重合樹脂を用いることにより、繰り返しの電子
写真プロセスによる残留電荷の蓄積がなく、安定した帯
電特性が得られる。The presence of the fluorine-based graft-polymerized resin improves the dispersibility of the fluorine-based resin particle group and prevents the agglomeration at the time of forming the coating film, so that an extremely uniform and smooth fluorine-based resin particle dispersion layer is formed. It Further, since the fluorine-based graft-polymerized resin has the above-mentioned structure, it has excellent compatibility with the coating liquid containing the binder resin for forming the resin layer, and therefore does not migrate or ooze onto the surface layer. Furthermore, by using a fluorine-based graft polymerization resin that has been refined and reprecipitated after passing through a narrow nozzle at high pressure, stable charging characteristics can be obtained without accumulation of residual charges due to repeated electrophotographic processes.

【００２２】分散されるフッ素系樹脂粒子群の含量は、
固形分重量に基づいて、１〜５０％が適当であり、特に
５〜３０％が好ましい。含量が１％未満ではフッ素系樹
脂粒子群の分散による改質効果が十分でなく、一方、５
０％を超えると光通過性が低下し、かつ、キャリアの移
動性も低下する。またフッ素系グラフト重合樹脂の含量
は、固形分重量に基づいて、０．０１〜１０％が適当で
あり、特に０．０２〜２％が好ましい。含量が０．０１
％未満ではフッ素系樹脂粒子群の分散性改良効果が十分
でなく、一方、１０％を超えるとフッ素系グラフト重合
樹脂が塗膜表面だけでなく、バルク中にも存在するよう
になるため樹脂との相溶性の問題から、繰り返し電子写
真プロセスを行ったときの残留電荷の蓄積が生じてく
る。The content of the dispersed fluororesin particles is
Based on the weight of the solid content, 1 to 50% is suitable, and 5 to 30% is particularly preferable. If the content is less than 1%, the modifying effect due to the dispersion of the fluororesin particles is not sufficient, while 5
If it exceeds 0%, the light transmitting property is deteriorated and the carrier mobility is also deteriorated. Further, the content of the fluorine-based graft polymerization resin is suitably 0.01 to 10%, particularly preferably 0.02 to 2%, based on the weight of the solid content. Content is 0.01
If it is less than 10%, the effect of improving the dispersibility of the fluorinated resin particles is not sufficient, while if it exceeds 10%, the fluorinated graft-polymerized resin is present not only on the surface of the coating film but also in the bulk. Due to the compatibility problem of (1), accumulation of residual charge occurs when the electrophotographic process is repeatedly performed.

【００２３】樹脂層を形成するためのバインダ−樹脂
は、成膜性のある高分子であればよいが、単独でもある
程度の硬さを有すること、キャリア輸送を妨害しないこ
と等の点から、ポリメタクリル酸エステル、ポリカ−ボ
ネ−ト、ポリアクリレ−ト、ポリエステル、ポリスルホ
ン等が好ましい。The binder resin for forming the resin layer may be a polymer having a film-forming property, but it can be used as a binder resin from the viewpoint that it has a certain degree of hardness when used alone and does not interfere with carrier transportation. Methacrylic acid ester, polycarbonate, polyacrylate, polyester, polysulfone and the like are preferable.

【００２４】本発明の電子写真感光体の表面層を形成す
るための塗布液の調製方法は、バインダ−樹脂、電荷輸
送物質等を溶媒と共にフッ素系樹脂粒子、フッ素系クシ
型グラフト重合樹脂を同時に分散してもよい。また、フ
ッ素系樹脂粒子、フッ素系クシ型グラフト重合樹脂、バ
インダ−樹脂を分散して分散液を調製し、電荷輸送物質
等を予め分散した塗布液に混合してもよい。電子写真感
光体用塗布液またはフッ素系樹脂粒子等の分散液の調製
においては、単なる撹拌混合でもよいが、必要に応じて
ボ−ルミル、ロ−ルミル、サンドミル、高圧ホモジナイ
ザ−等の分散手段を用いる。ここで用いる溶媒として
は、塗布液中のバインダ−樹脂、電荷輸送材に対する溶
解性、塗布性に対して良好な溶媒を選定する。The method for preparing the coating liquid for forming the surface layer of the electrophotographic photosensitive member of the present invention is as follows: a binder resin, a charge transporting substance and the like together with a solvent, together with a fluorine resin particle and a fluorine comb type graft polymer resin. It may be dispersed. Alternatively, the fluorine-based resin particles, the fluorine-based comb-type graft-polymerized resin, and the binder resin may be dispersed to prepare a dispersion liquid, and the dispersion liquid may be mixed with a coating liquid in which the charge transport material and the like are previously dispersed. In the preparation of the coating liquid for the electrophotographic photosensitive member or the dispersion liquid of the fluorine-based resin particles and the like, simple stirring and mixing may be used, but if necessary, a dispersing means such as a ball mill, a roll mill, a sand mill, a high pressure homogenizer, etc. To use. As the solvent used here, a solvent which is good in solubility in the binder resin in the coating liquid, the charge transport material, and the coating property is selected.

【００２５】本発明の電子写真感光体の導電性支持体の
例としては、アルミニウム、銅、ニッケル、銀等の金属
またはこれらの合金、酸化アンチモン、酸化インジウ
ム、酸化スズ等の導電性金属酸化物、カ−ボンファイバ
−、カ−ボンブラック、グラファイト粉末と樹脂を混合
成型したもの等が挙げられる。Examples of the conductive support of the electrophotographic photosensitive member of the present invention include metals such as aluminum, copper, nickel and silver or alloys thereof, and conductive metal oxides such as antimony oxide, indium oxide and tin oxide. , Carbon fiber, carbon black, a mixture of graphite powder and resin, and the like.

【００２６】導電性支持体上の欠陥の被覆、導電性支持
体の保護のため支持体上に導電層を設けることができ、
例えば、アルミニウム、銅、ニッケル、銀等の金属粉
体、酸化アンチモン、酸化インジウム、酸化スズ等の導
電性金属酸化物、ポリピロ−ル、ポリアニリン、高分子
電解質等の高分子導電材、カ−ボンファイバ−、カ−ボ
ンブラック、グラファイト粉末またはこれら導電性物質
で表面を被覆した導電性粉体等の導電性物質をアクリル
樹脂、ポリエステル、ポリアミド、ポリ酢酸ビニル、ポ
リカ−ボネ−ト、ポリビニルブチラ−ル等の熱可塑性樹
脂、ポリウレタン、フェノ−ル樹脂、エポキシ樹脂等の
熱硬化性樹脂、光硬化性樹脂等のバインダ−樹脂に分散
したもの、更に必要に応じた添加剤を加えたものを支持
体上に塗布したものが挙げられる。A conductive layer can be provided on the support to cover defects on the conductive support and protect the conductive support.
For example, metal powders of aluminum, copper, nickel, silver, etc., conductive metal oxides of antimony oxide, indium oxide, tin oxide, etc., polymer conductive materials such as polypropylene, polyaniline, polymer electrolytes, carbon, etc. Conductive substances such as fibers, carbon black, graphite powder, or conductive powders whose surfaces are coated with these conductive substances are used as acrylic resin, polyester, polyamide, polyvinyl acetate, polycarbonate, polyvinyl butyra. -Thermoplastic resins such as polyurethane, phenolic resins, thermosetting resins such as epoxy resins, binder resins such as photocurable resins, and those to which additives are added if necessary The thing coated on the support body is mentioned.

