JP4771895B2 - Electrophotographic photosensitive member, image forming method using the same, image forming apparatus, and process cartridge for image forming apparatus - Google Patents

Description

  The present invention provides an electronic device having high durability and high image quality over a long period of time by using a photosensitive layer having high wear resistance, smooth surface properties and good electrical characteristics. The present invention relates to a photographic photoreceptor. 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 abrasion 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.
As a technique for improving the abrasion resistance of the photosensitive layer, curing of 2,2′-diallylbisphenol A-type polycarbonate resin is known (Patent Document 1: Japanese Patent Laid-Open No. 4-291348). Further, a cured charge transport layer of 2,2′-diallyl bisphenol type polycarbonate resin and an acrylic group-substituted charge transport material has been proposed (Patent Document 2: Japanese Patent No. 3081705). The group reaction is not sufficient in terms of wear resistance such as hardness. Further, a stilbene carbonate resin is disclosed (for example, Patent Document 3: Japanese Patent Application Laid-Open No. 10-508064), which has high crystallinity, high secondary structure of molecular chains and high toughness.

JP-A-4-291348 Japanese Patent No. 3081705 Japanese National Patent Publication No. 10-508064

  The object of the present invention is high wear resistance, high scratch resistance, 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 problems are solved by the present invention described below.
(1) “From an electrophotographic photoreceptor having at least a photosensitive layer on a conductive support, a polycarbonate copolymer represented by the following general formula (2) and a charge transport material having a carbon-carbon double bond: An electrophotographic photosensitive member comprising a cured product as a top layer of the photosensitive layer ;

（式中、Ｒ _３ ，Ｒ _４ は水素原子、メチル基を表す。

ｈ、ｉは共重合ｍｏｌ％を表し、ｈは５〜８０、ｉは２０〜９５を表す。）」、
（２）「前記一般式（２）で示されるポリカーボネート共重合体と、炭素−炭素二重結合をもった電荷輸送物質と、アクリロイルオキシ基を有するラジカル重合性モノマーとからなる硬化物を最上層に含有することを特徴とする前記第（１）項に記載の電子写真感光体」、
（３）「前記炭素−炭素二重結合をもった電荷輸送物質が下記一般式（３）で示されるものであることを特徴とする前記第（１）項又は第（２）項に記載の電子写真感光体；

_(Wherein, R 3, _{R 4} represents a hydrogen atom, a methyl group.

h and i represent copolymerization mol%, h represents 5 to 80, and i represents 20 to 95. ) ",
(2) “The uppermost layer is a cured product composed of the polycarbonate copolymer represented by the general formula (2), a charge transport material having a carbon-carbon double bond, and a radical polymerizable monomer having an acryloyloxy group. The electrophotographic photosensitive member according to item (1), which is contained in
(3) “The charge transport material having a carbon-carbon double bond is represented by the following general formula (3)” , according to the above (1) or (2) Electrophotographic photoreceptor;

（式中、Ａｃｔはアクリロイルオキシ基、ビニル基から選択される炭素−炭素二重結合を表す。ｅ、ｆは０又は１の整数を表し、ｅ、ｆのうち少なくとも一方は１である。Ｒ ^７ 、Ｒ ^８ は水素原子、メチル基を表す。）」、
（４）「前記炭素−炭素二重結合をもった電荷輸送物質が下記一般式（５）で示されるものであることを特徴とする前記第（１）項又は第（２）項に記載の電子写真感光体；

(In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group and a vinyl group. E and f represent an integer of 0 or 1, and at least one of e and f is 1. R. ⁷ and R ⁸ represent a hydrogen atom or a methyl group.
(4) “The charge transport material having a carbon-carbon double bond is represented by the following general formula (5),” according to (1) or (2) , Electrophotographic photoreceptor;

（式中、Ａｃｔはアクリロイルオキシ基、ビニル基から選択される炭素−炭素二重結合を表す。ｇ、ｋ、ｏは０又は１の整数を表し、少なくとも、ｇ、ｋ、ｏのうちのいずれか一つは１である。Ａｒ ^１ はフェニレン基を表し、ｖは０又は１の整数を表す。Ｒ ^９ 、Ｒ ^１０ は水素原子、メチル基を表す。）」、
（５）「前記炭素−炭素二重結合をもった電荷輸送物質が下記一般式（６）で示されるものであることを特徴とする前記第（１）項又は第（２）項に記載の電子写真感光体；

(In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group and a vinyl group. G, k, and o represent an integer of 0 or 1, and at least any one of g, k, and o. One is 1. Ar ¹ represents a phenylene group, v represents an integer of 0 or 1. R ⁹ and R ¹⁰ represent a hydrogen atom and a methyl group.
(5) “The charge transport material having a carbon-carbon double bond is represented by the following general formula (6)”, according to the above (1) or (2) Electrophotographic photoreceptor;

（式中、Ａｃｔはアクリロイルオキシ基、ビニル基から選択される炭素−炭素二重結合を表す。ｐ，ｑは０又は１の整数を表し、ｐ、ｑのうち一方は少なくとも１である。Ｒ ^１１ 、Ｒ ^１２ は水素原子、メチル基を表す。）」、
（６）「前記炭素−炭素二重結合をもった電荷輸送物質が下記一般式（７）で示されるものであることを特徴とする前記第（１）項又は第（２）項に記載の電子写真感光体；

(In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group and a vinyl group. P and q represent an integer of 0 or 1, and one of p and q is at least 1. R ¹¹ and R ¹² represent a hydrogen atom or a methyl group .
(6) “The charge transport material having a carbon-carbon double bond is represented by the following general formula (7),” according to the above (1) or (2) Electrophotographic photoreceptor;

