JP5079397B2 - Electrophotographic photosensitive member, image forming method, image forming apparatus, and process cartridge for image forming apparatus - Google Patents

Description

  The present invention relates to an electrophotographic photosensitive member having high durability and high image quality over a long period of time by using a photosensitive layer having high wear resistance and good electrical characteristics. The present invention also relates to an image forming method, an image forming apparatus, and a process cartridge for the image forming apparatus using the long-life, high-performance photoconductor.

  In recent years, organic photoreceptors (OPC) have been widely used in copying machines, facsimile machines, laser printers, and composite machines in place of inorganic photoreceptors because of their good performance and various advantages. This is because, for example, (1) optical characteristics such as the light absorption wavelength range and the amount of absorption, (2) electrical characteristics such as high sensitivity and stable charging characteristics, and (3) material selection range (4) Ease of manufacturing, (5) Low cost, (6) Non-toxicity, and the like.

On the other hand, the diameter of the photoconductor has recently been reduced due to the downsizing of the image forming apparatus, and the high speed of the machine and the maintenance-free movement have been added to increase the durability of the photoconductor. From this point of view, organophotoreceptors are generally soft because the surface layer is mainly composed of low-molecular charge transport materials and inert polymers, and when used repeatedly in electrophotographic processes, they are mechanically driven by development systems and cleaning systems. There is a drawback that wear is likely to occur due to a typical load. In addition, due to the demand for higher image quality, the cleaning blade has to be increased in hardness and contact pressure with the aim of improving the cleaning properties as the particle size of the toner particles is reduced. This also promotes the wear of the photoreceptor. Is a factor. Such wear of the photoreceptor deteriorates electrical characteristics such as sensitivity deterioration and chargeability, and causes abnormal images such as image density reduction and background stains. Further, scratches where wear is locally generated cause streak-like stain images due to poor cleaning. Under the present circumstances, the wear and scratches are rate-determined and the life of the photoconductor has been replaced.
Therefore, it is indispensable to reduce the above-mentioned wear amount in order to increase the durability of the organic photoreceptor, and this is the most pressing issue in this field.
This is the most pressing issue in the field.

Techniques for improving the abrasion resistance of the photosensitive layer include (1) using a curable binder for the surface layer (see, for example, Patent Document 1), and (2) using a polymeric charge transport material ( For example, refer patent document 2), (3) what dispersed the inorganic filler in the surface layer (for example, refer patent document 3), etc. are mentioned. Among these technologies, those using the curable binder (1) have poor compatibility with the charge transport material, and the residual potential increases due to impurities such as polymerization initiators and unreacted residues, resulting in decreased image density. Tends to occur. In addition, although the polymer charge transport material (2) can improve the abrasion resistance to some extent, the durability required for the organic photoreceptor is not fully satisfied. Not reached. In addition, polymer charge transport materials are difficult to polymerize and purify, and it is difficult to obtain a high-purity material. Therefore, it is difficult to stabilize electrical characteristics between materials. Furthermore, production problems such as high viscosity of the coating solution may occur. The dispersion of the inorganic filler (3) exhibits higher wear resistance than a photoconductor in which a normal low molecular charge transport material is dispersed in an inert polymer, but traps present on the surface of the inorganic filler. As a result, the residual potential rises and the image density tends to decrease. In addition, when the unevenness of the inorganic filler and the binder resin on the surface of the photoconductor is large, defective cleaning may occur, which may cause toner filming and image flow. These technologies (1), (2), and (3) are sufficient to satisfy the overall durability including the electrical durability and mechanical durability required for the organic photoreceptor. Has not reached.
Furthermore, a photoreceptor containing a polyfunctional acrylate monomer cured product in order to improve the abrasion resistance and scratch resistance of (1) is also known (see Patent Document 4). However, in this photoreceptor, although there is a description that the polyfunctional acrylate monomer cured product is contained in the protective layer provided on the photosensitive layer, the protective layer may contain a charge transport material. However, when the surface layer contains a low-molecular charge transport material, there is a problem of compatibility with the cured product. In some cases, the molecular charge transport material is precipitated and the cloudiness phenomenon occurs, and the mechanical strength is also lowered.
Furthermore, since this photoconductor specifically reacts with a monomer in a state containing a polymer binder, curing does not proceed sufficiently, and there is a problem of compatibility between the cured product and the binder resin. There was a tendency for surface irregularities due to phase separation to cause poor cleaning.

As a wear resistance technology for a photosensitive layer that replaces these, a charge transport layer formed by using a coating liquid comprising a monomer having a carbon-carbon double bond, a charge transport material having a carbon-carbon double bond, and a binder resin. The binder resin has a carbon-carbon double bond and is reactive with the charge transfer agent, and the double resin is known to be provided. Those having no bond and no reactivity are included. This photoconductor is remarkably compatible with wear resistance and good electrical properties, but when a non-reactive binder resin is used, the binder resin, the monomer and the charge transport agent are used. The compatibility with the cured product produced by this reaction was poor, and surface irregularities were generated during cross-linking from layer separation, and a tendency to cause poor cleaning was observed. In addition, as described above, in this case, the binder resin prevents the curing of the monomer, and what is specifically described as the monomer used in the photoreceptor is a bifunctional one. The monomer has a small number of functional groups and a sufficient crosslinking density cannot be obtained, and these points have not yet been satisfactory in terms of wear resistance. In addition, even when a reactive binder is used, it is difficult to achieve both the binding amount and the crosslinking density of the charge transport material due to the low number of functional groups contained in the monomer and the binder resin, and the electrical characteristics. In addition, the wear resistance was not sufficient.
A photosensitive layer containing a compound obtained by curing a hole transporting compound having two or more chain polymerizable functional groups in the same molecule is also known (for example, see Patent Document 6).

JP 56-48637 A JP-A 64-1728 JP-A-4-281461 Japanese Patent No. 3262488 Japanese Patent No. 3194392 JP 2000-66425 A

  The object of the present invention is high wear resistance, high scratch resistance and good electrical characteristics, and particularly excellent smoothness of the film by uniform curing over the entire cross-linked surface layer, and a clear cross-linked surface By forming a photosensitive layer, an electrophotographic photosensitive member having good cleaning characteristics, high durability, and high image quality over a long period of time is provided. Another object of the present invention is to provide an image forming method, an image forming apparatus, and a process cartridge for an image forming apparatus using a high-performance photoconductor.

The above-mentioned problem is (1) “the uppermost layer of the present invention is a layer containing a charge transport material substituted with a vinyl group and a polycarbonate having a cyclohexyl group linked to the main chain, An electrophotographic photoreceptor, wherein the electrophotographic photoreceptor is a charge transport material substituted with a vinyl group represented by the following general formula 1, wherein the polycarbonate is a polycarbonate represented by the following general formula 2 :

ここでＡｒ^１は置換、もしくは無置換のアリール基を示し、ｈ、ｉは０〜２の数であり、両者同一に０はない。Ｒ^１、Ｒ^２は水素、分岐、もしくは直鎖のアルキル基、アリル基、ハロゲン、置換、もしくは無置換のアリール基を示し、ｍ、ｌは１〜２の整数、ｎは１５〜１０００で表される。」、
（２）「最上層が、ビニル基が置換された電荷輸送材と、主鎖にシクロヘキシル基が連結されたポリカーボネートとを含有させた層であり、前記電荷輸送材は、下記一般式３で示されるビニル基が置換された電荷輸送材であり、前記ポリカーボネートは下記一般式２で示されるポリカーボネートであることを特徴とする電子写真感光体；

Here, Ar ¹ represents a substituted or unsubstituted aryl group, h and i are numbers from 0 to 2, and 0 is not the same in both cases. R ¹ and R ² represent hydrogen, a branched or straight chain alkyl group, an allyl group, a halogen, a substituted or unsubstituted aryl group, m and l are integers of 1 to 2, and n is 15 to 1000. Is done. "
( 2 ) “The uppermost layer is a layer containing a charge transport material substituted with a vinyl group and a polycarbonate having a main chain connected to a cyclohexyl group, and the charge transport material is represented by the following general formula 3. An electrophotographic photosensitive member, wherein the polycarbonate is a polycarbonate represented by the following general formula 2 ;

Ａｒ^２、Ａｒ^３は置換、無置換のアリール基を表わし、Ｒ^１、Ｒ^２は水素、分岐、もしくは直鎖のアルキル基、アリル基、ハロゲン、置換、もしくは無置換のアリール基を示し、ａ、ｍ、ｌは１〜２の整数、ｎは１５〜１０００で表される。Ｘは単結合、−Ｏ−、−ＣＯ−、下記一般式４で示され、Ｒ^３は水素、炭素数１〜５のアルキル基、置換、無置換のアリール基を表わす。

Ar ² and Ar ³ represent a substituted or unsubstituted aryl group, and R ¹ and R ² represent a hydrogen, branched or straight chain alkyl group, an allyl group, a halogen, a substituted or unsubstituted aryl group, and a , M, l are integers of 1-2, and n is 15-1000. X represents a single bond, —O—, —CO—, represented by the following general formula 4, and R ³ represents hydrogen, an alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group.