【００２７】導電性支持体上に設けられる感光層は、単
一構造でも、電荷発生層と電荷輸送層に機能分離した積
層構造でもよい。The photosensitive layer provided on the conductive support may have a single structure or a laminated structure in which the charge generation layer and the charge transport layer are functionally separated.

【００２８】機能分離型感光体において、電荷発生層用
材料としては例えば、ジスアゾ顔料、トリスアゾ顔料等
のアゾ顔料、銅フタロシアニン顔料、チタニルフタロシ
アニン顔料等のフタロシアニン顔料、アントアントロン
等のキノン顔料、ペリレン顔料、インジゴ顔料等の電荷
発生物質をアクリル樹脂、ポリエステル、ポリアミド、
ポリ酢酸ビニル、ポリカ−ボネ−ト、ポリビニルブチラ
−ル等の熱可塑性樹脂、ポリウレタン、フェノ−ル樹
脂、エポキシ樹脂等の熱硬化性樹脂等のバインダ−樹脂
に分散したものが挙げられ、適当な溶媒に分散し、塗布
液を調製する。更に必要に応じた添加剤を加えることが
できる。In the function-separated type photoreceptor, examples of materials for the charge generation layer include azo pigments such as disazo pigments and trisazo pigments, phthalocyanine pigments such as copper phthalocyanine pigments and titanyl phthalocyanine pigments, quinone pigments such as anthanthrone, and perylene pigments. , Charge generating substances such as indigo pigment, acrylic resin, polyester, polyamide,
Those dispersed in a binder resin such as a thermoplastic resin such as polyvinyl acetate, polycarbonate, polyvinyl butyral, etc., a thermosetting resin such as polyurethane, a phenol resin, an epoxy resin, etc. are suitable. Disperse in a suitable solvent to prepare a coating solution. Further, additives can be added if necessary.

【００２９】電荷輸送層用材料としては例えば、ヒドラ
ゾン系化合物、スチルベン系化合物、ピラゾリン系化合
物、オキサゾ−ル系化合物、チアゾ−ル系化合物、トリ
アリ−ルメタン系化合物等の電荷輸送物質及びアクリル
樹脂、ポリエステル、ポリアリレ−ト、ポリ塩化ビニ
ル、ポリカ−ボネ−ト、ポリビニルブチラ−ル、ポリメ
タアクリレ−ト等の熱可塑性樹脂、ポリウレタン、フェ
ノ−ル樹脂、エポキシ樹脂等の熱硬化性樹脂等のバイン
ダ−樹脂をメタノ−ル、エタノ−ル、ブタノ−ル、イソ
プロピルアルコ−ル等のアルコ−ル類、メチルエチルケ
トン、アセトン、メチルイソプロピルブチルケトン、シ
クロヘキサン等のケトン類、ジエチルエ−テル、テトラ
ヒドロフラン等のエ−テル類、酢酸エチル、酢酸プロピ
ル等のエステル類、ノルマルヘキサン、石油エ−テル、
トルエン等の炭化水素類、クロロベンゼン、ジクロロメ
タン等のハロゲン化炭化水素等、その他適当な溶媒に分
散したもの、更に必要に応じた添加剤を加えたもの等の
塗布液が挙げられ、また、導電性ポリマ−を用いたもの
等が挙げられる。Examples of the material for the charge transport layer include charge transport materials such as hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, triarylmethane compounds, and acrylic resins, Thermoplastic resin such as polyester, polyarylate, polyvinyl chloride, polycarbonate, polyvinyl butyral, polymethacrylate, binder of thermosetting resin such as polyurethane, phenol resin, epoxy resin, etc. Resins include alcohols such as methanol, ethanol, butanol and isopropyl alcohol, ketones such as methyl ethyl ketone, acetone, methyl isopropyl butyl ketone and cyclohexane, ethers such as diethyl ether and tetrahydrofuran. , Esters such as ethyl acetate and propyl acetate, Rumaru hexane, petroleum Est - ether,
Coating liquids such as hydrocarbons such as toluene, halogenated hydrocarbons such as chlorobenzene and dichloromethane, and those dispersed in other suitable solvents, and those to which additives are added as necessary are also included. Examples include those using a polymer.

【００３０】本発明において用いられる塗布方法として
は、浸漬塗布、スプレ−塗布、ロ−ルコ−タ−塗布、グ
ラビアコ−タ−塗布等の方法が挙げられる。Examples of the coating method used in the present invention include dip coating, spray coating, roll coater coating and gravure coater coating.

【００３１】本発明においてフッ素系樹脂粒子及び加熱
処理した後再沈精製したフッ素系クシ型グラフト重合樹
脂を含有させる層としては感光体の表面層（直接トナ−
及び現像装置、クリ−ニング装置などに接触する層）に
適用することが有効である。感光体の層構成において、
単一層構造の感光体では感光層に、電荷発生層上に電荷
輸送層を設けた機能分離型感光体では電荷輸送層に、電
荷輸送層上に電荷発生層を設け、更にその上に導電層を
設けた感光体では導電層に、また、感光層上に保護層を
設けた感光体では保護層に用いる。In the present invention, the layer containing the fluorine-based resin particles and the fluorine-based comb-type graft-polymerized resin purified by re-precipitation after heat treatment is used as the surface layer of the photoreceptor (direct toner).
It is effective to apply it to a layer contacting a developing device and a cleaning device). In the layer structure of the photoreceptor,
In the case of a photoreceptor having a single-layer structure, a photosensitive layer is provided, a charge transport layer is provided on the charge generation layer, and in a function-separated type photoreceptor, a charge transport layer is provided, and a charge generation layer is provided on the charge transport layer. Is used for a conductive layer in a photoconductor provided with and a protective layer for a photoconductor in which a protective layer is provided on the photosensitive layer.

【００３２】本発明の電子写真感光体は複写機、レ−ザ
−プリンタ−、ＬＥＤプリンタ−、液晶シャッタ−プリ
ンタ−等の電子写真装置一般に用いる感光ドラムに適用
できる。The electrophotographic photosensitive member of the present invention can be applied to a photosensitive drum generally used in electrophotographic devices such as a copying machine, a laser printer, an LED printer, a liquid crystal shutter and a printer.

【００３３】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。The present invention also comprises an electrophotographic apparatus provided with the electrophotographic photosensitive member of the present invention.

