JP2007017933A - Electrophotographic photoreceptor, image forming method using same, image forming apparatus, and process cartridge for image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor, which is superior in abrasion resistance more than the conventional types, which is proper in electrical characteristics and reduced in image defects such as white spots with long lifetime in the electrophotographic photoreceptor, and also to provide the electrophotographic photoreceptor with the long lifetime, that is compatible with a blue-violet laser writing light source. <P>SOLUTION: The electrophotographic photoreceptor has a cured coating composition, obtained by radical polymerization of at least the following component A (where A: a radical polymerizing monomer obtained by linking an aliphatic group having two radical polymerizing groups with a charge transport group that does not contain radical polymerizing groups by a single bond) on the surface thereof. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a highly wear-resistant organic electrophotographic photosensitive member having an abnormal printing durability of 2 million sheets in terms of a photosensitive member having a diameter of 100 mm. Further, the present invention relates to chargeability, sensitivity, and residual potential accumulation. The present invention relates to a highly durable and reliable electrophotographic photosensitive member that has excellent electrical characteristics such as, and that maintains high image quality with few image defects, and also relates to an electrophotographic photosensitive member that is less prone to image defects such as white spots. It is. The present invention also relates to a highly durable organic electrophotographic photosensitive member having a wide correspondence range to a writing light source wavelength that can be applied to a blue-violet laser writing light source. The present invention also relates to an image forming method, an image forming apparatus, and a process cartridge for the image forming apparatus using a 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. For this reason, for example,
(1) Optical characteristics such as light absorption wavelength range and absorption amount (2) Electrical characteristics such as high sensitivity and stable charging characteristics (3) Wide selection range of materials (4) Manufacturing Ease (5) Low cost (6) Non-toxicity etc. are mentioned.

  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 charge transport layer is mainly composed of a low molecular charge transport material and an inert polymer. There is a drawback that wear is likely to occur due to a mechanical load.

  In addition, due to the demand for higher image quality, the cleaning blade is required to increase its rubber hardness and contact pressure for the purpose of improving the cleaning property as the particle size of the toner particles is reduced. This also promotes wear of the photoreceptor. It 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. Therefore, various improvements in wear resistance have been made.
(1) A material using a curable binder for the charge transport layer (see, for example, Patent Document 1).
(2) A material using a polymer type charge transport material (for example, see Patent Document 2).
(3) A material in which an inorganic filler is dispersed in a charge transport layer (see, for example, Patent Document 3).
(4) A polyfunctional acrylate monomer cured product (for example, see Patent Document 4).
(5) Provided with a charge transport layer formed 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 (for example, Patent Documents) 5).
(6) A compound containing a compound obtained by curing a hole transporting compound having two or more chain polymerizable functional groups in the same molecule (see, for example, Patent Documents 6 and 7).

  Although these improvements have improved wear resistance compared to conventional products, new problems have arisen. Conventional photoconductors are refaced due to wear even if foreign matter adheres to or scratches on the surface, and image defects are not dragged indefinitely. However, photoconductors with improved wear resistance once have strong foreign matter on the surface. When sticking or scratches occur, the state remains indefinitely and continues to produce image defects. Thus, there is a problem that image defects are likely to occur.

Particularly in recent years, due to the demand for higher image quality and energy saving, the particle size of the toner is small and the softening temperature is low. In order to ensure its fluidity, it is common to add inorganic fine particles such as silica to the toner. It has come to be. In some cases, the silica particles may pierce the OPC surface during the development process, and a wax component of toner or the like is deposited on the periphery of the silica particles, making it impossible to develop, resulting in the occurrence of white spot image defects.
In addition, along with further higher image quality and higher durability in recent years, it is necessary to make wear resistance and residual potential storage properties compatible at a higher level.

JP 56-48637 A JP-A 64-1728 JP-A-4-281461 Japanese Patent No. 3262488 Japanese Patent No. 3194392 JP 2000-66425 A JP 2004-221959 A

  Accordingly, an object of the present invention is to provide an electrophotographic photosensitive member that has a longer life than conventional ones, has better wear resistance, better electrical characteristics, and fewer image defects due to white spots or the like. Another problem is to provide the long-life electrophotographic photosensitive member that can be used for a blue-violet laser writing light source.

  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 that use a long-life photoconductor with few white spot image defects and realize high image quality over a long period of time.