（式中、Ａｃｔはアクリロイルオキシ基、ビニル基から選択される炭素−炭素二重結合を表す。ｒは１の整数を表す。Ａｒ ^２ 、Ａｒ ^３ は置換、無置換のアリール基を表わし、
Ｂは、

(In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group and a vinyl group. R represents an integer of 1. Ar ² and Ar ³ represent a substituted or unsubstituted aryl group;
B is

を表わし、ここでＲ^１３、Ｒ^１４は水素原子、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。）」、
（７）「前記炭素−炭素二重結合をもった電荷輸送物質が下記一般式（８）で示されるものであることを特徴とする前記第（１）項又は２に記載の電子写真感光体；

Wherein R ¹³ and R ¹⁴ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group. ) ",
( 7) The electrophotographic photosensitive member according to item (1) or 2 , wherein the charge transport material having a carbon-carbon double bond is represented by the following general formula (8): ;

（式中、Ａｃｔは、アクリロイルオキシ基、ビニル基から選択された炭素−炭素二重結合を表わす。ｓ、ｕはそれぞれ独立に０又は１の整数を表わし、ｓ、ｕのうち少なくとも一方は１である。Ａｒ^４は置換、無置換のアリール基を表わす。）、
（８）「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（７）項のいず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」、
（９）「前記第（１）項乃至第（７）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」。

(In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group and a vinyl group. S and u each independently represents an integer of 0 or 1, and at least one of s and u is 1) it is. Ar ⁴ represents a substituted or unsubstituted aryl group.)
(8) “In an image forming apparatus including 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 items (1) to ( 7)” . An image forming apparatus characterized in that the image forming apparatus is any of the above ",
(9) “ Integrally supports the electrophotographic photosensitive member according to any one of ( 1) to ( 7) and at least one means selected from a charging means, a developing means, and a cleaning means. An image forming apparatus process cartridge characterized by being detachable from the image forming apparatus main body.

（式中、Ｒ^１，Ｒ^２は水素、同一、又は異なる炭素数１〜４のアルキル基、Ｒ^３、Ｒ^４は水素、同一、又は異なる炭素数１〜４のアルキル基、炭素数５〜７のシクロアルキル基、炭素数６〜１２の置換若しくは無置換のアリール基を表わし、Ａは単結合、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＳｉＯ（ＣＨ_３）_２−、−ＣＲ^５Ｒ^６−（Ｒ^５及びＲ^６はそれぞれ独立に水素原子、トリフオロメチル基、炭素数１〜６のアルキル基、又は炭素数６〜１２の置換若しくは無置換のアリール基である。）、又は炭素数５〜１１の１，１−シクロアルキリデン基を表わし、ａ，ｂ，ｃ，ｄはそれぞれ独立に０〜４の整数を表わし、ｈ，ｉは共重合ｍｏｌ％を表わし、ｈは５〜８０、ｉは２０〜９５を表わす。）」、
（１０）「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（９）項のいず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」、
（１１）「前記第（１）項乃至第（９）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」。

(Wherein R ¹ and R ² are hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms, R ³ and R ⁴ are hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms, and 5 to 5 carbon atoms. 7 represents a cycloalkyl group having 7 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and A represents a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —SiO (CH ₃ ) ₂ —, —CR ⁵ R ⁶ — (R ⁵ and R ⁶ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms, or a substituted or non-substituted group having 6 to 12 carbon atoms. A substituted aryl group), or a 1,1-cycloalkylidene group having 5 to 11 carbon atoms, a, b, c and d each independently represent an integer of 0 to 4, and h and i are both Represents a polymerization mol%, h represents 5 to 80, and i represents 20 to 95).
(10) “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 items (1) to (9)”. An image forming apparatus characterized in that the image forming apparatus is any of the above ",
(11) “Integrally supports the electrophotographic photosensitive member according to any one of (1) to (9) and at least one means selected from a charging means, a developing means, and a cleaning means. An image forming apparatus process cartridge characterized by being detachable from the image forming apparatus main body.

  The present invention provides a highly durable photoreceptor by increasing the hardness, increasing the elastic modulus, improving the mechanical strength, and improving the wear resistance by cross-linking the polycarbonate resin having the steven unit and the charge transport material having the carbon-carbon double bond. It became possible.

  In the present invention, the surface layer of the photosensitive layer is cured from a (resinous) polycarbonate compound having at least a plurality of stilbene skeleton units represented by the following general formula (1) and a polymerizable charge transport material having a carbon-carbon double bond. A highly sensitive photoconductor containing a reaction (polymerization reaction) product is provided.

（式中、Ｒ^１，Ｒ^２は水素、同一、又は異なる炭素数１〜４のアルキル基、ａ，ｂは１〜４の整数を表わす。）

(In the formula, R ¹ and R ² represent hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms, and a and b each represents an integer of 1 to 4)

[Polycarbonate having a steven unit, copolymer represented by the general formula (2)]
The polycarbonate represented by the general formula (1) is synthesized according to the following scheme. For the synthesis of the monomer, stilbene was synthesized by a Wittig reaction between hydroxybenzaldehyde and methoxybenzyl phosphonate, and then dihydroxystilbene was synthesized by demethylation. Polycarbonate was synthesized by the action of triphosgene by interfacial polymerization in dichloromethane and an aqueous alkali solution.