【００３４】図１に本発明のドラム型感光体を用いた一
般的な転写式電子写真装置の概略構成を示した。図にお
いて、１は像担持体としてのドラム型感光体であり軸１
ａを中心に矢印方向に所定の周速度で回転駆動される。
該感光体１はその回転過程で帯電手段２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
部３にて不図示の像露光手段により光像露光Ｌ（スリッ
ト露光・レ−ザ−ビ−ム走査露光など）を受ける。これ
により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。その静電潜像は、次いで現像手段４でト
ナ−現像され、そのトナ−現像像が転写手段５により不
図示の給紙部から感光体１と転写手段５との間に感光体
１の回転と同期取りされて給送された転写材Ｐの面に順
次転写されていく。像転写を受けた転写材Ｐ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
て複写物（コピ−）として機外へプリントアウトされ
る。像転写後の感光体１の表面はクリ−ニング手段６に
て転写残りトナ−の除去を受けて清浄面化され、前露光
手段７により除電処理がされて繰り返して像形成に使用
される。感光体１の均一帯電手段２としてはコロナ帯電
装置が一般に広く使用されている。また、転写装置５も
コロナ転写手段が一般に広く使用されている。電子写真
装置として、上述の感光体や現像手段、クリ−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。例えば、感光体１と
クリ−ニング手段６とを一体化してひとつの装置ユニッ
トとし、装置本体のレ−ル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
トのほうに帯電手段および／または現像手段を伴って構
成してもよい。また、光像露光Ｌは、電子写真装置を複
写機やプリンタ−として使用する場合には、原稿からの
反射光や透過光を用いる、あるいは、原稿を読み取り信
号化に従って、この信号によりレ−ザ−ビ−ムの走査、
発光ダイオ−ドアレイの駆動、または液晶シャッタ−ア
レイの駆動などを行うことにより行われる。FIG. 1 shows a schematic structure of a general transfer type electrophotographic apparatus using the drum type photoreceptor of the present invention. In the figure, reference numeral 1 denotes a drum type photosensitive member as an image bearing member, and a shaft 1
It is rotationally driven around a at a predetermined peripheral speed in the arrow direction.
The photosensitive member 1 is uniformly charged at its peripheral surface by a charging unit 2 at a predetermined positive or negative potential in the course of its rotation, and then at an exposure unit 3 an optical image exposure L (slit exposure Laser beam scanning exposure). As a result, electrostatic latent images corresponding to the exposed image are sequentially formed on the peripheral surface of the photoconductor. The electrostatic latent image is then toner-developed by the developing means 4, and the toner-developed image is rotated by the transfer means 5 from a paper feeding portion (not shown) between the photosensitive body 1 and the transfer means 5. Then, the image is sequentially transferred onto the surface of the transfer material P that is fed in synchronization with the above. The transfer material P which has received the image transfer is separated from the surface of the photoconductor and is introduced into the image fixing means 8 where it is subjected to image fixing and printed out as a copy (copy). The surface of the photoconductor 1 after the image transfer is cleaned by the cleaning means 6 by removing the transfer residual toner, and is subjected to the charge removal processing by the pre-exposure means 7 to be repeatedly used for image formation. As a uniform charging means 2 for the photoconductor 1, a corona charging device is generally widely used. Also, as the transfer device 5, corona transfer means is generally widely used. As an electrophotographic apparatus, a plurality of constituent elements such as the above-mentioned photoconductor, developing means, and cleaning means are integrally combined and configured as an apparatus unit, and this unit is detachably attached to the apparatus main body. You may comprise. For example, the photosensitive member 1 and the cleaning means 6 may be integrated into one device unit, and the device body may be detachable by using a guide means such as a rail. At this time, the above-mentioned apparatus unit may be configured with a charging means and / or a developing means. When the electrophotographic apparatus is used as a copying machine or a printer, the light image exposure L uses reflected light or transmitted light from an original, or the original is read and converted into a signal by a laser. -Beam scanning,
This is performed by driving the light emitting diode array or the liquid crystal shutter array.

【００３５】[0035]

【実施例】【Example】

実施例１ 導電層塗布工程として、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２０００部
（重量部、以下同様）、フェノ−ル樹脂２５００部、メ
チルセロソルブ２０００部、メタノ−ル５００部をφ１
ｍｍガラスビ−ズを用いたサンドミルで２時間分散して
導電層用塗布液を調製した。アルミニウムシリンダ−
（φ３０ｍｍ×３６０ｍｍ、肉厚１ｍｍ）上に上記塗布
液を浸漬塗布した後、１６０℃で２５分間乾燥した。導
電層の膜厚は２０μｍとした。Example 1 In the conductive layer coating step, 2000 parts of conductive titanium oxide coated with tin oxide containing 10% antimony oxide (parts by weight, the same applies hereinafter), 2500 parts of phenol resin, 2000 parts of methyl cellosolve, methanol. 500 parts of φ1
A sand mill using mm glass beads was dispersed for 2 hours to prepare a conductive layer coating solution. Aluminum cylinder
(Φ30 mm × 360 mm, wall thickness 1 mm) was dip-coated with the above coating solution, and then dried at 160 ° C. for 25 minutes. The thickness of the conductive layer was 20 μm.

【００３６】次に、中間層塗布工程として、再沈精製し
たＮ−メトキシメチル化ナイロン６を１０００部、６，
１２，６６，６１０共重合ナイロン２５０部をメタノ−
ル５０００部、ブタノ−ル５０００部の混合溶媒に溶解
し、中間層用塗布液を調製した。前記導電層塗布済アル
ミニウムシリンダ−上に上記塗布液を浸漬塗布した後、
９５℃で７分間乾燥した。中間層の膜厚は０．７０μｍ
とした。Next, as an intermediate layer coating step, 1000 parts of N-methoxymethylated nylon 6 reprecipitated and purified, 6,
250 parts of 12,66,610 copolymer nylon are used as methano-
And 5000 parts of butanol were dissolved in a mixed solvent to prepare an intermediate layer coating solution. After dipping and coating the coating liquid on the conductive layer-coated aluminum cylinder,
It was dried at 95 ° C for 7 minutes. The thickness of the intermediate layer is 0.70 μm
And

【００３７】次に、電荷発生層の塗布工程として、下記
構造式のジスアゾ顔料４００部、Next, as a coating step of the charge generation layer, 400 parts of a disazo pigment having the following structural formula,

【化７】 ポリビニルブツラ−ル（ブチラ−ル化率６８％、平均分
子量２４０００）２００部、シクロヘキサノン５０００
部をφ１ｍｍガラスビ−ズを用いたサンドミルで２４時
間分散し、更にテトラヒドロフラン５０００部を加え塗
布液を調製した。更にこの液を遠心分離機（７０００ｒ
ｐｍ、３０分）でビ−ズかす、ごみ等を取り除いた。こ
の塗布液を前記中間層塗布済アルミニウムシリンダ−上
に浸漬塗布し、８５℃で７分間乾燥した。電荷発生層の
膜厚は０．１５μｍとした。[Chemical 7] Polyvinyl butyral (butyralization rate 68%, average molecular weight 24000) 200 parts, cyclohexanone 5000
Parts were dispersed in a sand mill using φ1 mm glass beads for 24 hours, and 5000 parts of tetrahydrofuran was further added to prepare a coating solution. Furthermore, this liquid is centrifuged (7000r
The bead residue, dust, etc. were removed at pm (30 minutes). This coating solution was applied onto the aluminum cylinder coated with the intermediate layer by dip coating, and dried at 85 ° C. for 7 minutes. The thickness of the charge generation layer was 0.15 μm.

【００３８】次に、フッ素系クシ型グラフト重合樹脂の
精製工程として、フッ素系クシ型グラフト重合樹脂（商
品名ＧＦ−３００、東亜合成化学（株）製）８００部
（固形分２５％）を図３に示す構成の装置にて５００ｋ
ｇ／ｃｍ² に加圧し、直径１４０μｍのノズルを通過さ
せた（ノズルの形状は図４の（ａ）で示すタイプを用い
た）。この時のノズル中の溶液の通過速度は２５０ｍ／
ｓｅｃであった。この樹脂溶液を１００ｍｌ／ｍｉｎの
滴下速度で９０００部のメタノ−ル中に滴下し、生成し
た沈殿物を吸引ろ過によりメタノ−ルと分離回収した
後、真空乾燥機により５０℃で２４時間乾燥し、精製フ
ッ素系クシ型グラフト重合樹脂を得た。Next, as a step of refining the fluorine-type comb-type graft-polymerized resin, 800 parts (solid content 25%) of fluorine-type comb-type graft-polymerized resin (trade name GF-300, manufactured by Toagosei Kagaku Co., Ltd.) are illustrated. 500k with the device of the configuration shown in 3
It was pressurized to g / cm ² and passed through a nozzle having a diameter of 140 μm (the nozzle has the shape shown in FIG. 4A). The passing speed of the solution in the nozzle at this time is 250 m /
It was sec. This resin solution was dropped into 9000 parts of methanol at a dropping rate of 100 ml / min, and the produced precipitate was separated and collected from the methanol by suction filtration, and then dried at 50 ° C. for 24 hours by a vacuum dryer. A purified fluorine-type comb-type graft polymerization resin was obtained.