」、
（３）「最上層が、ビニル基が置換された電荷輸送材と、主鎖にシクロヘキシル基が連結されたポリカーボネートとを含有させた層であり、前記電荷輸送材は、下記一般式５で示されるビニル基が置換された電荷輸送材であり、前記ポリカーボネートは下記一般式２で示されるポリカーボネートであることを特徴とする電子写真感光体；

"
( 3 ) "The uppermost layer is a layer containing a charge transporting material substituted with a vinyl group and a polycarbonate having a main chain linked to a cyclohexyl group. The charge transporting material is represented by the following general formula 5. An electrophotographic photosensitive member, wherein the polycarbonate is a polycarbonate represented by the following general formula 2 ;

Ａｒ^４は置換、無置換のアリール基を表わし、Ｒ^１、Ｒ^２は水素、分岐、もしくは直鎖のアルキル基、アリル基、ハロゲン、置換、もしくは無置換のアリール基を示し、ｂ、ｃ、ｍ、ｌは１〜２の整数、ｎは１５〜１０００で表される。Ｙ、Ｚは単結合、−Ｏ−、−ＣＯ−、下記一般式４で示され、Ｒ^３は水素、炭素数１〜５のアルキル基、置換、無置換のアリール基を表わす。

Ar ⁴ represents a substituted or unsubstituted aryl group, R ¹ and R ² represent a hydrogen, branched or straight chain alkyl group, an allyl group, a halogen, a substituted or an unsubstituted aryl group, b, c, m and l are integers of 1 to 2, and n is represented by 15 to 1000. Y and Z are a single bond, —O—, —CO—, represented by the following general formula 4, and R ³ represents hydrogen, an alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group.

」、
（４）「最上層が、ビニル基が置換された電荷輸送材と、主鎖にシクロヘキシル基が連結されたポリカーボネートとを含有させた層であり、前記電荷輸送材は、下記一般式６で示されるビニル基が置換された電荷輸送材であり、前記ポリカーボネートは下記一般式２で示されるポリカーボネートであることを特徴とする電子写真感光体；

"
( 4 ) "The uppermost layer is a layer containing a charge transport material substituted with a vinyl group and a polycarbonate having a main chain linked to a cyclohexyl group. The charge transport material is represented by the following general formula 6. An electrophotographic photosensitive member, wherein the polycarbonate is a polycarbonate represented by the following general formula 2 ;

Ａｒ^５、Ａｒ^６は置換、無置換のアリール基を表わし、Ｒ^１、Ｒ^２は水素、分岐、もしくは直鎖のアルキル基、アリル基、ハロゲン、置換、もしくは無置換のアリール基を示し、ｄ、ｅ、ｍ、ｌは１〜２の整数を表わし、ｎは１５〜１０００で表される。」、
（５）「少なくとも、帯電手段、画像露光手段、現像手段、転写手段および電子写真感光体を具備した画像形成装置において、該電子写真感光体が前記第（１）項乃至第（４）項の何れかに記載のものであることを特徴とする画像形成装置」、
（６）「前記第（１）項乃至第（４）項のいずれかに記載の電子写真感光体と、帯電手段、現像手段、クリーニング手段より選ばれる少なくとも１つの手段とを一体的に支持し、画像形成装置本体に着脱自在であることを特徴とする画像形成装置用プロセスカートリッジ」により達成させる。

Ar ⁵ and Ar ⁶ represent a substituted or unsubstituted aryl group, R ¹ and R ² represent hydrogen, a branched or straight chain alkyl group, an allyl group, a halogen, a substituted or unsubstituted aryl group, and d , E, m, and l represent an integer of 1 to 2, and n is represented by 15 to 1000. "
( 5 ) “In an image forming apparatus comprising at least a charging unit, an image exposing unit, a developing unit, a transferring unit, and an electrophotographic photosensitive member, the electrophotographic photosensitive member according to the above items (1) to ( 4 )”. An image forming apparatus characterized in that the image forming apparatus is described in any one of "
( 6 ) "The electrophotographic photosensitive member according to any one of (1) to ( 4 ), and at least one unit selected from a charging unit, a developing unit, and a cleaning unit are integrally supported. And an image forming apparatus process cartridge characterized by being detachable from the main body of the image forming apparatus.

  As will be apparent from the following detailed and specific invention, according to the present invention, the wear resistance is high, the scratch resistance is high, and the electrical characteristics are good. An electrophotographic photosensitive member that has excellent smoothness of the film, a clear crosslinked surface layer photosensitive layer, good cleaning characteristics, high durability, and high image quality over a long period of time. In addition, the image forming method, the image forming apparatus, and the process cartridge for the image forming apparatus can be provided.

As a result of intensive investigations, the inventors of the present invention formed a film having high mechanical strength by subjecting at least the surface layer of the photosensitive layer to a thermal crosslinking reaction between a vinyl-substituted charge transport material and a polycarbonate having a cyclohexyl group linked to the main chain. I found out. Although details of this are not yet understood, it is thought that it reacts with the vinyl group and the 4-position of the cyclohexyl ring to crosslink between the polycarbonates. Film after the reaction becomes solvent-insoluble, ^{1600 cm} -1 derived from the absorption of 1770 cm ^-1 derived from polycarbonate Looking After washing the film infrared absorption spectrum in THF is coating solvent, and the charge transport material, 1500 cm Absorption in the vicinity of ^-1 was confirmed and reacted. FIG. 7 shows the IR spectrum of the formed THF-insoluble CTL film together with the IR spectrum of Z-polyca used in the coating solution and the IR spectrum of No. 16 charge-transporting aromatic triamine compound. Z polycarbonate is weak absorption of 1600 cm ^-1 based on the stretching vibration of aromatic rings, and also the absorption of 1500 cm ^-1 is absorption and different in CTM. As a matter of course, absorption based on carbonyl at 1770 cm ⁻¹ is not observed in vinyl CTM, and Z-polyca and vinyl CTM react to form a crosslinked film. However, not all are reacting due to elution.

  The vinyl-substituted charge transport material of the present invention contains a compound represented by the following general formula 1 and a polycarbonate represented by the following general formula 2. As the vinyl-substituted charge transport material, an aldehyde was introduced by Vilsmeier reaction, and then a vinyl group was synthesized with a phosphonium salt.

ここでＡｒ^１は置換、もしくは無置換のアリル基を示し、ｈ、ｉは０〜２の数であり、両者同一に０はない。Ｒ^１、Ｒ^２は水素、分岐、もしくは直鎖のアルキル基、アリル基、ハロゲン、置換、もしくは無置換のアリール基を示し、ｍ、ｌは１〜２の整数、ｎは１５〜１０００で表される。
アリール基の具体例として、非縮合炭素環式基、縮合多環式炭化水素基、及び複素環基が挙げられる。
該縮合多環式炭化水素基としては、好ましくは環を形成する炭素数が１８個以下のもの例えば、ペンタニル基、インデニル基、ナフチル基、アズレニル基、ヘプタレニル基、ビフェニレニル基、as-インダセニル基、s-インダセニル基、フルオレニル基、アセナフチレニル基、プレイアデニル基、アセナフテニル基、フェナレニル基、フェナントリル基、アントリル基、フルオランテニル基、アセフェナントリレニル基、アセアントリレニル基、トリフェニレル基、ピレニル基、クリセニル基、及びナフタセニル基等が挙げられる。
また、該非縮合炭素環式基としてはベンゼン、ジフェニルエーテル、ポリエチレンジフェニルエーテル、ジフェニルチオエーテル及びジフェニルスルホン等の単環式炭化水素化合物の１価基、あるいはビフェニル、ポリフェニル、ジフェニルアルカン、ジフェニルアルケン、ジフェニルアルキン、トリフェニルメタン、ジスチリルベンゼン、１，１−ジフェニルシクロアルカン、ポリフェニルアルカン、及びポリフェニルアルケン等の非縮合多環式炭化水素化合物の１価基、あるいは９，９−ジフェニルフルオレン等の環集合炭化水素化合物の１価基が挙げられる。
更にまた、複素環基である場合、具体例としてカルバゾール、ジベンゾフラン、ジベンゾチオフェン、オキサジアゾール、及びチアジアゾール等の１価基が挙げられる。

Here, Ar ¹ represents a substituted or unsubstituted allyl group, h and i are numbers from 0 to 2, and 0 is not the same in both cases. R ¹ and R ² represent hydrogen, a branched or straight chain alkyl group, an allyl group, a halogen, a substituted or unsubstituted aryl group, m and l are integers of 1 to 2, and n is 15 to 1000. Is done.
Specific examples of the aryl group include a non-condensed carbocyclic group, a condensed polycyclic hydrocarbon group, and a heterocyclic group.
The condensed polycyclic hydrocarbon group preferably has a ring having 18 or less carbon atoms, for example, a pentanyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptaenyl group, a biphenylenyl group, an as-indacenyl group, s-indacenyl group, fluorenyl group, acenaphthylenyl group, pleyadenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, triphenylyl group, pyrenyl group, Examples include a chrycenyl group and a naphthacenyl group.
Examples of the non-condensed carbocyclic group include monovalent groups of monocyclic hydrocarbon compounds such as benzene, diphenyl ether, polyethylene diphenyl ether, diphenyl thioether and diphenyl sulfone, or biphenyl, polyphenyl, diphenylalkane, diphenylalkene, diphenylalkyne, Monovalent groups of non-condensed polycyclic hydrocarbon compounds such as triphenylmethane, distyrylbenzene, 1,1-diphenylcycloalkane, polyphenylalkane, and polyphenylalkene, or ring assemblies such as 9,9-diphenylfluorene And monovalent groups of hydrocarbon compounds.
Furthermore, when it is a heterocyclic group, specific examples include monovalent groups such as carbazole, dibenzofuran, dibenzothiophene, oxadiazole, and thiadiazole.