The above-mentioned problem is (1) “electrophotographic photoreceptor characterized in that it has on its surface a cured coating composition obtained by radical polymerization of at least the following component A;
(A: Radical polymerizable monomer in which an aliphatic group having two radical polymerizable groups and a charge transporting group not containing a radical polymerizable group are linked by a single bond)
(2) “Electrophotographic photosensitive member having a surface having a cured coating composition obtained by radical polymerization of at least the following components A and B;
(A: a radical polymerizable monomer in which an aliphatic group having two radical polymerizable groups and a charge transporting group not containing a radical polymerizable group are linked by a single bond)
(B: radical polymerizable monomer having three or more radical polymerizable groups in the molecule) ",
(3) “Electrophotographic photosensitive member having a surface having a cured coating composition obtained by radical polymerization of at least the following components A, B and C;
(A: a radical polymerizable monomer in which an aliphatic group having two radical polymerizable groups and a charge transporting group not containing a radical polymerizable group are linked by a single bond)
(B: radical polymerizable monomer having three or more radical polymerizable groups in the molecule)
(C: photopolymerization initiator) ",
(4) Any one of the items (1) to (3), wherein the radical polymerizable group of the component A and / or the component B is an acryloyloxy group and / or a methacryloyloxy group The electrophotographic photosensitive member described,
(5) The electrons according to the items (1) to (4), wherein the aliphatic group having two radical polymerizable groups of the component A is represented by the following general formula (1) Photographic photoreceptor;

（式中、Ｒａ、Ｒｂはそれぞれ水素原子またはメチル基を表わす。）」、
（６）「前記Ａ成分が下記一般式（２）で表わされるラジカル重合性モノマーであることを特徴とする前記第（１）項乃至第（５）項に記載の電子写真感光体；

(Wherein Ra and Rb each represents a hydrogen atom or a methyl group) "
(6) "The electrophotographic photosensitive member according to any one of (1) to (5) above, wherein the component A is a radical polymerizable monomer represented by the following general formula (2);

（式中、Ｒａ、Ｒｂはそれぞれ水素原子またはメチル基を表し、Ｒｃ、Ｒｄは、置換基を有しても良い炭素数１〜６のアルキル基、置換基を有しても良いアルコキシ基、置換基を有しても良いアリール基を表し、Ａｒ_１、Ａｒ_２は、置換基を有しても良いアリール基を表し、ｉ、ｊは０〜４の整数を表す。また、ＲｃとＲｄは結合してビフェニール環と共に炭素数５〜８の環状炭化水素環を形成しても良い。）」、
（７）「前記Ａ成分が下記一般式（３）で表されるラジカル重合性モノマーであることを特徴とする前記第（１）項乃至第（６）項に記載の電子写真感光体；

(In the formula, Ra and Rb each represent a hydrogen atom or a methyl group, and Rc and Rd each represents an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted alkoxy group, An aryl group that may have a substituent is represented, Ar ₁ and Ar ₂ represent an aryl group that may have a substituent, and i and j represent an integer of 0 to 4. Rc and Rd May be combined with a biphenyl ring to form a C5-C8 cyclic hydrocarbon ring.
(7) The electrophotographic photosensitive member according to any one of (1) to (6) above, wherein the component A is a radical polymerizable monomer represented by the following general formula (3);

（式中、Ｒａ、Ｒｂはそれぞれ水素原子またはメチル基を表し、Ｒｃ、Ｒｄ、Ｒｅ、Ｒｆは、置換基を有しても良い炭素数１〜６のアルキル基、置換基を有しても良いアルコキシ基、置換基を有しても良いアリール基を表し、ｉ、ｊは０〜４の整数をｋ、ｌは０〜５の整数を表わす。また、ＲｃとＲｄは結合してビフェニール環と共に炭素数５〜８の環状炭化水素環を形成しても良い。）」、
（８）「前記Ａ成分が下記一般式（４）で表されるラジカル重合性モノマーであることを特徴とする前記第（１）項乃至第（５）項のいずれかに記載の電子写真感光体；

(In the formula, Ra and Rb each represent a hydrogen atom or a methyl group, and Rc, Rd, Re, and Rf each have a C 1-6 alkyl group that may have a substituent or a substituent. Represents a good alkoxy group or an aryl group which may have a substituent, i and j represent an integer of 0 to 4 and k represents an integer of 0 to 5. Rc and Rd are bonded to form a biphenyl ring. And may form a cyclic hydrocarbon ring having 5 to 8 carbon atoms.
(8) The electrophotographic photosensitive member according to any one of (1) to (5), wherein the component A is a radical polymerizable monomer represented by the following general formula (4): body;