【００３９】次に、四フッ化エチレン樹脂粉末分散液の
調製工程として、四フッ化エチレン樹脂粉末（商品名ル
ブロンＬ−２、ダイキン工業（株）製）１００部、ポリ
カ−ボネ−ト（三菱瓦斯化学（株）製）１００部、前記
の工程において精製されたフッ素系クシ型グラフト重合
樹脂７部、クロロベンゼン５５０部を十分に混合した
後、高圧分散機（商品名ナノマイザ−、（株）ナノマイ
ザ−製）を用いて分散し、四フッ化エチレン樹脂粉末分
散液を調製した。Next, as a process for preparing a tetrafluoroethylene resin powder dispersion, 100 parts of tetrafluoroethylene resin powder (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.), polycarbonate (Mitsubishi) After thoroughly mixing 100 parts of Gas Chemical Co., Ltd., 7 parts of the fluorine-based comb-type graft polymerization resin purified in the above process, and 550 parts of chlorobenzene, a high pressure disperser (trade name: Nanomizer, Nanomizer Co., Ltd.) -Manufactured) was used to prepare a tetrafluoroethylene resin powder dispersion.

【００４０】次に、下記構造式のスチリル化合物１００
０部、Next, a styryl compound 100 having the following structural formula
0 copies,

【化８】 ポリカ−ボネ−ト８００部、四フッ化エチレン樹脂粉末
分散液１５００部をクロロベンゼン５０００部、ジクロ
ロメタン３０００部に溶解混合し、電荷輸送層用塗布液
を調製した。この塗布液を前記電荷発生層塗布済アルミ
ニウムシリンダ−上に浸漬塗布し、１３０℃で５０分間
乾燥した。電荷輸送層の膜厚を２５μｍとした。[Chemical 8] 800 parts of polycarbonate and 1500 parts of a tetrafluoroethylene resin powder dispersion were dissolved and mixed in 5000 parts of chlorobenzene and 3000 parts of dichloromethane to prepare a charge transport layer coating solution. This coating solution was applied by dip coating on the aluminum cylinder on which the charge generation layer had been coated, and dried at 130 ° C. for 50 minutes. The thickness of the charge transport layer was 25 μm.

【００４１】作成した電子写真感光体を３５℃、８０％
の高温高湿下において、電子写真感光体試験機（川口電
気（株）製）を用いて、帯電、露光、強露光のプロセス
を０．５秒サイクルデ１００００回繰り返し、残留電位
（強露光後の表面電位）の変化を測定した。結果を表１
に示す。The electrophotographic photosensitive member thus prepared was heated at 35 ° C. and 80%
Under high temperature and high humidity, using an electrophotographic photoconductor tester (manufactured by Kawaguchi Electric Co., Ltd.), the process of charging, exposure and strong exposure was repeated for 0.5 second cycle de 10000 times to obtain residual potential (after strong exposure). The change in surface potential) was measured. The results are shown in Table 1.
Shown in.

【００４２】この電子写真感光体を帯電、露光、現像、
転写、クリ−ニングのプロセスを０．５秒サイクルで繰
り返す複写機に取り付け、３５℃、８０％の高温高湿下
において１００００枚連続して複写を行った。結果は初
期においても１００００枚目においても画像欠陥のない
高品位の画像が得られた。This electrophotographic photosensitive member is charged, exposed, developed,
It was attached to a copying machine that repeats the process of transfer and cleaning in 0.5 second cycles, and 10000 sheets were continuously copied under high temperature and high humidity of 35 ° C. and 80%. As a result, a high-quality image having no image defect was obtained both in the initial stage and on the 10000th sheet.

【００４３】実施例２ フッ素系クシ型グラフト重合樹脂の精製工程として、フ
ッ素系クシ型グラフト重合樹脂（商品名ＬＦ−４０、綜
研化学（株）製）４００部を図３に示す構成の装置にて
（ノズルの形状は図３の（ｂ）で示すタイプを用いた）
２００ｋｇ／ｃｍ² に加圧し、直径８０μｍのノズルを
通過させた（この時のノズル中の溶液の通過速度は１２
０ｍ／ｓｅｃであった）。この樹脂溶液を５０ｍｌ／ｍ
ｉｎの滴下速度で８０００部のメタノ−ル中に滴下し、
生成した沈殿物を吸引ろ過によりメタノ−ルと分離回収
した後、真空乾燥機により６０℃で２４時間乾燥し、精
製フッ素系クシ型グラフト重合樹脂を得た。Example 2 As a step of refining a fluorine-type comb-type graft-polymerized resin, 400 parts of a fluorine-type comb-type graft-polymerized resin (trade name LF-40, manufactured by Soken Chemical Co., Ltd.) was installed in the apparatus shown in FIG. (The nozzle shape used was the type shown in FIG. 3B)
It was pressurized to 200 kg / cm ² and passed through a nozzle having a diameter of 80 μm (the passing speed of the solution in the nozzle at this time was 12
It was 0 m / sec). 50 ml / m of this resin solution
at a dropping rate of in to 8000 parts of methanol,
The produced precipitate was separated and collected from the methanol by suction filtration, and then dried at 60 ° C. for 24 hours by a vacuum dryer to obtain a purified fluorine-based comb-type graft polymerized resin.

【００４４】次に、四フッ化エチレン樹脂粉末分散液の
調製工程として、四フッ化エチレン樹脂粉末（前出）１
００部、ポリカ−ボネ−ト９０部、前記の工程において
精製されたフッ素系クシ型グラフト重合樹脂１０部、ク
ロロベンゼン５５０部を十分に混合した後、高圧分散機
（前出）を用いて分散し、四フッ化エチレン樹脂粉末分
散液を調製した。Next, as a step of preparing the tetrafluoroethylene resin powder dispersion liquid, tetrafluoroethylene resin powder (described above) 1
After thoroughly mixing 00 parts, 90 parts of polycarbonate, 10 parts of the fluorine-type comb-type graft polymerization resin purified in the above step, and 550 parts of chlorobenzene, the mixture was dispersed using a high pressure disperser (described above). A tetrafluoroethylene resin powder dispersion was prepared.

【００４５】この四フッ化エチレン樹脂粉末分散液を用
い実施例１と全く同様にして電荷輸送層用塗布液を調製
した。この塗布液を実施例１と同様の電荷発生層塗布済
アルミニウムシリンダ−上に浸漬塗布し、１３０℃で４
０分間乾燥した。電荷輸送層の膜厚を２５μｍとした。Using this tetrafluoroethylene resin powder dispersion, a charge transport layer coating solution was prepared in exactly the same manner as in Example 1. This coating solution was applied by dip coating onto an aluminum cylinder on which a charge generation layer had been coated, which was the same as in Example 1.
Dry for 0 minutes. The thickness of the charge transport layer was 25 μm.

【００４６】作成した電子写真感光体を３５℃、８０％
の高温高湿下において、電子写真感光体試験機（前出）
を用いて、帯電、露光、強露光のプロセスを０．５秒サ
イクルで１００００回繰り返し、残留電位の変化を測定
した。結果を表１に示す。The prepared electrophotographic photosensitive member was heated at 35 ° C. and 80%
Electrophotographic photoconductor tester under high temperature and high humidity (above)
The process of charging, exposure, and strong exposure was repeated 10000 times in a cycle of 0.5 seconds, and the change in residual potential was measured. The results are shown in Table 1.