The aryl group represented by Ar ¹ may have a substituent shown below.
(1) a halogen atom, a cyano group, a nitro group (2) an alkyl group, preferably a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and these alkyl groups Further, a phenyl group substituted with a fluorine atom, a hydroxyl group, a cyano group, an alkoxy group having 1 to 4 carbon atoms, a phenyl group or a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms It may contain. Specifically, methyl group, ethyl group, n-butyl group, i-propyl group, t-butyl group, s-butyl group, n-propyl group, trifluoromethyl group, allyl group, 2-hydroxyethyl group, 2 -Ethoxyethyl group, 2-cyanoethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-phenylbenzyl group and the like can be mentioned.
(3) Alkoxy group (—OR ¹⁰ ): R ¹⁰ represents an alkyl group defined in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, benzyloxy group And a trifluoromethoxy group.
(4) Aryloxy group: Examples of the aryl group include a phenyl group and a naphthyl group. This may contain a C1-C4 alkoxy group, a C1-C4 alkyl group, or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methoxyphenoxy group, and a 4-methylphenoxy group.
(5) Alkyl mercapto group or aryl mercapto group: Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(6)

式中、Ｒ^１５及びＲ^１６は各々独立に水素原子、（２）で定義したアルキル基、またはアリール基を表し、アリール基としては、例えばフェニル基、ビフェニル基又はナフチル基が挙げられ、これらは炭素数１〜４のアルコキシ基、炭素数１〜４のアルキル基またはハロゲン原子を置換基として含有してもよい。Ｒ^１５及びＲ^１６は共同で環を形成してもよい）
具体的には、アミノ基、ジエチルアミノ基、Ｎ−メチル−Ｎ−フェニルアミノ基、Ｎ，Ｎ−ジフェニルアミノ基、Ｎ，Ｎ−ジ（トリール）アミノ基、ジベンジルアミノ基、ピペリジノ基、モルホリノ基、ピロリジノ基等が挙げられる。
（７） メチレンジオキシ基、又はメチレンジチオ基等のアルキレンジオキシ基又はアルキレンジチオ基、等が挙げられる。
（８） 置換又は無置換のスチリル基、置換無置換のβ−フェニルスチリル基、ジフェニルアミノフェニル基、ジトリルアミノフェニル基等が挙げられる。
以下、具体例として

In the formula, each of R ¹⁵ and R ¹⁶ independently represents a hydrogen atom, an alkyl group defined in (2), or an aryl group, and examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group. You may contain a C1-C4 alkoxy group, a C1-C4 alkyl group, or a halogen atom as a substituent. R ¹⁵ and R ¹⁶ may form a ring together)
Specifically, amino group, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (tolyl) amino group, dibenzylamino group, piperidino group, morpholino group And pyrrolidino group.
(7) An alkylenedioxy group such as a methylenedioxy group or a methylenedithio group, or an alkylenedithio group.
(8) Substituted or unsubstituted styryl groups, substituted and unsubstituted β-phenylstyryl groups, diphenylaminophenyl groups, ditolylaminophenyl groups, and the like.
Below as a specific example

ポリカーボネートの具体例としては

Specific examples of polycarbonate include

Ｒ^１、Ｒ^２は水素、分岐、もしくは直鎖のアルキル基、アリル基、ハロゲン、置換、もしくは無置換のアリール基を示し、ｍ、ｌは１〜２の整数、ｎは１５〜１０００で表される。

R ¹ and R ² represent hydrogen, a branched or straight chain alkyl group, an allyl group, a halogen, a substituted or unsubstituted aryl group, m and l are integers of 1 to 2, and n is 15 to 1000. Is done.

The alkyl group is the same as described above, and the molecular weight is 3000 to 500,000 in terms of polystyrene (MPC), preferably 5000 to 300,000.
As a specific example

  Polyca is synthesized according to the above scheme. Bisphenol is synthesized by reacting cyclohexanone and a phenol compound with hydrochloric acid gas, and it is obtained by interfacial polymerization by adding triphosgene in an aqueous sodium hydroxide solution and dichloromethane. It is also commercially available. For example, PC1 is commercially available from Teijin Chemicals.

  An electrophotographic photosensitive member containing a charge transport material substituted with a vinyl group represented by the following general formula 3 and a polycarbonate represented by the following general formula 2

Ａｒ^２、Ａｒ^３は置換、無置換のアリール基を表わし、Ｒ^１、Ｒ^２は水素、分岐、もしくは直鎖のアルキル基、アリル基、ハロゲン、置換、もしくは無置換のアリール基を示し、ａ、ｍ、ｌは１〜２の整数、ｎは１５〜１０００で表される。Ｘは単結合、−Ｏ−、−ＣＯ−、下記一般式４で示され、Ｒ^３は水素、炭素数１〜５のアルキル基、置換、無置換のアリール基を表わす。

Ar ² and Ar ³ represent a substituted or unsubstituted aryl group, and R ¹ and R ² represent a hydrogen, branched or straight chain alkyl group, an allyl group, a halogen, a substituted or unsubstituted aryl group, and a , M, l are integers of 1-2, and n is 15-1000. X represents a single bond, —O—, —CO—, represented by the following general formula 4, and R ³ represents hydrogen, an alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group.

上記アリール基、アルキル基は前述したものと同様である。
これらビニル基をもつ電荷輸送材は一般的に下記スキームで合成される。

The aryl group and alkyl group are the same as described above.
These charge transport materials having a vinyl group are generally synthesized by the following scheme.

  An electrophotographic photosensitive member containing a charge transport material substituted with a vinyl group represented by the following general formula 5 and a polycarbonate represented by the following general formula 2

Ａｒ^４は置換、無置換のアリール基を表わし、Ｒ^１、Ｒ^２は水素、分岐、もしくは直鎖のアルキル基、アリル基、ハロゲン、置換、もしくは無置換のアリール基を示し、ｂ、ｃ、ｍ、ｌは１〜２の整数、ｎは１５〜１０００で表される。Ｙ、Ｚは単結合、−Ｏ−、−ＣＯ−、下記一般式４で示され、Ｒ^３は水素、炭素数１〜５のアルキル基、置換、無置換のアリール基を表わす。

Ar ⁴ represents a substituted or unsubstituted aryl group, R ¹ and R ² represent a hydrogen, branched or straight chain alkyl group, an allyl group, a halogen, a substituted or an unsubstituted aryl group, b, c, m and l are integers of 1 to 2, and n is represented by 15 to 1000. Y and Z are a single bond, —O—, —CO—, represented by the following general formula 4, and R ³ represents hydrogen, an alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group.

アルキル基、及びアリール基は前述したものと同様である。
合成法は下記スキームで示される。

The alkyl group and aryl group are the same as those described above.
The synthesis method is shown in the following scheme.

（注）ここでビニルベンジルホスホニウムクロライドはｍ、ｐ混合のクロロメチルスチレンとトリフェニルホスフィンから誘導した。

(Note) Here, vinylbenzylphosphonium chloride was derived from chloromethylstyrene and triphenylphosphine mixed in m and p.

  An electrophotographic photosensitive member containing a charge transport material substituted with a vinyl group represented by the following general formula 6 and a polycarbonate represented by the following general formula 2

Ａｒ^５，Ａｒ^６は置換、無置換のアリール基を表わし、Ｒ^１、Ｒ^２は水素、分岐、もしくは直鎖のアルキル基、アリル基、ハロゲン、置換、もしくは無置換のアリール基を示し、ｄ、ｅ、ｍ、ｌは１〜２の整数を表わす。ｎは１５〜１０００で表される。

Ar ⁵ and Ar ⁶ represent a substituted or unsubstituted aryl group, R ¹ and R ² represent hydrogen, a branched or straight chain alkyl group, an allyl group, a halogen, a substituted or unsubstituted aryl group, and d , E, m, and l represent integers of 1 to 2. n is represented by 15 to 1000.