（式中Ｒ^１，Ｒ^２は水素、同一、又は異なる炭素数１〜４のアルキル基を表わす。）
これらスチベンユニットをもつ芳香族ジオールは、上記特許文献３の特表平１０−５０８０６４号公報及び該公報中に記載の文献に記載されている。

(Wherein R ¹ and R ² represent hydrogen, the same or different alkyl groups having 1 to 4 carbon atoms)
These aromatic diols having a stibene unit are described in JP-A-10-508064 of Patent Document 3 and the documents described therein.

  In the present invention, a copolymer represented by the following general formula (2) can also be preferably used as the polycarbonate having a steven unit.

A monopolymer of dihydroxystilbene exhibits high crystallinity, precipitates during the reaction, and becomes insoluble in a solvent, but forms a film soluble in a solvent by copolymerization with other bisphenols.
The copolymerization ratio of 4,4′-dihydroxystilbene with other monomers is preferably 20% or less in terms of the total number of moles, or 20% or less in terms of weight ratio. The 3,4′-dihydroxy form is less crystalline than the 4,4′-dihydroxy form, but has crystallinity and is preferably 70% or less in terms of the total number of moles or 70% or less in terms of weight ratio.

  Examples of the dihydric phenol used for obtaining the copolymer represented by the general formula (2) include those represented by the following general formula (9).

（Ｒ^３、Ｒ^４は水素、同一、又は異なる炭素数１〜４のアルキル基、炭素数５〜７のシクロアルキル基、炭素数６〜１２の置換若しくは無置換のアリール基を表わし、Ａは単結合、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＳｉＯ（ＣＨ_３）_２−、−ＣＲ^５Ｒ^６−（Ｒ^５及びＲ^６はそれぞれ独立に水素原子、トリフオロメチル基、炭素数１〜６のアルキル基、又は炭素数６〜１２の置換若しくは無置換のアリール基である。）、炭素数５〜１１の１，１−シクロアルキリデン基を表わし、ｃ，ｄはそれぞれ独立に０〜４の整数を表わす。）

(R ³ and R ⁴ represent hydrogen, the same or different alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and A represents Single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —SiO (CH ₃ ) ₂ —, —CR ⁵ R ⁶ — (R ⁵ and R ⁶ are each independently hydrogen. An atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms), and a 1,1-cycloalkylidene group having 5 to 11 carbon atoms. , C and d each independently represents an integer of 0 to 4.)

  Specific examples include, for example, 4,4′-dihydroxybiphenyl, 3,3′-difluoro-4,4′-dihydroxybiphenyl, 4,4′-dihydroxy-3,3′-dimethylbiphenyl, 4,4′- 4,4′-dihydroxybiphenyls such as dihydroxy-2,2′-dimethylbiphenyl, 4,4′-dihydroxy-3,3′-dicyclohexylbiphenyl; bis (4-hydroxyphenyl) methane, 1,1-bis ( 4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2,2-bis (3-methyl-4) -Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) Octane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylmethane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis ( 3-methyl-4-hydroxyphenyl) propane, 2- (3-methyl-4-hydroxyphenyl) -2- (4-hydroxyphenyl) -1-phenylethane, bis (3-methyl-4-hydroxyphenyl) methane 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (2-methyl-4-hydroxy) Enyl) propane, 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane, 1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) propane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis ( 2-tert-butyl-4-hydroxy-5-methylphenyl) isobutane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) heptane, 1,1-bis (2-tert- Butyl-4-hydroxy-5-methylphenyl) -1-phenylmethane, 1,1-bis (4-hydroxy-2-methyl-5-tert-pentylphenyl) butyl Tan, bis (3-chloro-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2 -Bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane ( Also known as: tetrafluorobisphenol A), 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane (also known as: tetrachlorobisphenol A), 2,2-bis (3,5-dibromo-4-hydroxy) Phenyl) propane (also known as: tetrabromobisphenol A), 2,2-bis (3-bromo-4-hydroxy-5-chlorophene) Propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) butane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) butane, 1-phenyl-1,1- Bis (3-fluoro-4-hydroxyphenyl) ethane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (3-hydroxyphenyl) -1,1,1,3 Bis (4-hydroxyphenyl) such as 3,3-hexafluoropropane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane Alkanes; bis (4-hydro) such as bis (4-hydroxyphenyl) ether and bis (3-fluoro-4-hydroxyphenyl) ether Cyphenyl) ethers; bis (4-hydroxyphenyl) sulfides such as bis (4-hydroxyphenyl) sulfide and bis (3-methyl-4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfone, bis (3 -Methyl-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfones such as bis (3-phenyl-4-hydroxyphenyl) sulfone; 4,4′-dihydroxybenzophenone and the like.

Among these, dihydric phenols preferably used are 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1, 1-diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3- Phenylphenyl) propane, 4,4′-dihydroxybiphenyl and bis (4-hydroxyphenyl) sulfone, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used.
These dihydric phenols of the general formula (9) are described in JP-A-4-291348.

[Polymerizable charge transport material (substance) having a carbon-carbon double bond]
The polymerizable charge transport material having a carbon-carbon double bond is a benzidine compound represented by the following general formula (3) or general formula (4). In the structural formula, Act represents an acryloyloxy group, a methacryloyloxy group, R ⁷ , R ⁸ , R ³⁰ , R ³¹ , R ³² , and R ³³ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. E, f are represented by 1 ≦ e + f ≦ 4, and l and m are represented by 1 ≦ l + m ≦ 4.

アクリロイル基の導入は以下のルートで合成される。

Introduction of an acryloyl group is synthesized by the following route.

ビニル基の導入は以下のルートで合成される。

The introduction of the vinyl group is synthesized by the following route.