【００４７】この電子写真感光体を帯電、露光、現像、
転写、クリ−ニングのプロセスを０．５秒サイクルで繰
り返す複写機に取り付け、３５℃、８０％の高温高湿下
において１００００枚連続して複写を行った。結果は初
期においても１００００枚目においても画像欠陥のない
高品位の画像が得られた。This electrophotographic photosensitive member is charged, exposed, developed,
It was attached to a copying machine that repeats the process of transfer and cleaning in 0.5 second cycles, and 10000 sheets were continuously copied under high temperature and high humidity of 35 ° C. and 80%. As a result, a high-quality image having no image defect was obtained both in the initial stage and on the 10000th sheet.

【００４８】実施例３ フッ素系クシ型グラフト重合樹脂の精製工程として、フ
ッ素系クシ型グラフト重合樹脂（商品名ＧＦ−１５０、
東亜合成化学（株）製）４００部を１２００ｋｇ／ｃｍ
² に加圧し、直径８０μｍのノズルを通過させた。この
樹脂溶液を８０ｍｌ／ｍｉｎの滴下速度で６０００部の
メタノ−ル中に滴下し、生成した沈殿物を吸引ろ過によ
りメタノ−ルと分離回収した後、真空乾燥機により６０
℃で２４時間乾燥し、精製フッ素系クシ型グラフト重合
樹脂を得た。Example 3 As a step of purifying a fluorine-based comb-type graft polymerized resin, a fluorine-type comb-type graft polymerized resin (trade name: GF-150,
Toagosei Kagaku Co., Ltd.) 400 parts 1200 kg / cm
^It was pressurized to ² and passed through a nozzle having a diameter of 80 μm. This resin solution was dropped into 6000 parts of methanol at a dropping rate of 80 ml / min, and the produced precipitate was separated and recovered from the methanol by suction filtration, and then 60% by a vacuum dryer.
It was dried at ℃ for 24 hours to obtain a purified fluorine-type comb-type graft polymerization resin.

【００４９】次に、ポリ三フッ化塩化エチレン粉末分散
液の調製工程として、ポリ三フッ化塩化エチレン粉末
（商品名ダイフロン、ダイキン工業（株）製）１００
部、ポリカ−ボネ−ト８０部、前記の工程において精製
されたフッ素系クシ型グラフト重合樹脂４部、クロロベ
ンゼン６００部を十分に混合した後、ガラスビ−ズを用
いた分散機（商品名サンドグラインダ−、（株）アイメ
ックス製）を用いて分散し、ポリ三フッ化塩化エチレン
粉末分散液を調製した。Next, as a process for preparing a polytrifluoroethylene chloride powder dispersion liquid, polytrifluoroethylene chloride powder (trade name: Daiflon, manufactured by Daikin Industries, Ltd.) 100
Parts, 80 parts of polycarbonate, 4 parts of the fluorine-type comb-type graft-polymerized resin purified in the above step, and 600 parts of chlorobenzene were thoroughly mixed, and then a dispersing machine using a glass bead (trade name: sand grinder) was used. -, Manufactured by IMEX Co., Ltd., and dispersed to prepare a polytrifluoroethylene chloride powder dispersion.

【００５０】このポリ三フッ化塩化エチレン粉末分散液
を用いた他は実施例１と全く同様にして電荷輸送層用塗
布液を調製した。この塗布液を実施例１と同様の電荷発
生層塗布済アルミニウムシリンダ−上に浸漬塗布し、１
３０℃で６０分間乾燥した。電荷輸送層の膜厚を２５μ
ｍとした。A charge transport layer coating liquid was prepared in exactly the same manner as in Example 1 except that this polytrifluoroethylene chloride powder dispersion was used. This coating solution was applied by dip coating onto a charge generation layer-coated aluminum cylinder similar to that used in Example 1, and 1
It was dried at 30 ° C. for 60 minutes. The thickness of the charge transport layer is 25μ
m.

【００５１】作成した電子写真感光体を３５℃、８０％
の高温高湿下において、電子写真感光体試験機（前出）
を用いて、帯電、露光、強露光のプロセスを０．５秒サ
イクルデ１００００回繰り返し、残留電位の変化を測定
した。結果を表１に示す。The electrophotographic photosensitive member thus prepared was set at 35 ° C. and 80%
Electrophotographic photoconductor tester under high temperature and high humidity (above)
The process of charging, exposure and strong exposure was repeated 0.5 times with a cycle of 10,000 times, and the change in residual potential was measured. The results are shown in Table 1.

【００５２】この電子写真感光体を帯電、露光、現像、
転写、クリ−ニングのプロセスを０．５秒サイクルで繰
り返す複写機に取り付け、３５℃、８０％の高温高湿下
において１００００枚連続して複写を行った。結果は初
期においても１００００枚目においても画像欠陥のない
高品位の画像が得られた。This electrophotographic photosensitive member is charged, exposed, developed,
It was attached to a copying machine that repeats the process of transfer and cleaning in 0.5 second cycles, and 10000 sheets were continuously copied under high temperature and high humidity of 35 ° C. and 80%. As a result, a high-quality image having no image defect was obtained both in the initial stage and on the 10000th sheet.

【００５３】実施例４ ポリフッ化ビニリデン粉末分散液の調製工程として、ポ
リフッ化ビニリデン粉末１００部、ポリカ−ボネ−ト７
０部、実施例１と同様にして精製されたフッ素系クシ型
グラフト重合樹脂９部、クロロベンゼン６００部を十分
に混合した後、ガラスビ−ズを用いた分散機（前出）を
用いて分散し、ポリフッ化ビニリデン粉末分散液を調製
した。Example 4 As a step of preparing a polyvinylidene fluoride powder dispersion, 100 parts of polyvinylidene fluoride powder and polycarbonate 7 were used.
0 parts, 9 parts of a fluorine-type comb-type graft-polymerized resin purified in the same manner as in Example 1, and 600 parts of chlorobenzene were thoroughly mixed, and then dispersed using a disperser (described above) using glass beads. A polyvinylidene fluoride powder dispersion was prepared.

【００５４】このポリフッ化ビニリデン粉末分散液を用
いた他は実施例１と全く同様にして電荷輸送層用塗布液
を調製した。この塗布液を実施例１と同様の電荷発生層
塗布済アルミニウムシリンダ−上に浸漬塗布し、１３０
℃で６０分間乾燥した。電荷輸送層の膜厚を２０μｍと
した。A coating liquid for charge transport layer was prepared in exactly the same manner as in Example 1 except that this polyvinylidene fluoride powder dispersion was used. This coating solution was applied by dip coating onto a charge generation layer-coated aluminum cylinder similar to that used in Example 1 to obtain 130
Dried at 60 ° C. for 60 minutes. The thickness of the charge transport layer was 20 μm.

【００５５】作成した電子写真感光体を３５℃、８０％
の高温高湿下において、電子写真感光体試験機（前出）
を用いて、帯電、露光、強露光のプロセスを０．５秒サ
イクルで１００００回繰り返し、残留電位の変化を測定
した。結果を表１に示す。The prepared electrophotographic photosensitive member was heated at 35 ° C. and 80%
Electrophotographic photoconductor tester under high temperature and high humidity (above)
The process of charging, exposure, and strong exposure was repeated 10000 times in a cycle of 0.5 seconds, and the change in residual potential was measured. The results are shown in Table 1.