（式中、Ｒａ、Ｒｂは水素原子またはメチル基を表し、Ｒｃ、Ｒｄは、置換基を有しても良い炭素数１〜６のアルキル基、置換基を有しても良いアルコキシ基、置換基を有しても良いアリール基を表し、Ａｒ₁、Ａｒ₂は、置換基を有しても良いアリール基を表し、ｉ、ｊは０〜４の整数を表わす。）」、
（９）「前記Ａ成分が下記一般式（５）で表されるラジカル重合性モノマーであることを特徴とする前記第（１）項乃至第（５）項のいずれか前記第（１）項又は第（８）項に記載の電子写真感光体；

(In the formula, Ra and Rb represent a hydrogen atom or a methyl group, and Rc and Rd each represent an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted alkoxy group, and a substituted group. An aryl group which may have a group, Ar ₁ and Ar ₂ each represent an aryl group which may have a substituent, and i and j each represents an integer of 0 to 4).
(9) Any one of the above items (1) to (5), wherein the component A is a radical polymerizable monomer represented by the following general formula (5) Or the electrophotographic photosensitive member according to item (8);

（式中、Ｒａ、Ｒｂは水素原子またはメチル基を表し、Ｒｃ、Ｒｄ、Ｒｅ、Ｒｆは、置換基を有しても良い炭素数１〜６のアルキル基、置換基を有しても良いアルコキシ基、置換基を有しても良いアリール基を表し、ｉ、ｊは０〜４の整数をｋ、ｌは０〜５の整数を表わす。）」、
（１０）「導電性支持体上に少なくとも電荷発生層、電荷輸送層及び架橋型電荷輸送層を順次積層した電子写真感光体において、該架橋型電荷輸送層が前記第（１）項乃至第（９）項のいずれかに記載の硬化被覆組成物を含むことを特徴とする電子写真感光体」、
（１１）「前記架橋型電荷輸送層の膜厚が１μｍ以上、１０μｍ以下であることを特徴とする前記第（１０）項に記載の電子写真感光体」、
（１２）「前記架橋型電荷輸送層が有機溶剤に対し不溶性であることを特徴とする前記第（８）項又は第（１１）に記載の電子写真感光体」、
（１３）「前記架橋型電荷輸送層に用いられる硬化被覆組成物のＢ成分のラジカル重合性官能基数に対する分子量の割合（分子量／官能基数）が、２５０以下であることを特徴とする前記第（８）項乃至第（１２）項のいずれかに記載の電子写真感光体」により達成される。
（１４）また、上記課題は、本発明の「前記（１）項乃至前記（１３）項のいずれかに記載の電子写真感光体を用いて、少なくとも帯電、画像露光、現像、転写を繰り返し行なうことを特徴とする画像形成方法」により達成される。
（１５）また、上記課題は、本発明の「前記第（１）項乃至第（１３）項のいずれかに記載の電子写真感光体を有することを特徴とする画像形成装置」により達成される。
（１６）また、上記課題は、本発明の「前記第（１）項乃至第（１３）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、転写手段、クリーニング手段および除電手段よりなる群から選ばれた少なくとも一つの手段を有するものであって、画像形成装置本体に着脱可能とした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」により達成される。