The ratio of the vinyl group-substituted charge transporting material and the polycarbonate linked with the cyclohexyl group is such that the charge transporting layer is formed by 7 to 15 parts by weight of the polycarbonate linked with the cyclohexyl group with respect to 10 parts by weight of the vinyl group-substituted charge transporting material.
Methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetyl acetone peroxide, methyl cyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2, 4 -Dichlorobenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5 -(T-butyloxy) -hexane, 1,3-bis (t-butylperoxy-isopropyl) benzene, t-butylcumyl peroxide, di-tbutyl peroxide, 2,5-dimethyl -2,5- (di-t-butylperoxy) hexane-3, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1, 1-di-t-butylperoxycyclohexane, 2,2-di (t-butylperoxy) butane, 4,4-di-t-butylperoxyvaleric acid n-butyl ester, 2,2-bis ( 4,4-t-butylperoxycyclohexyl) propane, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3,5,5-trimethylhexaate, t- Peroxides such as butyl peroxybenzoate and di-t-butylperoxytrimethyladipate, or azobisisobutyronitrile, Bis dimethyl valeronitrile, azo-based, such as azo-bis-cyclohexyl nitrile is used. When used in combination, these initiators are added at 0.5 to 10% of the total weight of the polycarbonate having the vinyl group-substituted charge transport material and the cyclohexyl group linked.

  Furthermore, the coating liquid of the present invention can contain additives such as various plasticizers (for the purpose of stress relaxation and adhesion improvement), leveling agents, and low molecular charge transport materials having no radical reactivity as required. As these additives, known additives can be used, and as plasticizers, those used in general resins such as dibutyl phthalate and dioctyl phthalate can be used, and the amount used is the total solid content of the coating liquid. To 20% by weight or less, preferably 10% or less. As leveling agents, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, polymers or oligomers having a perfluoroalkyl group in the side chain can be used, and the amount used is based on the total solid content of the coating liquid. 3% by weight or less is appropriate.

  The film is formed by applying and curing a coating solution. Solvents used here include ethers such as tetrahydrofuran and dioxane, halogens such as dichloromethane, dichloroethane, trichloroethane and chlorobenzene, and aromatics such as benzene, toluene and xylene. These solvents may be used alone or in combination of two or more. The dilution ratio with the solvent varies depending on the solubility of the composition, the coating method, and the target film thickness, and is arbitrary. The coating can be performed using a dip coating method, spray coating, bead coating, ring coating method or the like.

  In the present invention, such a coating solution is applied and cured to form a cross-linked surface layer. As a method, the coating is performed using a gas such as air or nitrogen, steam, various heat media, infrared rays, or electromagnetic waves. It is performed by heating from the work surface side or the support side. The heating temperature is preferably 80 ° C. or more and 170 ° C. or less, and if it is less than 80 ° C., the reaction rate is slow and the reaction is not completely completed. At a temperature higher than 170 ° C., the reaction proceeds non-uniformly and a large strain is generated in the crosslinked surface layer. In order to advance the curing reaction uniformly, it is also effective to complete the reaction by heating at a relatively low temperature of less than 50 ° C. and then heating to 100 ° C. or more.

Hereinafter, the present invention will be described according to the layer structure.
<About the layer structure of the electrophotographic photoreceptor>
The electrophotographic photosensitive member used in the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view showing an electrophotographic photosensitive member of the present invention, in which a single layer structure in which a photosensitive layer (33) having a charge generating function and a charge transporting function is provided on a conductive support (31). This is a photoreceptor. FIG. 1A shows the case where the cross-linked surface layer is the entire photosensitive layer, and FIG. 1-B shows the case where the cross-linked surface layer is the surface portion of the photosensitive layer.
FIG. 2 shows a photoreceptor having a laminated structure in which a charge generation layer (35) having a charge generation function and a charge transport layer (37) having a charge transport material function are laminated on a conductive support (31). is there. FIG. 2-A shows the case where the cross-linked surface layer is the entire charge transport layer, and FIG. 2-B shows the case where the cross-linked surface layer is the surface portion of the charge transport layer.

<About conductive support>
As the conductive support (31), a material having a volume resistance of 10 ¹⁰ Ω · cm or less, for example, a metal such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, oxidation Metal oxide such as indium is deposited or sputtered to form film or cylindrical plastic, paper coated, or aluminum, aluminum alloy, nickel, stainless steel, etc. After conversion, a tube that has been subjected to surface treatment such as cutting, superfinishing, or polishing can be used. Further, an endless nickel belt and an endless stainless steel belt disclosed in Japanese Patent Application Laid-Open No. 52-36016 can be used as the conductive support (31).
In addition, the conductive support dispersed in a suitable binder resin and coated on the support can also be used as the conductive support (31) of the present invention.

  Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc and silver, or metal oxide powder such as conductive tin oxide and ITO. Can be mentioned. The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, Examples thereof include thermoplastic, thermosetting resins, and photocurable resins such as melamine resin, urethane resin, phenol resin, and alkyd resin. Such a conductive layer can be provided by dispersing and coating these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.

  Furthermore, it is electrically conductive by a heat-shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon (registered trademark) on a suitable cylindrical substrate. Those provided with a conductive layer can also be used favorably as the conductive support (31) of the present invention.

<About photosensitive layer>
Next, the photosensitive layer will be described. The photosensitive layer may have a laminated structure or a single layer structure.
In the case of a laminated structure, the photosensitive layer is composed of a charge generation layer having a charge generation function and a charge transport layer having a charge transport function. In the case of a single layer structure, the photosensitive layer is a layer having a charge generation function and a charge transport function at the same time.

Hereinafter, each of the photosensitive layer having a laminated structure and the photosensitive layer having a single layer structure will be described.
<Photosensitive layer comprising a charge generation layer and a charge transport layer>
(Charge generation layer)
The charge generation layer (35) is a layer mainly composed of a charge generation material having a charge generation function, and a binder resin can be used in combination as necessary. As the charge generation material, inorganic materials and organic materials can be used.
Inorganic materials include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, and amorphous silicon. In amorphous silicon, dangling bonds that are terminated with hydrogen atoms or halogen atoms, or those that are doped with boron atoms, phosphorus atoms, or the like are preferably used.
On the other hand, a known material can be used as the organic material. For example, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azulenium salt pigments, squaric acid methine pigments, azo pigments having carbazole skeleton, azo pigments having triphenylamine skeleton, azo pigments having diphenylamine skeleton, dibenzothiophene skeleton Azo pigments having a fluorenone skeleton, azo pigments having an oxadiazole skeleton, azo pigments having a bis-stilbene skeleton, azo pigments having a distyryl oxadiazole skeleton, azo pigments having a distyrylcarbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinoneimine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, Goido based pigments, and bisbenzimidazole pigments. These charge generation materials can be used alone or as a mixture of two or more.

  The binder resin used as necessary for the charge generation layer (35) is polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-. Examples thereof include vinyl carbazole and polyacrylamide. These binder resins can be used alone or as a mixture of two or more. In addition to the binder resin described above as a binder resin for the charge generation layer, a polymer charge transport material having a charge transport function, such as an arylamine skeleton, benzidine skeleton, hydrazone skeleton, carbazole skeleton, stilbene skeleton, pyrazoline skeleton, etc. Polymer materials such as polycarbonate, polyester, polyurethane, polyether, polysiloxane, and acrylic resin, polymer materials having a polysilane skeleton, and the like can be used.

Specific examples of the former include JP-A-01-001728, JP-A-01-009964, JP-A-01-013061, JP-A-01-019049, JP-A-01-241559, Japanese Unexamined Patent Publication Nos. 04-011627, 04-175337, 04-183719, 04-2225014, 04-230767, 04-320420, 05 -232727, JP-A 05-310904, JP-A 06-234836, JP-A 06-234837, JP-A 06-234838, JP-A 06-234839, JP-A 06-234840. No. 1, JP-A 06-234841, JP-A 06-239049, Japanese Unexamined Patent Publication Nos. 06-236050, 06-236051, 06-295077, 07-0756374, 08-176293, 08-208820, 08 No. -21640, JP 08-253568, JP 08-269183, JP 09-062019, JP 09-043883, JP 09-71642, JP 09-87376. No. 1, JP-A 09-104746, JP 09-110974, JP 09-110976, JP 09-157378, JP 09-221544, JP 09-227669. JP 09-235367 A, JP 09-241369 A Charge transporting polymer materials described in JP 09-268226 A, JP 09-272735 A, JP 09-302084 A, JP 09-302085 A, JP 09-328539 A, etc. Can be mentioned.
Specific examples of the latter include polysilylene polymers described in, for example, JP-A No. 63-285552, JP-A No. 05-19497, JP-A No. 05-70595, JP-A No. 10-73944, and the like. Illustrated.
The charge generation layer (35) may contain a low molecular charge transport material.
Low molecular charge transport materials that can be used in combination with the charge generation layer (35) include hole transport materials and electron transport materials.
Examples of the electron transporting material include chloroanil, bromanyl, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-tri Examples thereof include electron-accepting substances such as nitrodibenzothiophene-5,5-dioxide and diphenoquinone derivatives. These electron transport materials can be used alone or as a mixture of two or more.
Examples of the hole transporting material include the electron donating materials shown below and are used favorably. As hole transport materials, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triaryls Other known materials such as methane derivatives, 9-styrylanthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives, and the like can be given. These hole transport materials can be used alone or as a mixture of two or more.