【００５６】この電子写真感光体を帯電、露光、現像、
転写、クリ−ニングのプロセスを０．５秒サイクルで繰
り返す複写機に取り付け、３５℃、８０％の高温高湿下
において１００００枚連続して複写を行った。結果は初
期においても１００００枚目においても画像欠陥のない
高品位の画像が得られた。This electrophotographic photosensitive member is charged, exposed, developed,
It was attached to a copying machine that repeats the process of transfer and cleaning in 0.5 second cycles, and 10000 sheets were continuously copied under high temperature and high humidity of 35 ° C. and 80%. As a result, a high-quality image having no image defect was obtained both in the initial stage and on the 10000th sheet.

【００５７】実施例５ 実施例１で用いたと同様のスチリル化合物１２００部、
ポリカ−ボネ−ト１０００部をクロロベンゼン５０００
部、ジクロロメタン３０００部に溶解し、電荷輸送層用
塗布液を調製した。Example 5 1200 parts of a styryl compound similar to that used in Example 1,
Chlorobenzene 5000 was added to 1000 parts of polycarbonate.
Parts and dichloromethane 3000 parts to prepare a charge transport layer coating solution.

【００５８】この塗布液を実施例１と同様の電荷発生層
塗布済アルミニウムシリンダ−上に浸漬塗布、１３０℃
で６０分間乾燥した。電荷輸送層の膜厚を２０μｍとし
た。This coating solution was applied by dip coating on an aluminum cylinder on which a charge generation layer had been coated as in Example 1 at 130 ° C.
And dried for 60 minutes. The thickness of the charge transport layer was 20 μm.

【００５９】次に、四フッ化エチレン樹脂粉末分散液の
調製工程として、実施例１で用いたと同様のスチリル化
合物５０部、四フッ化エチレン樹脂粉末（商品名ルブロ
ンＬ−２、ダイキン工業（株）製）（実施例２と同様の
方法で３回洗浄精製）５０部、ポリカ−ボネ−ト１２０
部、実施例１と同様にして精製されたフッ素系クシ型グ
ラフト重合樹脂４部、クロロベンゼン５００部を十分に
混合した後、ガラスビ−ズを用いたサンドグラインダ−
（前出）を用いて分散し、四フッ化エチレン樹脂粉末分
散液を調製した。この液を前記電荷輸送層を塗布した感
光体ドラム上にスプレ−塗布し、１３０℃で１０分間乾
燥し、保護層を設けた。保護層の膜厚は４μｍとした。Next, as a step of preparing a tetrafluoroethylene resin powder dispersion, 50 parts of the same styryl compound as used in Example 1, tetrafluoroethylene resin powder (trade name: Lubron L-2, Daikin Industries Ltd. )) (Washing and purifying 3 times in the same manner as in Example 2) 50 parts, polycarbonate 120
Parts, 4 parts of a fluorine-type comb-type graft-polymerized resin purified in the same manner as in Example 1, and 500 parts of chlorobenzene were sufficiently mixed, and then a sand grinder using a glass bead was used.
Dispersion was carried out using the above-mentioned method to prepare a tetrafluoroethylene resin powder dispersion liquid. This solution was spray-coated on the photoconductor drum coated with the charge transport layer and dried at 130 ° C. for 10 minutes to form a protective layer. The thickness of the protective layer was 4 μm.

【００６０】この電子写真感光体を帯電、露光、現像、
転写、クリ−ニングのプロセスを０．５秒サイクルで繰
り返す複写機に取り付け、３５℃、８０％の高温高湿下
において１００００枚連続して複写を行った。結果は初
期においても１００００枚目においても画像欠陥のない
高品位の画像が得られた。結果を表１に示す。This electrophotographic photosensitive member is charged, exposed, developed,
It was attached to a copying machine that repeats the process of transfer and cleaning in 0.5 second cycles, and 10000 sheets were continuously copied under high temperature and high humidity of 35 ° C. and 80%. As a result, a high-quality image having no image defect was obtained both in the initial stage and on the 10000th sheet. The results are shown in Table 1.

【００６１】比較例１ 実施例１におけるフッ素系クシ型グラフト重合樹脂を加
圧しノズルを通過させる工程を行わず、再沈精製のみと
したフッ素系クシ型グラフト重合樹脂を用いた他は、実
施例１と全く同様にして電子写真感光体を作成した。Comparative Example 1 In Example 1, except that the step of pressurizing the fluorine-based comb-type graft polymer resin and passing through the nozzle was not performed, and the fluorine-type comb-type graft polymer resin used only for reprecipitation purification was used. An electrophotographic photosensitive member was prepared in exactly the same manner as 1.

【００６２】作成した電子写真感光体を３５℃、８０％
の高温高湿下において、電子写真感光体試験機（前出）
を用いて、帯電、露光、強露光のプロセスを０．５秒サ
イクルで１００００回繰り返し、残留電位の変化を測定
した。結果を表１に示す。The prepared electrophotographic photosensitive member was heated at 35 ° C. and 80%
Electrophotographic photoconductor tester under high temperature and high humidity (above)
The process of charging, exposure, and strong exposure was repeated 10000 times in a cycle of 0.5 seconds, and the change in residual potential was measured. The results are shown in Table 1.

【００６３】この電子写真感光体を帯電、露光、現像、
転写、クリ−ニングのプロセスを０．５秒サイクルで繰
り返す複写機に取り付け、３５℃、８０％の高温高湿下
において１００００枚連続して複写を行った。結果は初
期においては良好な画像が得られたが、１００００枚目
においてはカブリが生じ、良好な画像は得られなかっ
た。残留電位の変化を測定した結果、初期に比べて高く
なっていた。This electrophotographic photosensitive member is charged, exposed, developed,
It was attached to a copying machine that repeats the process of transfer and cleaning in 0.5 second cycles, and 10000 sheets were continuously copied under high temperature and high humidity of 35 ° C. and 80%. As a result, a good image was obtained in the initial stage, but fog occurred on the 10000th sheet, and a good image was not obtained. As a result of measuring the change in residual potential, it was higher than in the initial stage.

【００６４】比較例２ 実施例１におけるフッ素系クシ型グラフト重合樹脂を加
圧しノズルを通過させる工程において加圧する圧力を４
０ｋｇ／ｃｍ² （この時の通過速度は２５ｍ／ｓｅｃで
あった）で処理し再沈精製したフッ素系クシ型グラフト
重合樹脂を用いた他は、実施例１と全く同様にして電子
写真感光体を作成した。Comparative Example 2 The pressure applied in the step of pressing the fluorine-type comb-type graft polymer resin in Example 1 and passing it through the nozzle was 4
An electrophotographic photoconductor was carried out in the same manner as in Example 1 except that the fluorine-type comb-type graft polymerization resin treated with 0 kg / cm ² (passing speed at this time was 25 m / sec) and purified by reprecipitation was used. It was created.

【００６５】作成した電子写真感光体を３５℃、８０％
の高温高湿下において、電子写真感光体試験機（前出）
を用いて、帯電、露光、強露光のプロセスを０．５秒サ
イクルで１００００回繰り返し、残留電位の変化を測定
した。結果を表１に示す。The prepared electrophotographic photosensitive member was heated at 35 ° C. and 80%
Electrophotographic photoconductor tester under high temperature and high humidity (above)
The process of charging, exposure, and strong exposure was repeated 10000 times in a cycle of 0.5 seconds, and the change in residual potential was measured. The results are shown in Table 1.

【００６６】この電子写真感光体を帯電、露光、現像、
転写、クリ−ニングのプロセスを０．５秒サイクルで繰
り返す複写機に取り付け、３５℃、８０％の高温高湿下
において１００００枚連続して複写を行った。結果は初
期においては良好な画像が得られたが、１００００枚目
においてはカブリが生じ、良好な画像は得られなかっ
た。残留電位の変化を測定した結果、初期に比べて高く
なっていた。This electrophotographic photosensitive member is charged, exposed, developed,
It was attached to a copying machine that repeats the process of transfer and cleaning in 0.5 second cycles, and 10000 sheets were continuously copied under high temperature and high humidity of 35 ° C. and 80%. As a result, a good image was obtained in the initial stage, but fog occurred on the 10000th sheet, and a good image was not obtained. As a result of measuring the change in residual potential, it was higher than in the initial stage.