(In the formula, Ra and Rb represent a hydrogen atom or a methyl group, and Rc, Rd, Re, and Rf may have a C 1-6 alkyl group or substituent which may have a substituent. An alkoxy group and an aryl group which may have a substituent, i and j represent an integer of 0 to 4 and k represents an integer of 0 to 5). "
(10) In the electrophotographic photosensitive member in which at least a charge generation layer, a charge transport layer, and a crosslinkable charge transport layer are sequentially laminated on a conductive support, the crosslinkable charge transport layer includes the above items (1) to ( 9) an electrophotographic photoreceptor comprising the cured coating composition according to any one of items 9),
(11) “The electrophotographic photosensitive member according to (10) above, wherein the cross-linked charge transport layer has a thickness of 1 μm or more and 10 μm or less”,
(12) "The electrophotographic photosensitive member according to (8) or (11) above, wherein the cross-linked charge transport layer is insoluble in an organic solvent",
(13) The ratio of the molecular weight to the number of radically polymerizable functional groups of the B component of the cured coating composition used for the crosslinkable charge transport layer (molecular weight / functional group number) is 250 or less. This is achieved by the electrophotographic photosensitive member according to any one of items 8) to (12).
(14) Further, the above-described problem is that at least charging, image exposure, development, and transfer are repeatedly performed using the electrophotographic photosensitive member according to any one of the items (1) to (13) of the present invention. This is achieved by an “image forming method”.
(15) Further, the above object is achieved by “an image forming apparatus comprising the electrophotographic photosensitive member according to any one of (1) to (13)” of the present invention. .
(16) Further, the above-described problems are solved by the electrophotographic photosensitive member according to any one of the above-mentioned items (1) to (13), a charging unit, a developing unit, a transfer unit, a cleaning unit, and a static eliminating unit. It is achieved by an image forming apparatus process cartridge having at least one means selected from the group consisting of means and detachable from the main body of the image forming apparatus.

  As described above, as is clear from the detailed and specific description, according to the present invention, an electrophotographic photosensitive member provided with a surface layer of a cured coating composition obtained by radical polymerization of at least the component A is resistant. It is possible to provide an electrophotographic photosensitive member having both excellent wear characteristics and electrical characteristics, and a long-life photosensitive member with few image defects due to white spots. In particular, by having a cured coating composition obtained by radical polymerization of the A component and the B component on the surface, an electrophotographic photosensitive member having excellent charge mobility with low residual potential while having excellent wear resistance, which has never been achieved before. The body can be provided.

In particular, an electrophotographic photoreceptor having a cured coating composition obtained by radical polymerization of the A, B, and C components on the surface can easily produce a photoreceptor having the above-described excellent characteristics in a short time. It can be offered to the market at a low price.
In addition, when the A component represented by the general formula (4) and the general formula (5) is used, it is possible to provide a photoconductor with few image defects and excellent wear resistance and potential stability at a very high level. Become.

  Therefore, by using this photoconductor, it is possible to provide an image forming method, an image forming apparatus, and a process cartridge for an image forming apparatus that realize high image quality over a long period of time.

Hereinafter, the present invention will be described in detail.
The present invention is based on an electrophotographic photosensitive member having a cured film obtained by radical polymerization of a specific radical polymerizable monomer on its surface, an image forming method using the same, an image forming apparatus, and a process cartridge for the image forming apparatus. Yes.

  The radical polymerizable monomer here has both a structure exhibiting a charge transporting function and a radical polymerizable structure, and a cured film obtained by polymerization functions as a charge transporting film. A number of radically polymerizable monomers having such a structure that expresses a charge transporting function and a radically polymerizable group have been proposed so far. For example, JP-A-2004-212959 discloses four hundred and ten kinds of compounds. An example is given.

  However, these conventional radical polymerizable monomers cannot achieve both high wear resistance and electrical characteristics with small residual potential at a high level. The cause is considered as follows.

  In order to achieve a high degree of wear resistance that can hardly be scraped, it has been found that the crosslinking density needs to be increased sufficiently, but in order to do so, it is necessary to increase the content ratio of radically polymerizable groups. It is necessary to polyfunctionalize the polymerizable group or reduce the molecular weight of the charge transporting structure. However, there is a limit to lowering the molecular weight of a structure that exhibits good charge transport properties. On the other hand, polyfunctionalization of the radical polymerizable group is effective for increasing the content ratio, but the charge transportability after curing is deteriorated. The cause of this is not well understood, but it is presumed that the molecular movement of the charge-transporting structure is restricted by cross-linking, reducing the range of free movement and reducing charge hopping mobility. Is done.

  Therefore, a new radical polymerizable monomer that can achieve both high-density radical polymerizability and charge transportability was studied, and an aliphatic group having two radical polymerizable groups and a charge transporting group not containing a radical polymerizable group were found. It has been found that a film cured using a radically polymerizable monomer linked by a single bond is effective in achieving both high-density radical polymerizability and good charge transportability.

  Its charge transport is composed of aromatic compounds that are bulky and difficult to move at the cross-linked part of the aliphatic structure that is relatively easy to move so as to reduce the molecular movement constraints of the charge-transporting group as much as possible despite the high cross-linking density. The sex groups were linked in a pendant form so that they could be easily rotated with a single bond. It is considered that such a structure can achieve both high-density radical curability and good charge transportability.