以下に具体例を示すが、これらに限定されるものでない。

Although a specific example is shown below, it is not limited to these.

  Examples of the polymerizable charge transport material having a carbon-carbon double bond include aminobiphenyl compounds represented by the following general formula (5).

式中、Ａｃｔは炭素−炭素二重結合を表わし、アクリロイルオキシ基、メタクリロイルオキシ基、ビニル基を表わし、Ｒ^９，Ｒ^１０は水素原子、炭素数１〜４のアルキル基を表わし、Ａｒ^１は置換、無置換のアリーレン基を表わし、ｇ，ｋ、ｏはそれぞれ独立に０〜２の整数、好ましくは１≦ｇ＋ｋ＋ｏ≦４を満たす整数を表わし、ｖは０〜１の整数を表わす。
以下に具体例を示すが、これらに限定されるものでない。これらは、前記特許文献２の特許第３０８１７０５号明細書に記載されている。

In the formula, Act represents a carbon-carbon double bond, represents an acryloyloxy group, a methacryloyloxy group, and a vinyl group, R ⁹ and R ¹⁰ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and Ar ¹ represents A substituted or unsubstituted arylene group is represented, g, k, and o each independently represent an integer of 0 to 2, preferably 1 ≦ g + k + o ≦ 4, and v represents an integer of 0 to 1.
Although a specific example is shown below, it is not limited to these. These are described in Japanese Patent No. 3081705 of Patent Document 2.

  Examples of the polymerizable charge transport material having a carbon-carbon double bond include a phenylenediamine compound represented by the following general formula (6).

式中、Ａｃｔは炭素−炭素二重結合を表わし、アクリロイルオキシ基、メタクリロイルオキシ基、ビニル基を表わし、Ｒ^１１，Ｒ^１２は水素原子、炭素数１〜４のアルキル基を表わし、ｐ，ｑは、それぞれ独立に０〜２の整数、好ましくは１≦ｐ＋ｑ≦４を満たす整数を表わす。
以下に具体例を示すが、これらに限定されるものでない。

In the formula, Act represents a carbon-carbon double bond, represents an acryloyloxy group, a methacryloyloxy group, and a vinyl group, R ¹¹ and R ¹² represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, p, q Each independently represents an integer of 0 to 2, preferably 1 ≦ p + q ≦ 4.
Although a specific example is shown below, it is not limited to these.

炭素−炭素二重結合をもった重合性電荷輸送材としては、下記一般式（７）で示される化合物が挙げられる。

Examples of the polymerizable charge transport material having a carbon-carbon double bond include compounds represented by the following general formula (7).

式中、Ａｃｔは、アクリロイルオキシ基、メタクリロイルオキシ基、ビニル基から選択された炭素−炭素二重結合を表わし、Ａｒ^２，Ａｒ^３は置換、無置換のアリール基を表わし、Ｂは

In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group, a methacryloyloxy group, and a vinyl group, Ar ² and Ar ³ represent a substituted or unsubstituted aryl group, and B represents

を表わし、ここでＲ^１３，Ｒ^１４は水素原子、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。ｒは１〜２の整数を表わす。）
以下に具体例を示すが、これらに限定されるものではない。

Wherein R ¹³ and R ¹⁴ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group. r represents an integer of 1 to 2; )
Specific examples are shown below, but are not limited thereto.

炭素−炭素二重結合をもった重合性電荷輸送材としては、下記一般式（８）で示されるトリフェニルアミン化合物が挙げられる。

Examples of the polymerizable charge transport material having a carbon-carbon double bond include a triphenylamine compound represented by the following general formula (8).

式中、Ａｃｔは、アクリロイルオキシ基、メタクリロイルオキシ基、ビニル基から選択された炭素−炭素二重結合を表わしを表わし、Ａｒ^４は置換、無置換のアリール基を表わし、ｓ，ｕはそれぞれ独立に０〜２の整数、好ましくは１≦ｓ＋ｕ≦４を満たす整数を表わす。
以下に具体例を示すが、これらに限定されるものでない。

In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group, a methacryloyloxy group, and a vinyl group, Ar ⁴ represents a substituted or unsubstituted aryl group, and s and u are independent of each other. Represents an integer satisfying 0 to 2, preferably 1 ≦ s + u ≦ 4.
Although a specific example is shown below, it is not limited to these.

  The mixing ratio of the charge transport material having the carbon-carbon double bond of the general formulas (3) to (8) and the polycarbonate resin having the unit represented by the general formula (1) has a carbon-carbon double bond. The polycarbonate resin is 6 to 20 weights, preferably 7 to 15 weights with respect to 10 weights of the charge transport material.

Here, the alkyl group having 1 to 5 carbon atoms specifically includes methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i- A butyl group, n-pentyl group, etc. are mentioned.
Examples of the aryl group include phenyl group, naphthyl group, biphenylyl group, terphenylyl group, pyrenyl group, fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, and the like. Examples of the substituent include the aforementioned alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, specifically, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like.

In the present invention, preferably, a polycarbonate resin having a unit represented by the general formula (1), a radical polymerizable monomer having an acryloyloxy group and / or a methacryloyloxy group together with a charge transport material having a carbon-carbon double bond ( Alternatively, a photosensitive layer is formed with these cured products).
The acryloyloxy group and / or methacryloyloxy group compound is a bifunctional monomer, oligomer, and polymer such as diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meta ) Acrylate, 1,6-hexanediol di (meth) acrylate, etc .; trifunctional monomers, oligomers, polymers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, aliphatic tri (meth) acrylate Etc .; tetrafunctional monomer, oligomer, polymer such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, aliphatic Examples include tetra (meth) acrylates; 5-functional or higher monomers, oligomers, and polymers such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, as well as polyester skeleton, urethane skeleton, and phosphazene skeleton. (Meth) acrylate etc. which have this. In this invention, the said monomer can be used as a 1 type, or 2 or more types of mixture.