Methods for forming the charge generation layer (35) include a vacuum thin film preparation method and a casting method from a solution dispersion system.
As the former method, a vacuum deposition method, a glow discharge decomposition method, an ion plating method, a sputtering method, a reactive sputtering method, a CVD method, or the like is used, and the above-described inorganic materials and organic materials can be satisfactorily formed.
In addition, in order to provide a charge generation layer by the casting method described later, if necessary, the inorganic or organic charge generation material together with a binder resin, tetrahydrofuran, dioxane, dioxolane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, cyclohexane. Can be formed by dispersing with a ball mill, attritor, sand mill, bead mill, etc. using a solvent such as pentanone, anisole, xylene, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, etc. . Moreover, leveling agents, such as a dimethyl silicone oil and a methylphenyl silicone oil, can be added as needed. The coating can be performed using a dip coating method, spray coating, bead coating, ring coating method or the like.
The thickness of the charge generation layer provided as described above is suitably about 0.01 to 5 μm, preferably 0.05 to 2 μm.

(About charge transport layer)
When the charge transport layer (37) is a layer having a charge transport function and the polycarbonate cross-linked surface layer obtained by linking the vinyl group-substituted charge transport material of the present invention and the cyclohexyl group is the entire charge transport layer (37), As described in the method for preparing a crosslinked surface layer, a coating liquid is applied onto the charge generation layer (35), and a curing reaction is started by external energy, whereby a crosslinked surface layer is formed. At this time, the film thickness of the crosslinked surface layer is 10 to 30 μm, preferably 10 to 25 μm. If it is thinner than 10 μm, a sufficient charging potential cannot be maintained, and if it is thicker than 30 μm, peeling from the lower layer tends to occur due to volume shrinkage during curing.
When the cross-linked surface layer is formed on the surface portion of the charge transport layer (37) and the charge transport layer (37) has a laminated structure, the lower layer portion of the charge transport layer has a charge transport material having a charge transport function and a binder. The resin is dissolved or dispersed in a suitable solvent, and this is formed on the charge generation layer (35) by coating and drying, and the vinyl group-substituted charge transport material of the present invention and the cyclohexyl group are connected thereto. A polycarbonate coating solution is applied and crosslinked and cured by external energy.
As the charge transport material, the electron transport material, hole transport material and polymer charge transport material described in the charge generation layer (35) can be used. As described above, the use of the polymer charge transport material can reduce the solubility of the lower layer when the surface layer is applied, and is particularly useful.

As the binder resin, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, Polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin And thermoplastic or thermosetting resins such as phenol resins and alkyd resins.
The amount of the charge transport material is 20 to 300 weights, preferably 40 to 150 weights per 100 weight of the binder resin. However, when a polymer charge transport material is used, it can be used alone or in combination with a binder resin.
As the solvent used for coating the lower layer portion of the charge transport layer, the same solvent as that for the charge generation layer can be used, but a solvent that dissolves the charge transport material and the binder resin well is suitable. These solvents may be used alone or in combination of two or more. The lower layer portion of the charge transport layer can be formed by a coating method similar to that for the charge generation layer (35).

If necessary, a plasticizer and a leveling agent can be added.
As a plasticizer that can be used in combination with the lower layer portion of the charge transport layer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is 100 parts by weight of the binder resin. On the other hand, about 0 to 30 parts by weight is appropriate.
As a leveling agent that can be used in combination with the lower layer portion of the charge transport layer, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain are used. About 0 to 1 part by weight is appropriate for 100 parts by weight of the binder resin.
The thickness of the lower layer portion of the charge transport layer is appropriately about 5 to 40 μm, preferably about 10 to 30 μm.
When the cross-linked surface layer is the surface portion of the charge transport layer (37), it is represented by the general formulas 1 and 2 of the present invention on the lower layer portion of the charge transport layer as described in the cross-linked surface layer preparation method described above. A coating liquid containing an aliamine compound and a polyfunctional acrylate compound represented by the general formula 2 and a polycarbonate represented by the general formulas 3 and 4 is applied, and if necessary, dried and then externally applied by heat or light. The curing reaction is initiated and a crosslinked surface layer is formed. At this time, the film thickness of the crosslinked surface layer is 1 to 20 μm, preferably 2 to 10 μm. If the thickness is less than 1 μm, the durability varies due to uneven film thickness. If the thickness is more than 20 μm, the entire thickness of the charge transport layer is increased, and the reproducibility of the image is reduced due to the diffusion of charges.

<Single photosensitive layer>
The photosensitive layer having a single layer structure is a layer having a charge generation function and a charge transport function at the same time, and the crosslinked surface layer having the charge transport structure of the present invention contains a charge generation material having a charge generation function, thereby providing a single layer structure. It is useful as a photosensitive layer. As described in the above method for casting a charge generation layer, a charge generation material is dispersed together with a coating solution containing a polycarbonate in which a vinyl group-substituted charge transport material and a cyclohexyl group are linked according to the present invention. (31) After coating on the substrate and drying as necessary, the curing reaction is started to form a crosslinked surface layer. In addition, you may add the liquid in which the charge generation material was previously disperse | distributed with the solvent to this coating material for bridge | crosslinking surface layers. At this time, the film thickness of the crosslinked surface layer is 10 to 30 μm, preferably 10 to 25 μm. If the thickness is less than 10 μm, a sufficient charging potential cannot be maintained. If the thickness is more than 30 μm, peeling from the conductive substrate or the undercoat layer tends to occur due to volume shrinkage during curing.
Further, when the crosslinked surface layer is a surface portion of a photosensitive layer having a single layer structure, the lower layer portion of the photosensitive layer is composed of a charge generating material having a charge generating function, a charge transporting material having a charge transport function, and a binder resin in an appropriate solvent. It can be formed by dissolving or dispersing in, coating and drying. Moreover, a plasticizer, a leveling agent, etc. can also be added as needed. As the charge generation material dispersion method, the charge generation material, the charge transport material, the plasticizer, and the leveling agent may be the same as those already described in the charge generation layer (35) and the charge transport layer (37). As the binder resin, in addition to the binder resin previously mentioned in the section of the charge transport layer (37), the binder resin mentioned in the charge generation layer (35) may be mixed and used. In addition, the above-described polymer charge transport materials can also be used, which is useful in that contamination of the lower photosensitive layer composition into the crosslinked surface layer can be reduced. The thickness of the lower layer portion of the photosensitive layer is suitably about 5 to 30 μm, preferably about 10 to 25 μm.
When the cross-linked surface layer is a surface portion of a photosensitive layer having a single layer structure, as described above, the polycarbonate having the vinyl group-substituted charge transporting material and the cyclohexyl group linked to the lower layer portion of the photosensitive layer and the charge generating material A coating solution containing is applied, and if necessary, dried and cured to form a crosslinked surface layer. At this time, the film thickness of the crosslinked surface layer is 1 to 20 μm, preferably 2 to 10 μm. When the thickness is less than 1 μm, the durability varies due to the film thickness unevenness.
The charge generation material contained in the photosensitive layer having a single layer structure is preferably 1 to 30% by weight based on the total amount of the photosensitive layer, and the binder resin contained in the lower layer portion of the photosensitive layer is 20 to 80% by weight of the total amount. The transport material is preferably used in an amount of 10 to 70 parts by weight.

<About the intermediate layer>
In the photoreceptor of the present invention, when the crosslinked surface layer becomes the surface portion of the photosensitive layer, an intermediate layer can be provided between the crosslinked surface layer and the lower photosensitive layer. This intermediate layer prevents inhibition of the curing reaction and unevenness of the crosslinked surface layer caused by mixing of the lower photosensitive layer composition in the crosslinked surface layer containing the radical polymerizable composition. It is also possible to improve the adhesion between the lower photosensitive layer and the surface cross-linked layer.
In the intermediate layer, a binder resin is generally used as a main component. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As a method for forming the intermediate layer, a generally used coating method is employed as described above. In addition, about 0.05-2 micrometers is suitable for the thickness of an intermediate | middle layer.