  In addition, when a conventional polyfunctional charge transporting monomer is used, there is a problem that distortion at the time of curing increases, cracks such as cracks occur, and a problem that insufficient curability occurs despite the polyfunctionality. In the curing of the specific radical polymerizable monomer of the present application, a uniform and smooth film that is sufficiently crosslinked and cured without generation of cracks or the like is obtained, and functions as a good photoreceptor surface layer.

  In addition, the formation of a high-density charge-transporting cured film enables the film strength to be sufficiently high and prevents external additives in extremely hard toner such as silica fine particles from sticking to the photoreceptor. In addition, image defects such as white spots can be reduced.

  In addition, in order to realize a high-density crosslinked cured film, a radical polymerizable monomer having 3 or more radical polymerizable groups as the B component in the molecule is used in combination with the radical polymerizable monomer of the A component. Will be more achieved.

  Various conventionally known methods can be applied to initiate radical polymerization. A photopolymerization initiator having a high crosslink density and excellent mechanical strength can be obtained by adding a photopolymerization initiator and curing in a short time by light irradiation. .

Next, each component will be described.
First, the A component will be described.
Regarding radically polymerizable monomers in which an aliphatic group having two radically polymerizable groups and a charge transporting group not containing a radically polymerizable group are linked by a single bond, any conventionally known radically polymerizable group may be used. Applicable. For example, vinyl group, allyl group, acryloyloxy group, methacryloyloxy group, acrylamide group and the like.

  In particular, an acryloyloxy group or a methacryloyloxy group is preferable from the viewpoint of polymerization characteristics. By using an acryloyloxy group or a methacryloyloxy group, it is possible to produce a smooth film that is sufficiently cured in a short time.

  Although there is no restriction | limiting in particular as an aliphatic group, The aliphatic group formed combining a C1-C10 alkyl group and an ether bond is preferable.

One particularly preferred example of the aliphatic group having two radically polymerizable groups is a group represented by the general formula (1). In the formula, Ra and Rb each represent a hydrogen atom or a methyl group, and Ra and Rb may be the same or different.
This group has a good balance between high radical polymerization curability and appropriate flexibility, and is extremely effective in achieving both radical reaction curability and charge transportability.

  The charge transporting group that does not contain a radical polymerizable group may be a monovalent group derived from a charge transporting compound that does not contain the vinyl group, allyl group, acryloyloxy group, methacryloyloxy group, acrylamide group, or the like.

  The charge transporting compound is a compound having a property of transporting charges generated by light reception in the photosensitive layer by hopping conduction or the like. The charge transport compound includes a hole transport material and an electron transport material. Specific examples of the electron transport material include, for example, chloranil, bromoanil, 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, Examples thereof include electron accepting substances such as 7-trinitrodibenzothiophene-5,5-dioxide and diphenoquinone derivatives.

  Specific examples of hole transport materials include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives. And other known materials such as triarylmethane derivatives, 9-styrylanthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives, and the like.

Of the radically polymerizable monomers of the component A described above, those represented by the general formula (2) are particularly preferable.
Furthermore, what is represented by the said General formula (3) as a thing which can respond | correspond well also to a blue-violet laser writing light source in General formula (2) is mentioned as a more preferable material.

In the general formulas (2) and (3) and (4) and (5), Ra and Rb represent a hydrogen atom or a methyl group. Since a difference in radical polymerizability occurs between a hydrogen atom and a methyl group, the hydrogen atom and the methyl group are appropriately selected depending on the use environment. Ra and Rb may be the same or different.
Examples of the aryl group which may have a substituent for Ar ₁ and Ar ₂ include a phenyl group, a naphthyl group, a biphenylyl group, a terphenylyl group, a pyrenyl group, a fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, and an azulenyl group. , Anthryl group, triphenylenyl group, chrycenyl group, and the like, and also a group represented by the following general formula (6).

〔式中、Ｘは−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−及び以下の２価基を表わす。

Wherein, X is -O -, - S -, - SO -, - SO 2 -, - CO- and represent divalent groups below.