  These radically polymerizable monomers having an acryloyloxy group and / or a methacryloyloxy group are 2 with respect to the total weight of the polycarbonate resin having a unit represented by the general formula (1) and the charge transport material having a carbon-carbon double bond. -50% by weight is added, preferably 10-30% by weight.

  Radical polymerization of a coating film to which a polycarbonate resin having a repeating unit represented by the general formula (1) and a charge transport material having a carbon-carbon double bond, or an appropriate acryloyloxy group and / or methacryloyloxy group compound are added. For this purpose, a thermal polymerization initiator or a photopolymerization initiator is contained and cured. The following are mentioned as a thermal-polymerization initiator and a photoinitiator.

  As thermal polymerization initiators, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, methylcyclohexanone 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) he Sun-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-butylperoxybenzoate, di-t-butylperoxytrimethyladipate Peroxides such as azobisisobutyronitrile, azobisdimethylvaleronitrile, azobissi Azo-based, such as Russia hexyl nitrile is used.

  Examples of the photopolymerization initiator include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Acetophenone-based or ketal-based photopolymerization initiators such as methyl-2-morpholino (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether Benzoin ether photopolymerization initiators such as benzoin isopropyl ether, benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoylphenyl ether, acrylated benzophenone, Benzophenone photopolymerization initiators such as 1,4-benzoylbenzene, thioxanthones such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Examples of other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoic acid. Phenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10 -Phenanthrene, an acridine type compound, a triazine type compound, an imidazole type compound is mentioned. Moreover, what has a photopolymerization acceleration effect can also be used individually or in combination with the said photoinitiator. Examples include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4,4'-dimethylaminobenzophenone, and the like.

  These heat and photopolymerization initiators may be added to the formulation solution, respectively, and one or more thermal polymerization initiators, or one or more photopolymerization initiators may be mixed and used. The content of the polymerization initiator is 0.5 to 40 parts by weight, preferably 1 to 20 parts by weight with respect to 100 parts by weight of the total content having radical polymerizability. The half-life of the thermal polymerization initiator is preferably 80 ° C. or higher, and if it is 50 ° C. or lower, the storage stability of the coating solution is deteriorated and the coating is cured.

  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.

  Coating comprising a polycarbonate resin having a unit represented by the general formula (1), a charge transporting substance having a carbon-carbon double bond, and an appropriately added acryloyloxy group and / or methacryloyloxy group compound radical polymerizable compound. It is formed by applying and curing a working fluid. When the radically polymerizable monomer is a liquid, such a coating liquid can be applied by dissolving other components in the liquid, but if necessary, it is diluted with a solvent and applied. Solvents used at this time include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, tetrahydrofuran, dioxane and propyl ether. Ethers such as dichloromethane, halogens such as dichloromethane, dichloroethane, trichloroethane, and chlorobenzene, aromatics such as benzene, toluene, and xylene, and cellosolves such as methyl cellosolve, ethyl cellosolve, and cellosolve acetate. 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 this invention, after apply | coating this coating liquid, an external energy is given and it hardens | cures and forms a crosslinked surface layer, As an external energy used at this time, there exist a heat | fever, light, and a radiation. The heat energy is applied by heating from the coating surface side or the support side using a gas such as air or nitrogen, steam, various heat media, infrared rays, or electromagnetic waves. 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. As the energy of light, UV irradiation light sources such as high-pressure mercury lamps and metal halide lamps, which mainly have an emission wavelength in ultraviolet light, can be used, but a visible light source can also be selected according to the absorption wavelength of radically polymerizable substances and photopolymerization initiators. Is possible. Irradiation light amount is 50 mW / cm ² or more, preferably 1000 mW / cm ² or less, it takes time for the curing reaction is less than 50 mW / cm ^2. If it is higher than 1000 mW / cm ^2, the progress of the reaction becomes non-uniform and the cross-linked surface layer becomes very rough. Examples of radiation energy include those using electron beams. Among these energies, those using heat and light energy are useful because of easy reaction rate control and simple apparatus.
In the system to which the photocuring initiator and the thermosetting initiator of the present invention are added, either the light energy or the heat energy may be given first, and when the light energy such as a high-pressure mercury lamp is given, the projectile is heated to a high temperature. Becomes 80 ° C. or higher, and thermal polymerization curing proceeds,
Since the film thickness of the crosslinked surface layer of the present invention varies depending on the layer structure of the photoreceptor in which the crosslinked surface layer is used, it will be described later together with the layer structure.