<About the undercoat layer>
In the photoreceptor of the present invention, an undercoat layer can be provided between the conductive support (31) and the photosensitive layer. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is coated with a solvent on these resins, the resin may be a resin having high solvent resistance with respect to a general organic solvent. desirable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, a metal oxide fine powder pigment exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential.
These undercoat layers can be formed using an appropriate solvent and a coating method like the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention. In addition, in the undercoat layer of the present invention, Al ₂ O ₃ is provided by anodization, organic substances such as polyparaxylylene (parylene), SiO ₂ , SnO ₂ , TiO ₂ , ITO, CeO ₂ A material provided with an inorganic material such as a vacuum thin film can also be used favorably. In addition, known ones can be used. The thickness of the undercoat layer is suitably from 0 to 5 μm.

<Addition of antioxidant to each layer>
In the present invention, in order to improve environmental resistance, in order to prevent a decrease in sensitivity and an increase in residual potential, a surface cross-linked layer, a photosensitive layer, a charge generation layer, a charge transport layer, an undercoat layer, an intermediate layer An antioxidant can be added to each layer such as a layer.

The following are mentioned as antioxidant which can be used for this invention.
(Phenolic compounds)
2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol), 4, 4'-thiobis- (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-4 -Hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene- -(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid ] Cryol ester, tocopherols and the like.
(Paraphenylenediamines)
N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine, N, N'- Di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine and the like.
(Hydroquinones)
2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2- (2-octadecenyl) ) -5-methylhydroquinone and the like.
(Organic sulfur compounds)
Dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like.
(Organic phosphorus compounds)
Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine, and the like.
These compounds are known as antioxidants such as rubbers, plastics and fats and oils, and commercially available products can be easily obtained.
The addition amount of the antioxidant in the present invention is 0.01 to 10% by weight based on the total weight of the layer to be added.

<Image Forming Method and Apparatus>
Next, the image forming method and the image forming apparatus of the present invention will be described in detail with reference to the drawings.
The image forming method and the image forming apparatus of the present invention use a photoconductor having a smooth charge transporting surface cross-linked layer. For example, at least after the photoconductor is charged, exposed to an image, and developed, the image is held. An image forming method and an image forming apparatus including a process of transferring a toner image onto a body (transfer paper), fixing, and cleaning of the surface of a photoreceptor.
In some cases, an image forming method or the like in which an electrostatic latent image is directly transferred to a transfer member and developed does not necessarily have the above-described process arranged on a photosensitive member.

  FIG. 3 is a schematic diagram illustrating an example of an image forming apparatus. In the image forming apparatus of this example, a charging charger (3), an eraser (4), an image exposure unit (5), a developing unit (6), a transfer unit, which are examples of charging means, are provided around the photoreceptor (1). A separation charger (11) formed integrally with a front charger (7) and a transfer charger (10) for transferring a toner image to a transfer paper (9) conveyed by a registration roller (8) from a transfer paper tray (not shown). A separation claw (12), a pre-cleaning charger (13), a cleaning fur brush (14), a cleaning blade (15), and a static elimination lamp (2) are arranged. As a means for charging the photoconductor (1) on average, a charging charger (3) is used. As the charging means, a corotron device, a scorotron device, a solid discharge element, a needle electrode device, a roller charging device, a conductive brush device, or the like is used, and a known method can be used.

  In particular, the constitution of the present invention is effective when a charging unit such as a contact charging method or a non-contact proximity arrangement charging method in which the photosensitive member composition is decomposed by proximity discharge from the charging unit is used. The contact charging method referred to here is a charging method in which a charging roller, a charging brush, a charging blade, or the like is in direct contact with the photosensitive member. On the other hand, the proximity charging method is, for example, a type in which the charging roller is arranged in a non-contact state so as to have a gap of 200 μm or less between the surface of the photoreceptor and the charging means. If this gap is too large, the charging tends to become unstable, and if it is too small, the surface of the charging member may be contaminated when toner remaining on the photoreceptor exists. is there. Accordingly, the gap is suitably 10 to 200 μm, preferably 10 to 100 μm.

Next, the image exposure unit (5) is used to form an electrostatic latent image on the uniformly charged photoreceptor (1). As the light source, all luminescent materials such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL) can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
Next, the developing unit (6) is used to visualize the electrostatic latent image formed on the photoreceptor (1). Development methods include a one-component development method using a dry toner, a two-component development method, and a wet development method using a wet toner. When the photosensitive member is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.
Next, a transfer charger (10) is used to transfer the toner image visualized on the photoconductor onto the transfer body (9). In addition, a pre-transfer charger (7) may be used for better transfer. As these transfer means, a transfer charger, an electrostatic transfer method using a bias roller, a mechanical transfer method such as an adhesive transfer method and a pressure transfer method, and a magnetic transfer method can be used. As the electrostatic transfer method, the charging means can be used.
Next, a separation charger (11) and a separation claw (12) are used as means for separating the transfer body (9) from the photoreceptor (1). As other separation means, electrostatic adsorption induction separation, side end belt separation, tip grip conveyance, curvature separation, and the like are used. As the separation charger (11), the charging means can be used.
Next, a fur brush (14) and a cleaning blade (15) are used to clean the toner remaining on the photoreceptor after transfer. Further, a pre-cleaning charger (13) may be used in order to perform cleaning more efficiently. Other cleaning means include a web method, a magnet brush method, and the like, but each may be used alone or in combination.
Next, a neutralizing unit is used for the purpose of removing the latent image on the photoreceptor as required. As the charge removal means, a charge removal lamp (2) and a charge removal charger are used, and the exposure light source and the charging means can be used respectively.
In addition, known processes can be used for reading, feeding, fixing, paper discharge and the like that are not close to the photoconductor.

The present invention is an image forming method and an image forming apparatus using the electrophotographic photoreceptor according to the present invention for such image forming means.
The image forming means may be fixedly incorporated in a copying apparatus, facsimile, or printer, but may be incorporated in these apparatuses in the form of a process cartridge and detachable. An example of the process cartridge is shown in FIG.
The process cartridge for the image forming apparatus includes a photoreceptor (101), and in addition, a charging unit (102), a developing unit (104), a transfer unit (106), a cleaning unit (107), and a discharging unit (not shown). ), And an apparatus (part) that can be attached to and detached from the image forming apparatus main body.
Referring to the image forming process by the apparatus illustrated in FIG. 4, the surface of the photoreceptor (101) is exposed by charging by the charging means (102) and exposure by the exposure means (103) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the image is formed, and the electrostatic latent image is developed with toner by the developing means (104). The toner development is transferred to the transfer body (105) by the transfer means (106), and printed. Out. Next, the surface of the photoconductor after the image transfer is cleaned by a cleaning unit (107), and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.
The present invention provides a process cartridge for an image forming apparatus in which a photosensitive member having a smooth charge transporting surface cross-linked layer and at least one of charging, developing, transferring, cleaning, and neutralizing means are integrated.
As is apparent from the above description, the electrophotographic photosensitive member of the present invention is not only used in electrophotographic copying machines, but also in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making. Can also be used widely.

Hereinafter, the present invention will be described specifically by way of examples. First, a method for synthesizing the vinylarylamine compound used in the examples will be described.
[Synthesis of Vinyl Arylamine Compound No. 12]
4-methoxy-4 ', 4 "-diformyltriphenylamine 10.15 g (0.0306 mol), 1,3-dimethyl-2-imidazolidinone 150 ml, (m, p mix) vinylbenzyltriphenylphosphonium chloride 33 g (0.0306 × 2 × 1.3 mol) was suspended and stirred, and 18.9 g of 28% sodium methoxide methanol solution was added dropwise at 22-30 ° C. over 1 hour. After reacting at room temperature for 6 hours, the solution was poured into 300 ml of water. Acidified with acetic acid, extracted with 200 ml of toluene and extracted with 200 ml of toluene, the extract was washed twice with 200 ml of water, dehydrated with magnesium sulfate, and chromatographed on silica gel / toluene. Toluene (50 ml) was added, and the mixture was heated and cooled to obtain a solid, yield 6.5 g. The IR chart of the alkenyl arylamine compound No.12.

[Synthesis of Vinyl Arylamine Compound No. 16]
15.4 g (0.0277 mol) of 4,4′-diformyltetraphenylbenzidine, 150 ml of 1,3-dimethyl-2-imidazolidinone, 25.7 g (0.0277 × 2 × 1.3 mol) of methyltriphenylphosphonium bromide The mixture was stirred and added dropwise at 20 to 25 ° C. for 1 hour, then reacted for 5 hours, poured into 300 ml of water, extracted with acetic acid with toluene, washed twice with 200 ml of water, dehydrated with magnesium sulfate, silica gel and Purification with toluene gave 12 g. m. p. : 127 ° C. FIG. 6 shows an IR chart of the vinyl arylamine compound No. 16.
Vinyl arylamine compound No. 14 is also synthesized in the same manner as these No. 12 and No. 16 compounds.