（ここで、Ｒ_２６、Ｒ_２７は水素原子、ハロゲン原子、置換基を有しても良いアルキル基、置換基を有しても良いアルコキシ基、置換基を有しても良いアリール基を表し、ａは１〜１２の整数、ｂは１〜３の整数を表わす。）〕

(Here, R ₂₆ and R ₂₇ represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. A represents an integer of 1 to 12, and b represents an integer of 1 to 3)]

As R <_26> , R < ₂₇ > of the said General formula (6), (8), the C1-C6 alkyl group which may have a halogen atom, a substituent, and the alkoxy group which may have a substituent. Can be mentioned. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, and i-butyl. Group, n-pentyl group, n-hexyl group, cyclohexyl group and the like, and examples of the substituent include a halogen atom and a phenyl group. Moreover, the alkoxy group which may have a substituent represents the alkoxy group which has the C1-C6 alkyl group which may have the said substituent, As a specific example, a methoxy group, an ethoxy group, Examples include n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, benzyloxy group and the like.
Examples of the aryl group which may have a substituent include a phenyl group, a naphthyl group, a biphenylyl group, a terphenylyl group, a pyrenyl group, a fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, and a triphenylenyl group. And a chrysenyl group, and examples of these substituents include halogen atoms and alkyl groups having 1 to 6 carbon atoms. The halogen atom and the alkyl group having 1 to 6 carbon atoms are the same as described above.
Specific examples of the halogen atom so far include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Rc, Rd, Re, and Rf represent an alkyl group having 1 to 6 carbon atoms that may have a substituent, an alkoxy group that may have a substituent, and an aryl group that may have a substituent. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, An n-pentyl group, an n-hexyl group, a cyclohexyl group and the like can be mentioned. Examples of the substituent include a halogen atom and a phenyl group. Specific examples of the alkyl group having 1 to 6 carbon atoms which may have a substituent include a methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n- A butyl group, i-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, trifluoromethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group and the like can be mentioned.

  The alkoxy group represents an alkoxy group having an alkyl group having 1 to 6 carbon atoms which may have the above substituent, and specific examples thereof include methoxy group, ethoxy group, n-propoxy group, i-propoxy group. Group, t-butoxy group, n-butoxy group, benzyloxy group and the like.

  Examples of the aryl group include a phenyl group, a naphthyl group, a biphenylyl group, a terphenylyl group, a pyrenyl group, a fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, and a chrysenyl group. It is done.

Examples of these substituents include halogen atoms and alkyl groups having 1 to 6 carbon atoms. The halogen atom and the alkyl group having 1 to 6 carbon atoms are the same as described above.
Specific examples of the halogen atom so far include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the general formulas (2) and (3), Rc and Rd may be bonded to form a cyclic hydrocarbon ring having 5 to 8 carbon atoms together with the biphenyl ring. The following partial structure is mentioned as a specific example in that case.

Specific examples of the present compound are shown below as a typical example in which Ra is a hydrogen atom and Rb is a methyl group in the general formula (2).
The same applies when Ra is a methyl group and Rb is a hydrogen atom, when Ra and Rb are both hydrogen atoms, and when both Ra and Rb are methyl groups.

Specific examples of the present compound are shown below as a representative example where Ra and Rb are hydrogen atoms in the general formula (4).
The same applies when Ra is a methyl group and Rb is a hydrogen atom, when Ra is a hydrogen atom and Rb is a methyl group, and when both Ra and Rb are methyl groups.

  The radical polymerizable monomer represented by the general formula (2) is a novel substance and can be easily synthesized by, for example, the following production method.

  At this time, the following similar structure is by-produced depending on the opening direction of the epoxy ring.

これらの分離は容易ではなく、混合体として使用することもできる。混合体として使用しても特性に影響がなく、コスト的に有利である。

These separations are not easy and can be used as a mixture. Even if it is used as a mixture, there is no effect on the properties, which is advantageous in terms of cost.

  Further, it can be easily synthesized even if the step A-2 is changed to the following method.

  The following similar compounds are by-produced depending on the ring opening direction of the epoxy ring as in the step A-2.

Also in this case, it can be used as a mixture. When Ra and Rb are different in the next step A-3, a mixture of similar compounds is obtained.
Moreover, it is compoundable also with the following method which goes through the following hydrolyzate of the epoxy compound in the B-1 process, or the compound represented by General formula (9).

  This synthesis method is easy to apply when Ra and Rb in the general formula (1) are the same.

  The radical polymerizable monomer represented by the general formula (4) is a novel substance and can be easily synthesized by, for example, the following production method.