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-vinyl carbazole, 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)
The charge transport layer (37) is a layer having a charge transport function, and a polycarbonate resin having a unit represented by the general formula (1) of the present invention and a cross-linked surface layer having a charge transport material having a carbon-carbon double bond are charged. It is useful as a transport layer. When the cross-linked surface layer is the entire charge transport layer (37), a coating liquid is applied onto the charge generation layer (35) as described in the above-mentioned cross-linked surface layer preparation method, and after drying, if necessary, external The curing reaction is initiated by energy, and 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. A polycarbonate resin having a unit represented by the general formula (1) of the present invention is formed by dissolving or dispersing the resin in a suitable solvent, coating the resin on the charge generation layer (35) and drying it. Then, a coating liquid containing a charge transport material having a carbon-carbon double bond is applied and cross-linked 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 the 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 a surface portion of the charge transport layer (37), as described in the above cross-linked surface layer preparation method, it is represented by the general formula (1) of the present invention on the lower layer portion of the charge transport layer. Apply a coating liquid containing a polycarbonate resin with a unit and a charge transport material having a carbon-carbon double bond, and if necessary, after drying, initiate a curing reaction by external energy of heat or light, It 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 forming a charge generation layer, the charge generation material contains a polycarbonate resin having a unit represented by the general formula (1) of the present invention and a charge transport material having a carbon-carbon double bond. After being dispersed together with the coating liquid, coated on the conductive support (31), and dried if necessary, a curing reaction is initiated by light and heat energy 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, a polycarbonate resin having a unit represented by the general formula 1 of the present invention and a carbon-carbon double bond on the lower layer portion of the photosensitive layer as described above A coating liquid containing a charge transporting material and a charge generating material is applied, dried as necessary, and then cured by external energy of heat and light 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 configuration of the present invention is effective when a charging unit such as a contact charging method or a non-contact proximity arrangement charging method is used in which the photosensitive composition is decomposed by proximity discharge from the charging unit. 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. Be 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.
[Copolymer]
About GPC Mn (number average molecular weight) and Mw (weight average molecular weight) of the copolymer used in the examples are those in terms of standard polystyrene by gel permeation chromatography (GPC). Hereinafter, the measurement conditions of this gel permeation chromatography (GPC) will be described.
Apparatus: HLC-8020GPC (manufactured by Tosoh Corporation)
column:
TSKgel SuperH5000 6mmID × 15cm (manufactured by Tosoh Corporation)
TSKgel SuperH4000 6mmID × 15cm (manufactured by Tosoh Corporation)
TSKgel SuperH3000 6mmID × 15cm (manufactured by Tosoh Corporation)
TSKgel SuperH1000 6mmID × 15cm (manufactured by Tosoh Corporation)
Connect the four.
Eluent: THF (tetrahydrofuran) Wako Pure Chemical Industries, Ltd. Flow rate: 0.6 ml / min
Sample concentration: 0.2%
Sample injection volume: 10 μl
Column temperature: 40 ° C
Detector: Differential refractometer (IR detector)
Data analysis: Multi Station GPC-8020 (manufactured by Tosoh Corporation)
Standard polystyrene: TSK standard polystyrene F288, F-128, F-80, F-40, F-20, F4, F-1, A-5000, A-2500, A-1000 (Tosoh Corporation) Made)

  The apparatus, column, and standard polystyrene for measuring these molecular weights are described in the catalog of the apparatus manufacturer, and the measurement procedure is also described in the instruction manuals of the respective companies. For example, it is described in the HPLC hardware edition of the general catalog made by Tosoh Corporation in 1997, the TSK-GEL / Toyopearl / consumables edition in the general catalog made by Tosoh Corporation in 1998, and the instruction manual of the Tosoh high speed GPC apparatus HLC-8120GPC.

The weight average molecular weight in terms of polystyrene is a value calculated using a molecular weight measurement method based on polystyrene having a known molecular weight, and a GPC column is used to measure multiple standard polystyrenes and measurement samples that cover the molecular weight range of the sample. If the measurement is performed under the same conditions, an accurate value can be obtained regardless of the type of apparatus and the type of column. In recent GPC measurement apparatuses, measurement conditions affecting the elution time such as solvent transport and temperature can be made to be the same with high accuracy, and anyone can measure accurately.
Moreover, Tg (glass transition temperature) described simultaneously is measured by a well-known method.
<Copolymer Synthesis Example 1>
4,4′-dihydroxystilbene 1.435 g (6.76 mmol), 2,2-bis (4-hydroxyphenyl) propane 5 g (21.9 mmol), sodium hydroxide 8.88 g (0.222 mol) / ion-exchanged water 108 g of aqueous solution and 0.24 g of hydrosulfite soda were placed in a 300 ml four-diameter flask and dissolved. The mixture was cooled to 7 ° C. in an ice-water bath, 40 mg of 4-tertiary butylphenol was added, and a solution of 5.27 g (17.745 mmol) of triphosgene in 60 ml of methylene chloride was added at once with vigorous stirring. Stirring was continued and the temperature rose to 15 ° C. 15 minutes after the addition, 2 ml of a solution of 75 mg of triethylamine in 10 ml of methylene chloride was added. The temperature rose to 30 ° C and reacted at 29-30 ° C for 1.5 hours. Thereafter, 150 ml of methylene chloride was added to terminate the reaction, and the organic layer was separated, washed with 200 ml of 2% aqueous hydrochloric acid and washed 5 times with 200 ml of ion-exchanged water, and the organic layer was precipitated with 2.5 L of methanol. Yield 6.9g. Mn = 31820, Mw = 75940, Tg (° C.) = 194.