<Example 1>
By coating and drying an undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution in the following order on a φ30 mm aluminum cylinder in sequence, an undercoat layer of 3.5 μm A 0.2 μm charge generation layer and a 22 μm charge transport layer were formed. The electrophotographic photosensitive member of the present invention was obtained by drying at 150 ° C. for 30 minutes.
[Coating liquid for undercoat layer]
Alkyd resin 6 parts (Beckosol 1307-60-EL, manufactured by Dainippon Ink & Chemicals, Inc.)
Melamine resin 4 parts (Super Becamine G-821-60, manufactured by Dainippon Ink & Chemicals, Inc.)
Titanium oxide 40 parts Methyl ethyl ketone 50 parts [Coating liquid for charge generation layer]
Bisazo pigment of the following structural formula (I) 2.5 parts Polyvinyl butyral (XYHL, manufactured by UCC) 0.5 part Cyclohexanone 200 parts Methyl ethyl ketone 80 parts

〔電荷輸送層用塗工液〕

[Coating liquid for charge transport layer]

１０部
（帝人化成社製 パンライトＴＳ２０５０ 分子量ポリスチレン換算Ｍｗ１５万）
Ｎｏ．１４ １０部
ＴＨＦ ９０部
シリコーンオイル（ＫＦ５０ 信越化学社製） ０．０２部
実施例１と同様にして下引き層、電荷発生層を設けた上に下記表１の電荷輸送層液で２２μｍの電荷輸送層を形成した。１５０℃で３０分間乾燥し本発明の電子写真感光体を得た。

10 parts (manufactured by Teijin Chemicals Ltd. Panlite TS2050 molecular weight polystyrene equivalent Mw 150,000)
No. 14 10 parts THF 90 parts Silicone oil (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.02 parts In the same manner as in Example 1, an undercoat layer and a charge generation layer were provided, and the charge transport layer solution shown in Table 1 below was used to charge 22 μm. A transport layer was formed. The electrophotographic photosensitive member of the present invention was obtained by drying at 150 ° C. for 30 minutes.

上記表１中のＰＣ番号は、前記段落［００３０］に記載されたポリカを示す。

The PC number in Table 1 indicates the polycarbonate described in the paragraph [0030].

<Comparative Example 1>
In the same manner as in Example 1, an undercoat layer and a charge generation layer were provided, and the following charge transport layer 22 μm was provided.
[Coating liquid for charge transport layer]
Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals Ltd. Molecular weight polystyrene equivalent Mw 150,000)
Low molecular charge transport material (D-1) of the following structural formula (II) 10 parts Tetrahydrofuran 90 parts Silicone oil (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.02 parts Structural formula (II)

表２には比較例２〜８を示し、比較例２〜４ビニル基未置換アリールアミンを同じにしてポリカーボネートを代え、また比較例５〜８はビニル基未置換アリールアミン構造式（III）に代え比較例１と同様にして感光体を得た。
構造式（III）

Table 2 shows Comparative Examples 2 to 8, Comparative Examples 2 to 4 are the same for the vinyl group unsubstituted arylamine to replace the polycarbonate, and Comparative Examples 5 to 8 are the vinyl group unsubstituted arylamine structural formula (III). Instead, a photoconductor was obtained in the same manner as in Comparative Example 1.
Structural formula (III)

実施例１〜８、比較例１〜８電子写真感光体について、Ａ４サイズ２万枚の通紙試験を実施した。まず、前記感光体を電子写真装置用プロセスカートリッジに装着し、画像露光光源として６５５ｎｍの半導体レーザーを用いたリコー製ｉｍａｇｉｏ Ｎｅｏ ２７０改造機にて初期暗部電位を−７００Ｖに設定した。その後通紙試験を開始し、２万枚複写後の膜厚減少量の測定を行なった。結果を以下に示す。 膜厚計測は、フィシャー・インストルメンツ社製 渦電流膜厚計フィシャースコープＭＭＳで計測した。結果を表３，４に示した。摩耗はしたもののビニル置換電荷輸送材の感光体は従来のビニル未置換電荷輸送材に較べると約半分になり、耐久性が２倍延びたことがいえる。

Examples 1 to 8 and Comparative Examples 1 to 8 The electrophotographic photosensitive member was subjected to a paper passing test of 20,000 sheets of A4 size. First, the photosensitive member was mounted on a process cartridge for an electrophotographic apparatus, and the initial dark portion potential was set to −700 V with a Ricoh imagio Neo 270 remodeling machine using a 655 nm semiconductor laser as an image exposure light source. Thereafter, a paper passing test was started, and the amount of film thickness reduction after copying 20,000 sheets was measured. The results are shown below. The film thickness was measured with an eddy current film thickness meter Fischerscope MMS manufactured by Fischer Instruments. The results are shown in Tables 3 and 4. Although worn, the photoreceptor of the vinyl-substituted charge transport material was about half that of the conventional vinyl-unsubstituted charge transport material, and the durability was doubled.

<Example 9>
By coating and drying an intermediate layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution of the following composition in sequence on a φ100 mm aluminum cylinder, a 3.5 μm intermediate layer, 0.2 μm And a charge transport layer of 20 μm were formed. Further, a crosslinked surface layer coating solution was applied thereon by a spray method, and then dried at 150 ° C. for 30 minutes to provide a 7 μ-cured charge transport layer.
[Coating liquid for intermediate layer]
The following composition was dispersed and adjusted with a ball mill for 24 hours.
Alkyd resin 6 parts (Beccosol 1307-60-EL, manufactured by Dainippon Ink & Chemicals, Inc.)
Melamine resin 4 parts (Super Becamine G-821-60, manufactured by Dainippon Ink and Chemicals)
Titanium oxide (CREL Ishihara Sangyo Co., Ltd.) 40 parts Methyl ethyl ketone 200 parts [Coating liquid for charge generation layer]
The following composition was dispersed and adjusted with a ball mill for 24 hours.
Oxotinium phthalocyanine pigment 2 parts Polyvinyl butyral (UCC: XYHL) 0.2 part Tetrahydrofuran 50 parts [Coating liquid for charge transport layer]
The following composition was dissolved and adjusted.
Polystyrene (MW1C, manufactured by Toyo Styrene Co., Ltd.) 12 parts Low molecular charge transport material of the following structural formula (IV) 12 parts Structural formula (IV)

ＴＨＦ ９０部
シリコーンオイル（ＫＦ５０信越シリコーン社製） ０．０２部
〔架橋表面層用塗工液〕
Ｎｏ．２化合物 １部
ＰＣ１ポリカーボネート １部
アゾビスイソブチロニトリル重合開始剤 ０．０５部
テトラヒドロフラン ３０部

THF 90 parts Silicone oil (KF50 Shin-Etsu Silicone Co., Ltd.) 0.02 parts [Coating liquid for crosslinked surface layer]
No. 2 compounds 1 part PC1 polycarbonate 1 part Azobisisobutyronitrile polymerization initiator 0.05 parts Tetrahydrofuran 30 parts

<Example 10>
In the same manner as in Example 9, an undercoat layer, a charge generation layer, and a charge transport layer were provided, and the following surface cross-linked layer was provided in the same manner as in Example 9.
[Coating liquid for cross-linked surface layer]
No. 7 vinylarylamine 1 part PC2 polycarbonate 1 part Azobisdimethylvaleronitrile photopolymerization initiator 0.05 part Tetrahydrofuran 30 parts

<Comparative Example 9>
In the same manner as in Example 6, the intermediate layer and the charge generation layer were provided, and the charge transport layer binder resin was changed to Z polycarbonate resin (TS2050 manufactured by Teijin Kasei Co., Ltd.), and a film thickness of 27 μm was sequentially applied and dried. It was created.
The photoconductors of Examples 9 and 10 and Comparative Example 9 were mounted on the apparatus shown in FIG. 3 and Imagio Neo1050Pro manufactured by Ricoh Co., Ltd., and 500,000 sheets were tested.

本来比較例は架橋表面層がないものではあるが、使用した電荷輸送層バインダー樹脂がポリスチレン表層であると機械的強度がなく耐久試験には適さないため強靱なＺポリカ樹脂とした。
５０万枚の画像出し試験の結果では実施例、比較例共に鮮明な画像であった、しかし摩耗量が従来の電荷輸送層に比較すると２倍の耐摩耗性を示し、従来の感光体よりも２倍の耐久性があるといえる。

The comparative example originally has no cross-linked surface layer, but if the charge transport layer binder resin used is a polystyrene surface layer, it has mechanical strength and is not suitable for a durability test, so it was made a tough Z-polyca resin.
As a result of the image output test of 500,000 sheets, both the example and the comparative example were clear images, but the wear amount was twice as high as that of the conventional charge transport layer, which was higher than that of the conventional photoconductor. It can be said that it is twice as durable.