  At this time, the following similar structure is by-produced depending on the opening direction of the epoxy ring.

これらの分離は容易ではなく、混合体として使用することもできる。混合体として使用しても特性に影響がなく、コスト的に有利である。

These separations are not easy and can be used as a mixture. Even if it is used as a mixture, there is no effect on the properties, which is advantageous in terms of cost.

  Moreover, it can be easily synthesized even if the A-2 ′ step is changed to the following method.

  Similar to the A-2 ′ step, the following similar compounds are by-produced depending on the opening direction of the epoxy ring.

この場合も混合体として使用することができ、次のＡ−３‘工程でＲａとＲｂが異なる場合は、類似化合物の混合体が得られる。
また、Ｂ−１‘工程におけるエポキシ化合物又は一般式（１０）で表わされる化合物の下記加水分解物を経由する次の方法でも合成出来る。

Also in this case, it can be used as a mixture. When Ra and Rb are different in the next step A-3 ′, a mixture of similar compounds is obtained.
Moreover, it is compoundable also with the following method which goes through the following hydrolyzate of the epoxy compound in a B-1 'process, or the compound represented by General formula (10).

この合成法では、一般式（４）のＲａとＲｂを同じとする場合に適用しやすい。

This synthesis method is easy to apply when Ra and Rb in the general formula (4) are the same.

  Steps A-3 and A-3 'and steps C-1 and C-1' are acrylation steps and can be synthesized in the same manner as in the esterification of a conventional hydroxy compound. That is, (meth) acrylic acid or its ester compound is allowed to act on the alcohol derivative. For example, an alcohol derivative and (meth) acrylic acid can be synthesized by heating and stirring while dehydrating in an organic solvent together with an esterification catalyst such as p-toluenesulfonic acid. It can also be easily synthesized by reacting an alcohol derivative and acrylic acid chloride in an organic solvent in the presence of an alkali.

As the alkali, for example, an alkali aqueous solution such as sodium hydroxide or potassium hydroxide, or an amine base such as triethylamine or pyridine can be used.
As the organic solvent, a hydrocarbon solvent such as toluene, an ether solvent such as tetrahydrofuran, an ester solvent such as ethyl acetate, or the like can be used.

In the esterification in the steps C-1 and C-1 ′, instead of using acrylic acid chloride, 3-chloropropanoic acid chloride is used to form a 3-chloropropanoic acid ester derivative, and then a base catalyst such as triethylamine is used. In addition, an acrylic ester derivative can be synthesized by heating and stirring and dehydrochlorination. By using this method, high yielding acrylation is possible.
A preferable solvent in this case is N, N-dimethylacetamide, and the reaction temperature is 0 to 100 ° C., preferably 10 to 80 ° C.

Next, the B component will be described.
Examples of the radical polymerizable monomer having three or more radical polymerizable groups in the molecule include hole transport structures such as triarylamine, hydrazone, pyrazoline, carbazole, such as condensed polycyclic quinone, diphenoquinone, cyano group, and nitro group. A monomer that does not have an electron transport structure such as an electron-withdrawing aromatic ring and has three or more radically polymerizable functional groups. The radical polymerizable functional group may be any group as long as it has a carbon-carbon double bond and is capable of radical polymerization. Examples of these radical polymerizable functional groups include 1-substituted ethylene functional groups and 1,1-substituted ethylene functional groups shown below.

(1) Examples of the 1-substituted ethylene functional group include a functional group represented by the general formula (11).

（ただし、式中、Ｘ_１は、置換基を有していてもよいフェニレン基、ナフチレン基等のアリーレン基、置換基を有していてもよいアルケニレン基、−ＣＯ−基、−ＣＯＯ−基、−ＣＯＮ（Ｒ_１０）−基（Ｒ_１０は、水素、メチル基、エチル基等のアルキル基、ベンジル基、ナフチルメチル基、フェネチル基等のアラルキル基、フェニル基、ナフチル基等のアリール基を表わす。）、または−Ｓ−基を表わす。）

(In the formula, X ₁ is an arylene group such as a phenylene group or a naphthylene group which may have a substituent, an alkenylene group which may have a substituent, a —CO— group, a —COO— group. , —CON (R ₁₀ ) — group (R ₁₀ represents an alkyl group such as hydrogen, methyl group or ethyl group, an aralkyl group such as benzyl group, naphthylmethyl group or phenethyl group, or an aryl group such as phenyl group or naphthyl group. Or the —S— group.)