<Copolymer synthesis example 2>
3,4′-dihydroxystilbene 3 g (14.33 mmol), 1,1-bis (4-hydroxyphenyl) cyclohexane 3.845 g (14.33 mmol), sodium hydroxide 8.88 g (0.222 mol) / ion-exchanged water 108 g of aqueous solution and 0.24 g of hydrosulfite soda were placed in a 300 ml four-diameter flask and dissolved. The mixture was cooled to 7 ° C. in an ice-water bath, 40 mg of 4-tertiary butylphenol was added, and a solution of 5.27 g (17.745 mmol) of triphosgene in 60 ml of methylene chloride was added at once with vigorous stirring. Stirring was continued and the temperature rose to 15 ° C. 15 minutes after the addition, 2 ml of a solution of 75 mg of triethylamine in 10 ml of methylene chloride was added. The temperature rose to 30 ° C and reacted at 29-30 ° C for 1.5 hours. Thereafter, 150 ml of methylene chloride was added to terminate the reaction, and the organic layer was separated, washed with 200 ml of 2% aqueous hydrochloric acid and washed 5 times with 200 ml of ion-exchanged water, and the organic layer was precipitated with 2.5 L of methanol. Yield 7.3g. Mn = 38880, Mw = 105720, Tg (° C.) = 224.
Similarly, polymerization was carried out at the quantitative ratios shown in Table 1.
A stilbene polycarbonate copolymer was obtained as described above.

<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. Metal halide lamp: 160 W / cm, irradiation distance: 120 mm, irradiation intensity: 500 mW / cm ² , irradiation time: irradiation for 30 seconds, and then drying at 150 ° C. for 30 minutes to obtain the electrophotographic photoreceptor of the present invention. It was.
[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〕
合成例１のポリカーボネート共重合体 ２部
炭素−炭素二重結合をもつ電荷輸送物質Ｎｏ．１ ２部
トリメチロールプロパントリアクリレート（ＴＭＰＴＡ） ０．５部
光重合開始剤 ０．２部
１−ヒドロキシ−シクロヘキシル−フェニル−ケトン
（イルガキュア１８４、チバ・スペシャルティ・ケミカルズ製）
テトラヒドロフラン（ＴＨＦ） １６部
１％シリコーンオイル（ＫＦ５０ 信越化学社製）ＴＨＦ溶液 ０．１部

[Coating liquid for charge transport layer]
Polycarbonate copolymer of Synthesis Example 1 2 parts Charge transport material No. 1 having a carbon-carbon double bond 1 2 parts Trimethylolpropane triacrylate (TMPTA) 0.5 part Photopolymerization initiator 0.2 part 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
Tetrahydrofuran (THF) 16 parts 1% silicone oil (KF50 manufactured by Shin-Etsu Chemical) THF solution 0.1 part

<Examples 2 to 5>
A photoconductor of the present invention was prepared in the same manner as in Example 1 except that the polycarbonate resin and charge transport material of the charge transport layer coating solution shown in Table 2 were used.

<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)
Low molecular charge transport material (D-1) having the following structural formula (II) 7 parts Tetrahydrofuran 100 parts 1% silicone oil tetrahydrofuran solution 0.2 part (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)

<Comparative example 2>
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]
Polycarbonate copolymer of Synthesis Example 1 2 parts Low molecular charge transport material (D-1) having the following structural formula (II) 1.4 parts Tetrahydrofuran 14 parts Tetrahydrofuran solution of 1% silicone oil 0.1 part (KF50-100CS, (Shin-Etsu Chemical)

<Evaluation>
For hardness measurement, a microhardness meter H-100 manufactured by Fischer Instruments Co., Ltd., was pressed in 30 seconds with a force of Vickers indenter of 9.8 mN, held for 5 seconds, and extracted with a force of 9.8 mN in 30 seconds. Martens hardness and deformation recovery rate were determined. The results are shown below.

The electrophotographic photoreceptors of Examples 1 to 5 and Comparative Examples 1 and 2 were subjected to a paper passing test of 10,000 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 10,000 sheets was measured. The results are shown below. In addition, the sheet passing test was stopped for the photoconductor having a remarkable image defect from the beginning.
The film thickness was measured with an eddy current film thickness meter Fischerscope MMS manufactured by Fischer Instruments.

以上のように本発明の感光体は機械的強度が高く、耐摩耗性が高いものであり、高耐久性が高い。

As described above, the photoreceptor of the present invention has high mechanical strength, high wear resistance, and high durability.

<Example 6>
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, photocured with a photocuring apparatus, and then dried at 150 ° C. for 30 minutes to provide a 7 μm cured charge transporting 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 (V) 12 parts

ＴＨＦ ９０部
１％シリコーンオイル（ＫＦ５０信越シリコーン社製）ジクロルメタン溶液
１部

90 parts of THF 1% silicone oil (KF50 manufactured by Shin-Etsu Silicone) dichloromethane solution
1 copy

[Coating liquid for cross-linked surface layer]
1 part of the polycarbonate copolymer of Synthesis Example 2 20 compounds 1 part Pentaerythritol tetraacrylate (SR-295, manufactured by Nippon Kayaku) 0.5 part Ditrimethylolpropane tetraacrylate (SR-355, manufactured by Nippon Kayaku) 0.25 part Photopolymerization initiator 0.2 part 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
Tetrahydrofuran 30 parts Cyclohexanone 10 parts

<Example 7>
In the same manner as in Example 6, 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 6.
[Coating liquid for cross-linked surface layer]
1 part of the polycarbonate copolymer of Synthesis Example 4 35 compounds 1 part Pentaerythritol tetraacrylate (SR-295, manufactured by Nippon Kayaku) 0.5 part Ditrimethylolpropane tetraacrylate (SR-355, manufactured by Nippon Kayaku) 0.25 part Photopolymerization initiator 0.2 part 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
Tetrahydrofuran 30 parts Cyclohexanone 10 parts

<Comparative Example 3>
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 photoreceptors of Examples 6 and 7 and Comparative Example 3 were mounted on the apparatus shown in FIG. 3 and Imagio Neo1050Pro manufactured by Ricoh Co., Ltd., and 1,000,000 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。

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.