<Example 11>
The following charge generating substance and solvent were charged in a 15 cm ball mill pot, ball milled for 48 hours using 10φ zirconia media, and then 500 parts of cyclohexanone was added to prepare a mill base (dispersion 1).

２２部
シクロヘキサノン ４００部
（塗工液１）
テトラヒドロフラン（ＴＨＦ） ６６部
ＰＣ３のポリカーボネート ４部
Ｎｏ．１８ビニルアリールアミン ４部
ポリエチレングリコール（イオネットＭＣ１４００ 三洋化成社） ０．２部
シリコーンオイル（ＫＦ５０ 信越化学社製） ０．０１部
分散液１ １２部、塗工液１ ２０部、混合攪拌して塗工液２を調整した。
φ３０ｍｍアルミニウムシリンダー上にポリアミド樹脂（ＣＭ８０００ 東レ社製）１０部、メタノール ２２０部、ｎ−ブタノール １００部の溶液を５ｍｍ／ｓｅｃで浸漬塗工し、１００℃で１０分間乾燥して０．３μｍの下引き層をもうけた。この上に上記塗工液２を塗工して２０μｍの単層感光体を設けた。１５０℃で３０分間乾燥し本発明の電子写真感光体を得た。

22 parts Cyclohexanone 400 parts (Coating fluid 1)
Tetrahydrofuran (THF) 66 parts PC3 polycarbonate 4 parts No. 18 parts vinyl arylamine 4 parts Polyethylene glycol (Ionette MC1400 Sanyo Chemical Co., Ltd.) 0.2 parts Silicone oil (KF50, Shin-Etsu Chemical Co., Ltd.) 0.01 parts Dispersion 1 12 parts, Coating liquid 1 20 parts, mixed and stirred to coat The working fluid 2 was adjusted.
A solution of 10 parts of polyamide resin (CM8000 manufactured by Toray Industries, Inc.), 220 parts of methanol, and 100 parts of n-butanol is dip coated at 5 mm / sec on a 30 mm aluminum cylinder, dried at 100 ° C. for 10 minutes, and 0.3 μm below I made a pulling layer. The coating solution 2 was coated thereon to provide a 20 μm single layer photoreceptor. The electrophotographic photosensitive member of the present invention was obtained by drying at 150 ° C. for 30 minutes.

<Comparative Example 10>
(Coating fluid 3)
Tetrahydrofuran (THF) 66 parts PC3 polycarbonate 4 parts

４部
ポリエチレングリコール（イオネットＭＣ１４００ 三洋化成社） ０．２部
シリコーンオイル（ＫＦ５０ 信越化学社製） ０．０１部
分散液１ １２部、塗工液３ ２０部、混合攪拌して塗工液４を調整した。
φ３０ｍｍアルミニウムシリンダー上にポリアミド樹脂（ＣＭ８０００ 東レ社製）１０部、メタノール ２２０部、ｎ−ブタノール １００部の溶液を浸漬塗工し、１００℃で１０分間乾燥して０．３μｍの下引き層をもうけた。この上に塗工液４を塗工して２０μｍの比較感光体を作成した。

4 parts Polyethylene glycol (Ionette MC1400 Sanyo Chemical Co., Ltd.) 0.2 parts Silicone oil (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.01 parts Dispersion liquid 1 12 parts, coating liquid 3 20 parts, mixed and stirred to give coating liquid 4 It was adjusted.
A solution of 10 parts of polyamide resin (CM8000 manufactured by Toray Industries, Inc.), 220 parts of methanol, and 100 parts of n-butanol is dip-coated on a 30 mm aluminum cylinder and dried at 100 ° C. for 10 minutes to form an undercoat layer of 0.3 μm. It was. A coating liquid 4 was applied thereon to prepare a 20 μm comparative photoconductor.

An initial dark portion was obtained with a modified Rigoh imagio Neo 270 machine in which the photoconductors of Example 11 and Comparative Example 10 were mounted on a process cartridge for an electrophotographic apparatus, a semiconductor laser of 655 nm was used as an image exposure light source, and the charge polarity was positively charged. The potential was set to 700V. Thereafter, a paper passing test was started and a 1000 sheet copying test was conducted.
Example 8 was a clear image, but it was confirmed that white and black streaks were generated on the comparative photoconductor. This is considered to be due to the difference in surface hardness, and it is considered that the photoconductor of the example was cross-linked to improve the scratch resistance with increasing hardness and to obtain a clear image.

1 is an example of a cross-sectional view of an electrophotographic photosensitive member of the present invention. It is another example of sectional drawing of the electrophotographic photosensitive member of this invention. 1 is a schematic diagram illustrating an example of an image forming apparatus of the present invention. FIG. 2 is a schematic diagram illustrating an example of a process cartridge for an image forming apparatus according to the present invention. It is the figure which showed IR chart of No. 12 of the vinyl arylamine compound used in the Example of this invention. It is the figure which showed IR chart of No. 16 of the vinyl arylamine compound used in the Example of this invention. It is the figure which showed IR spectrum of the formed TF film | membrane insoluble in THF with the IR spectrum of Z polyca used for the coating liquid, and the IR spectrum of No.16 charge transportable aromatic triamine compound.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Static elimination lamp 3 Charger 4 Eraser 5 Image exposure part 6 Developing unit 7 Pre-transfer charger 8 Registration roller 9 Transfer paper 10 Transfer charger 11 Separation charger 12 Separation claw 13 Pre-cleaning charger 14 Fur brush 15 Cleaning blade 31 Conductivity Support 33 Photosensitive layer 35 Charge generation layer 37 Charge transport layer 101 Photosensitive drum 102 Charging means 103 Exposure means 104 Development means 105 Transfer body 106 Transfer device 107 Cleaning means

Claims (6)

The uppermost layer is a layer containing a charge transport material substituted with a vinyl group and a polycarbonate having a cyclohexyl group linked to the main chain, and the charge transport material has a vinyl group represented by the following general formula 1. An electrophotographic photoreceptor, which is a substituted charge transport material, wherein the polycarbonate is a polycarbonate represented by the following general formula 2 .

Here, Ar ¹ represents a substituted or unsubstituted aryl group, h and i are numbers from 0 to 2, and 0 is not the same in both cases. R ¹ and R ² represent hydrogen, a branched or straight chain alkyl group, an allyl group, a halogen, a substituted or unsubstituted aryl group, m and l are integers of 1 to 2, and n is 15 to 1000. Is done. The uppermost layer is a layer containing a charge transport material substituted with a vinyl group and a polycarbonate having a cyclohexyl group linked to the main chain, and the charge transport material has a vinyl group represented by the following general formula 3. An electrophotographic photoreceptor, which is a substituted charge transport material, wherein the polycarbonate is a polycarbonate represented by the following general formula 2 .

Ar ² and Ar ³ represent a substituted or unsubstituted aryl group, and R ¹ and R ² represent a hydrogen, branched or straight chain alkyl group, an allyl group, a halogen, a substituted or unsubstituted aryl group, and a , M, l are integers of 1-2, and n is 15-1000. X represents a single bond, —O—, —CO—, represented by the following general formula 4, and R ³ represents hydrogen, an alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group.

The uppermost layer is a layer containing a charge transport material substituted with a vinyl group and a polycarbonate having a cyclohexyl group linked to the main chain, and the charge transport material has a vinyl group represented by the following general formula 5. An electrophotographic photoreceptor, which is a substituted charge transport material, wherein the polycarbonate is a polycarbonate represented by the following general formula 2 .

Ar ⁴ represents a substituted or unsubstituted aryl group, R ¹ and R ² represent a hydrogen, branched or straight chain alkyl group, an allyl group, a halogen, a substituted or an unsubstituted aryl group, b, c, m and l are integers of 1 to 2, and n is represented by 15 to 1000. Y and Z are a single bond, —O—, —CO—, represented by the following general formula 4, and R ³ represents hydrogen, an alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group.

The uppermost layer is a layer containing a charge transport material substituted with a vinyl group and a polycarbonate having a cyclohexyl group linked to the main chain, and the charge transport material has a vinyl group represented by the following general formula 6. An electrophotographic photoreceptor, which is a substituted charge transport material, wherein the polycarbonate is a polycarbonate represented by the following general formula 2 .

Ar ⁵ and Ar ⁶ represent a substituted or unsubstituted aryl group, R ¹ and R ² represent hydrogen, a branched or straight chain alkyl group, an allyl group, a halogen, a substituted or unsubstituted aryl group, and d , E, m, and l represent an integer of 1 to 2, and n is represented by 15 to 1000. 5. An image forming apparatus comprising at least a charging unit, an image exposing unit, a developing unit, a transferring unit, and an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is one according to any one of claims 1 to 4. An image forming apparatus. An electrophotographic photosensitive member according to any one of claims 1 to 4, charging means that, developing means, and integrally supported and at least one means selected from a cleaning means, which is detachably attached to the image forming apparatus main body A process cartridge for an image forming apparatus.

Images