【００６７】比較例３ 実施例２におけるフッ素系クシ型グラフト重合樹脂の精
製工程において加圧しノズルを通過させる工程を行わ
ず、再沈精製のみとしたフッ素系クシ型グラフト重合樹
脂を用いた他は、実施例２と全く同様にして電子写真感
光体を作成した。Comparative Example 3 In the refining step of the fluorine-type comb-type graft polymer resin in Example 2, the step of pressurizing and passing through the nozzle was not carried out, and the fluorine-type comb-type graft polymer resin used only for reprecipitation purification was used. An electrophotographic photosensitive member was prepared in exactly the same manner as in Example 2.

【００６８】作成した電子写真感光体を３５℃、８０％
の高温高湿下において、電子写真感光体試験機（前出）
を用いて、帯電、露光、強露光のプロセスを０．５秒サ
イクルで１００００回繰り返し、残留電位の変化を測定
した。結果を表１に示す。The prepared electrophotographic photosensitive member was heated at 35 ° C. and 80%
Electrophotographic photoconductor tester under high temperature and high humidity (above)
The process of charging, exposure, and strong exposure was repeated 10000 times in a cycle of 0.5 seconds, and the change in residual potential was measured. The results are shown in Table 1.

【００６９】この電子写真感光体を帯電、露光、現像、
転写、クリ−ニングのプロセスを０．５秒サイクルで繰
り返す複写機に取り付け、３５℃、８０％の高温高湿下
において１００００枚連続して複写を行った。結果は初
期においては良好な画像が得られたが、１００００枚目
においてはカブリが生じ、良好な画像は得られなかっ
た。残留電位の変化を測定した結果、初期に比べて高く
なっていた。This electrophotographic photoreceptor is charged, exposed, developed,
It was attached to a copying machine that repeats the process of transfer and cleaning in 0.5 second cycles, and 10000 sheets were continuously copied under high temperature and high humidity of 35 ° C. and 80%. As a result, a good image was obtained in the initial stage, but fog occurred on the 10000th sheet, and a good image was not obtained. As a result of measuring the change in residual potential, it was higher than in the initial stage.

【００７０】比較例４ 実施例３におけるフッ素系クシ型グラフト重合樹脂の精
製工程において加圧しノズルを通過させる工程を行わ
ず、再沈精製のみとしたフッ素系クシ型グラフト重合樹
脂を用いた他は、実施例３と全く同様にして電子写真感
光体を作成した。Comparative Example 4 In the refining step of the fluorine-based comb-type graft-polymerized resin in Example 3, the step of pressurizing and passing through the nozzle was not carried out, and the fluorine-type comb-type graft-polymerized resin used only for reprecipitation purification was used. An electrophotographic photosensitive member was prepared in exactly the same manner as in Example 3.

【００７１】作成した電子写真感光体を３５℃、８０％
の高温高湿下において、電子写真感光体試験機（前出）
を用いて、帯電、露光、強露光のプロセスを０．５秒サ
イクルで１００００回繰り返し、残留電位の変化を測定
した。結果を表１に示す。The prepared electrophotographic photosensitive member was heated at 35 ° C. and 80%
Electrophotographic photoconductor tester under high temperature and high humidity (above)
The process of charging, exposure, and strong exposure was repeated 10000 times in a cycle of 0.5 seconds, and the change in residual potential was measured. The results are shown in Table 1.

【００７２】この電子写真感光体を帯電、露光、現像、
転写、クリ−ニングのプロセスを０．５秒サイクルで繰
り返す複写機に取り付け、３５℃、８０％の高温高湿下
において１００００枚連続して複写を行った。結果は初
期においては良好な画像が得られたが、１００００枚目
においてはカブリが生じ、良好な画像は得られなかっ
た。残留電位の変化を測定した結果、初期に比べて高く
なっていた。This electrophotographic photosensitive member is charged, exposed, developed,
It was attached to a copying machine that repeats the process of transfer and cleaning in 0.5 second cycles, and 10000 sheets were continuously copied under high temperature and high humidity of 35 ° C. and 80%. As a result, a good image was obtained in the initial stage, but fog occurred on the 10000th sheet, and a good image was not obtained. As a result of measuring the change in residual potential, it was higher than in the initial stage.

【００７３】比較例５ 実施例４におけるフッ素系クシ型グラフト重合樹脂の精
製工程において加圧しノズルを通過させる工程２回の再
沈精製のみとしたフッ素系クシ型グラフト重合樹脂を用
いた他は、実施例４と全く同様にして電子写真感光体を
作成した。Comparative Example 5 In the step of purifying the fluorine-type comb-type graft polymer resin in Example 4, the step of applying pressure and passing through a nozzle was used. An electrophotographic photosensitive member was prepared in exactly the same manner as in Example 4.

【００７４】作成した電子写真感光体を３５℃、８０％
の高温高湿下において、電子写真感光体試験機（前出）
を用いて、帯電、露光、強露光のプロセスを０．５秒サ
イクルで１００００回繰り返し、残留電位の変化を測定
した。結果を表１に示す。The prepared electrophotographic photosensitive member was heated at 35 ° C. and 80%
Electrophotographic photoconductor tester under high temperature and high humidity (above)
The process of charging, exposure, and strong exposure was repeated 10000 times in a cycle of 0.5 seconds, and the change in residual potential was measured. The results are shown in Table 1.

【００７５】この電子写真感光体を帯電、露光、現像、
転写、クリ−ニングのプロセスを０．５秒サイクルで繰
り返す複写機に取り付け、３５℃、８０％の高温高湿下
において１００００枚連続して複写を行った。結果は初
期においては良好な画像が得られたが、１００００枚目
においてはカブリが生じ、良好な画像は得られなかっ
た。残留電位の変化を測定した結果、初期に比べて高く
なっていた。This electrophotographic photosensitive member is charged, exposed, developed,
It was attached to a copying machine that repeats the process of transfer and cleaning in 0.5 second cycles, and 10000 sheets were continuously copied under high temperature and high humidity of 35 ° C. and 80%. As a result, a good image was obtained in the initial stage, but fog occurred on the 10000th sheet, and a good image was not obtained. As a result of measuring the change in residual potential, it was higher than in the initial stage.

【００７６】比較例６ 実施例５におけるフッ素系クシ型グラフト重合樹脂の精
製工程において加圧しノズルを通過させることなく、再
沈精製のみとしたフッ素系クシ型グラフト重合樹脂を用
いた他は、実施例５と全く同様にして電子写真感光体を
作成した。Comparative Example 6 Implementation was carried out in the same manner as in Example 5, except that the fluorine-type comb-type graft polymer resin used in the purification step of the fluorine-type comb-type graft polymer resin was pressurized and passed through the nozzle without re-precipitation purification. An electrophotographic photosensitive member was prepared in exactly the same manner as in Example 5.

【００７７】作成した電子写真感光体を３５℃、８０％
の高温高湿下において、電子写真感光体試験機（前出）
を用いて、帯電、露光、強露光のプロセスを０．５秒サ
イクルで１００００回繰り返し、残留電位の変化を測定
した。結果を表１に示す。The prepared electrophotographic photosensitive member was heated at 35 ° C. and 80%
Electrophotographic photoconductor tester under high temperature and high humidity (above)
The process of charging, exposure, and strong exposure was repeated 10000 times in a cycle of 0.5 seconds, and the change in residual potential was measured. The results are shown in Table 1.