<Example 8>
(Dispersion 1)
A 15 cm ball mill pot was charged with the following charge generation material and solvent, and ball milled for 48 hours using 10φ zirconia media, and then 500 parts of cyclohexanone was added to adjust the mill base.
22 parts of charge generating substance of the following structural formula

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
合成例２のポリカーボネート共重合体 ８部
Ｎｏ．５化合物 ４部
ポリエチレングリコール ０．２部
（イオネットＭＣ１４００ 三洋化成社）
シリコーンオイル（ＫＦ５０ 信越化学社製） ０．０１部
分散液１を１２部、塗工液１を２０部、混合攪拌して塗工液２を調整した。

400 parts of cyclohexanone (coating solution 1)
Tetrahydrofuran (THF) 66 parts Polycarbonate copolymer of Synthesis Example 2 8 parts 5 compounds 4 parts Polyethylene glycol 0.2 parts (Ionette MC1400 Sanyo Kasei)
Silicone oil (KF50, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.01 part 12 parts of dispersion 1 and 20 parts of coating liquid 1 were mixed and stirred to prepare coating liquid 2.

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 φ30 mm aluminum cylinder, dried at 100 ° C. for 10 minutes, and below 0.3 μm. A pull layer was provided. The coating solution 2 was coated thereon to provide a 20 μm single layer photoreceptor. This was irradiated with light under the conditions of a metal halide lamp: 160 W / cm, irradiation distance: 120 mm, irradiation intensity: 500 mW / cm ² , irradiation time: 60 seconds, and then dried at 150 ° C. for 30 minutes, and the electrophotographic photoreceptor of the present invention. Got.

<Comparative example 4>
(Coating fluid 3)
Tetrahydrofuran (THF) 66 parts Polycarbonate resin (C1400, manufactured by Teijin Chemicals Ltd.) 8 parts Low molecular charge transport material (D-1) of the following structural formula (II) 4 parts

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を１２部、塗工液３を２０部、混合攪拌して塗工液４を調整した。

Polyethylene glycol (Ionette MC1400, Sanyo Chemical Co., Ltd.) 0.2 part Silicone oil (KF50, Shin-Etsu Chemical Co., Ltd.) 0.01 part Dispersion 1 is 12 parts, coating liquid 3 is 20 parts, and the mixture is stirred and applied to coating liquid 4 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 φ30 mm aluminum cylinder and dried at 100 ° C. for 10 minutes to provide an undercoat layer of 0.3 μm. It was. A coating liquid 4 was applied thereon to prepare a 20 μm comparative photoconductor.

Example 8 and Comparative Example 4 were mounted on a process cartridge for an electrophotographic apparatus, a 655 nm semiconductor laser was used as an image exposure light source, and an initial dark portion was obtained using a RICOH Imagio Neo 270 remodeled machine with a positive charge polarity. 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.

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 39 Protective layer 101 Photosensitive drum 102 Charging device 103 Exposure device 104 Development device 105 Transfer body 106 Transfer device 107 Cleaning blade

Claims (9)

An electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, a cured product comprising a polycarbonate copolymer represented by the following general formula (2) and a charge transport material having a carbon-carbon double bond: An electrophotographic photoreceptor, which is contained in the uppermost layer of the photosensitive layer .

_(Wherein, R 3, _{R 4} represents a hydrogen atom, a methyl group.

h and i represent copolymerization mol%, h represents 5 to 80, and i represents 20 to 95. )
A cured product comprising a polycarbonate copolymer represented by the general formula (2), a charge transport material having a carbon-carbon double bond, and a radical polymerizable monomer having an acryloyloxy group is contained in the uppermost layer. The electrophotographic photosensitive member according to claim 1.
The electrophotographic photoreceptor according to claim 1 or 2 , wherein the charge transport material having a carbon-carbon double bond is represented by the following general formula (3) .

(In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group and a vinyl group. E and f represent an integer of 0 or 1, and at least one of e and f is 1. R. ⁷ and R ⁸ represent a hydrogen atom or a methyl group.)
3. The electrophotographic photosensitive member according to claim 1, wherein the charge transport material having a carbon-carbon double bond is represented by the following general formula (5).

(In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group and a vinyl group. G, k, and o represent an integer of 0 or 1, and at least any one of g, k, and o. One is 1. Ar ¹ represents a phenylene group, v represents an integer of 0 or 1. R ⁹ and R ¹⁰ represent a hydrogen atom and a methyl group.)
The electrophotographic photoreceptor according to claim 1 or 2 , wherein the charge transport material having a carbon-carbon double bond is represented by the following general formula (6).

(In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group and a vinyl group. P and q represent an integer of 0 or 1, and one of p and q is at least 1. R ¹¹ and R ¹² represent a hydrogen atom or a methyl group .)
The electrophotographic photoreceptor according to claim 1 or 2, wherein the charge transport material having a carbon-carbon double bond is represented by the following general formula (7).

(In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group and a vinyl group. R represents an integer of 1. Ar ² and Ar ³ represent a substituted or unsubstituted aryl group;
B is

Wherein R ¹³ and R ¹⁴ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group. )
The electrophotographic photoreceptor according to claim 1 or 2 , wherein the charge transport material having a carbon-carbon double bond is represented by the following general formula (8).

(In the formula, Act represents a carbon-carbon double bond selected from an acryloyloxy group and a vinyl group. S and u each independently represents an integer of 0 or 1, and at least one of s and u is 1) is. Ar ⁴ are a substituted or unsubstituted aryl group. 8. 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 7. An image forming apparatus. An electrophotographic photosensitive member according to any one of claims 1 to 7, a 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.

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