【００７８】この電子写真感光体を帯電、露光、現像、
転写、クリ−ニングのプロセスを０．５秒サイクルで繰
り返す複写機に取り付け、３５℃、８０％の高温高湿下
において１００００枚連続して複写を行った。結果は初
期においては良好な画像が得られたが、１００００枚目
においてはカブリが生じ、良好な画像は得られなかっ
た。残留電位の変化を測定した結果、初期に比べて高く
なっていた。This electrophotographic photosensitive member is charged, exposed, developed,
It was attached to a copying machine that repeats the process of transfer and cleaning in 0.5 second cycles, and 10000 sheets were continuously copied under high temperature and high humidity of 35 ° C. and 80%. As a result, a good image was obtained in the initial stage, but fog occurred on the 10000th sheet, and a good image was not obtained. As a result of measuring the change in residual potential, it was higher than in the initial stage.

【００７９】[0079]

【表１】 [Table 1]

【００８０】実施例１と比較例１、実施例２と比較例
３、実施例３と比較例４、実施例４と比較例５、実施例
５と比較例６を比較すると、表面層にフッ素系樹脂粒子
及び加圧し狭いノズルを通過させた後、再沈精製したフ
ッ素系クシ型グラフト重合樹脂を含有させた電子写真感
光体は、繰り返しの帯電、露光による残留電位の上昇が
少なく、帯電、露光、現像、転写、クリ−ニングのプロ
セスの繰り返しに対しても電位が安定しているばかりで
なく、初期においても１００００枚目においても画像欠
陥のない高品位の画像が得られた。一方、単なる再沈精
製のもの、加圧処理が不十分なもの（比較例２）は繰り
返しの使用に対して残留電位の上昇が見られる画像カブ
リが発生した。Comparison of Example 1 with Comparative Example 1, Example 2 with Comparative Example 3, Example 3 with Comparative Example 4, Example 4 with Comparative Example 5, and Example 5 with Comparative Example 6 revealed that fluorine was added to the surface layer. After passing through a system resin particles and a narrow nozzle under pressure, the electrophotographic photoreceptor containing the reprecipitated and refined fluorine-based comb-type graft polymerization resin, repeated charging, little increase in residual potential due to exposure, charging, The potential was not only stable against repeated exposure, development, transfer, and cleaning processes, but high-quality images free of image defects were obtained both in the initial stage and on the 10,000th sheet. On the other hand, in the case of simple reprecipitation purification and the case of insufficient pressure treatment (Comparative Example 2), image fog in which the residual potential increased with repeated use was observed.

【００８１】[0081]

【発明の効果】本発明の電子写真感光体は、摩擦による
表面の摩耗や傷に対して耐久性を有し、また、高湿環境
においても安定した高品位の画像を形成するという顕著
な効果を奏する。EFFECT OF THE INVENTION The electrophotographic photoreceptor of the present invention has durability against abrasion and scratch on the surface due to friction, and has a remarkable effect of forming a stable and high-quality image even in a high humidity environment. Play.

【図面の簡単な説明】[Brief description of drawings]

【図１】本発明の電子写真感光体を用いた電子写真画像
形成装置の概略構成図である。FIG. 1 is a schematic configuration diagram of an electrophotographic image forming apparatus using an electrophotographic photosensitive member of the present invention.

【図２】本発明のフッ素系クシ型グラフト重合樹脂溶液
を加圧し狭いノズルを通過させる装置の概略構成図であ
る。FIG. 2 is a schematic configuration diagram of an apparatus for pressurizing the fluorine-based comb-type graft polymerization resin solution of the present invention and passing it through a narrow nozzle.

【図３】本発明のフッ素系クシ型グラフト重合樹脂溶液
を加圧し通過させるノズルの概略構成図（断面図）であ
る。 （ａ）クランク型 （ｂ）分岐衝突型FIG. 3 is a schematic configuration diagram (cross-sectional view) of a nozzle that pressurizes and passes the fluorine-based comb-type graft polymerization resin solution of the present invention. (A) Crank type (b) Branch collision type

【符号の説明】[Explanation of symbols]

１ 像担持体としてのドラム型感光体（本発明の電子
写真感光体） １ａ 軸 ２ コロナ帯電装置 ３ 露光部 ４ 現像手段 ５ 転写手段 ６ クリ−ニング手段 ７ 前露光手段 ８ 像定着手段 ９ 転写用紙 Ｌ 光像露光 １０ 樹脂溶液タンク（処理前） １１ ポンプ １２ ノズル １３ 樹脂溶液タンク（処理後） １４ 溶液導入口 １５ 溶液排出口DESCRIPTION OF SYMBOLS 1 Drum type photoconductor as an image carrier (electrophotographic photoconductor of the present invention) 1a axis 2 Corona charging device 3 Exposure section 4 Developing means 5 Transfer means 6 Cleaning means 7 Pre-exposure means 8 Image fixing means 9 Transfer paper L light image exposure 10 resin solution tank (before processing) 11 pump 12 nozzle 13 resin solution tank (after processing) 14 solution inlet 15 solution outlet

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】 表面層にフッ素系樹脂粒子及びフッ素系
クシ型グラフト重合樹脂を含有する電子写真感光体にお
いて、該表面層に高圧で狭いノズルを通過させた後再沈
精製されたフッ素系クシ型グラフト重合樹脂を含有する
ことを特徴とする電子写真感光体。1. An electrophotographic photosensitive member having a surface layer containing fluorine-based resin particles and a fluorine-type comb-type graft-polymerized resin, which is refined by reprecipitation after passing through a narrow nozzle at a high pressure on the surface layer. An electrophotographic photoreceptor comprising a type graft polymerization resin. 【請求項２】 請求項１記載の電子写真感光体におい
て、表面層に含有する高圧で狭いノズルを通過させた後
再沈精製されたフッ素系クシ型グラフト重合樹脂がアク
リル酸エステル類、メタクリル酸エステル、スチレン化
合物より選ばれたマクロモノマ−及びパ−フルオロアル
キルエチルメタクリレ−トよりグラフト重合された樹脂
からなる請求項１記載の電子写真感光体。2. The electrophotographic photosensitive member according to claim 1, wherein the fluorine-type comb-type graft polymerization resin contained in the surface layer and purified by re-precipitation after passing through a narrow nozzle at high pressure is acrylic acid ester or methacrylic acid. The electrophotographic photosensitive member according to claim 1, which comprises a resin graft-polymerized from a macromonomer selected from an ester and a styrene compound and perfluoroalkylethyl methacrylate. 【請求項３】 請求項１記載の電子写真感光体におい
て、表面層に含有するフッ素系樹脂粒子が四フッ化エチ
レン樹脂、三フッ化塩化エチレン樹脂、六フッ化エチレ
ンプロピレン樹脂、フッ化ビニル樹脂、フッ化ビニリデ
ン樹脂、二フッ化二塩化エチレン樹脂及びこれら共重合
体から選ばれる樹脂からなる請求項１記載の電子写真感
光体。3. The electrophotographic photosensitive member according to claim 1, wherein the fluororesin particles contained in the surface layer are tetrafluoroethylene resin, trifluorochloroethylene resin, hexafluoroethylenepropylene resin, vinyl fluoride resin. The electrophotographic photosensitive member according to claim 1, which comprises a resin selected from the group consisting of, vinylidene fluoride resin, ethylene difluoride dichloride resin and copolymers thereof. 【請求項４】 請求項１記載の電子写真感光体を備えた
電子写真装置 【０００１】4. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1.