  Specific examples of these substituents include a vinyl group, a styryl group, a 2-methyl-1,3-butadienyl group, a vinylcarbonyl group, an acryloyloxy group, an acryloylamide group, and a vinyl thioether group.

(2) Examples of the 1,1-substituted ethylene functional group include a functional group represented by the general formula (12).

（ただし、式中、Ｙは、置換基を有していてもよいアルキル基、置換基を有していてもよいアラルキル基、置換基を有していてもよいフェニル基、ナフチル基等のアリール基、ハロゲン原子、シアノ基、ニトロ基、メトキシ基あるいはエトキシ基等のアルコキシ基、−ＣＯＯＲ_１１基（Ｒ_１１は、水素原子、置換基を有していてもよいメチル基、エチル基等のアルキル基、置換基を有していてもよいベンジル、フェネチル基等のアラルキル基、置換基を有していてもよいフェニル基、ナフチル基等のアリール基、または−ＣＯＮＲ_１２Ｒ_１３（Ｒ_１２およびＲ_１３は、水素原子、置換基を有していてもよいメチル基、エチル基等のアルキル基、置換基を有していてもよいベンジル基、ナフチルメチル基、あるいはフェネチル基等のアラルキル基、または置換基を有していてもよいフェニル基、ナフチル基等のアリール基を表わし、互いに同一または異なっていてもよい。）、また、Ｘ_２は上記式（１１）のＸ_１と同一の置換基及び単結合、アルキレン基を表わす。ただし、Ｙ，Ｘ_２の少なくとも何れか一方がオキシカルボニル基、シアノ基、アルケニレン基、及び芳香族環である。）

(In the formula, Y is an aryl group such as an alkyl group which may have a substituent, an aralkyl group which may have a substituent, a phenyl group which may have a substituent, or a naphthyl group. Group, halogen atom, cyano group, nitro group, alkoxy group such as methoxy group or ethoxy group, -COOR ₁₁ group (R ₁₁ is a hydrogen atom, an alkyl such as an optionally substituted methyl group or ethyl group) Group, an aralkyl group such as benzyl which may have a substituent, a phenethyl group or the like, an aryl group such as a phenyl group or a naphthyl group which may have a substituent, or -CONR ₁₂ R ₁₃ (R ₁₂ and R ₁₃ is a hydrogen atom, which may have a substituent an alkyl group such as methyl group and ethyl group, which may have a substituent group benzyl group, naphthylmethyl group, or Ara such phenethyl group, Kill group or substituent a phenyl group which may have a, an aryl group such as a naphthyl group, which may be the same or different from each other.) Further, X ₂ and X ₁ in the formula (11) Represents the same substituent, a single bond, and an alkylene group, provided that at least one of Y and X ₂ is an oxycarbonyl group, a cyano group, an alkenylene group, and an aromatic ring.)

Specific examples of these substituents include an α-acryloyloxy chloride group, a methacryloyloxy group, an α-cyanoethylene group, an α-cyanoacryloyloxy group, an α-cyanophenylene group, and a methacryloylamino group. In addition, examples of the substituent further substituted with the substituent for X ₁ , X ₂ , and Y include, for example, a halogen atom, a nitro group, a cyano group, a methyl group, an alkyl group such as an ethyl group, a methoxy group, an ethoxy group, and the like And an aryloxy group such as a phenoxy group, an aryl group such as a phenyl group and a naphthyl group, and an aralkyl group such as a benzyl group and a phenethyl group. Among these radical polymerizable functional groups, acryloyloxy group and methacryloyloxy group are particularly useful, and a compound having three or more acryloyloxy groups is, for example, a compound having three or more hydroxyl groups in the molecule and an acrylic group. It can be obtained by using an acid (salt), an acrylic acid halide, or an acrylic ester to cause an ester reaction or a transesterification reaction. A compound having three or more methacryloyloxy groups can be obtained in the same manner. Further, the radical polymerizable functional groups in the monomer having three or more radical polymerizable functional groups may be the same or different.

  Examples of the radical polymerizable monomer having three or more radical polymerizable groups in the molecule include the following, but are not limited to these compounds. That is, as the radical polymerizable monomer used in the present invention, for example, trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate trimethylolpropane alkylene-modified triacrylate, trimethylolpropane ethyleneoxy modification (hereinafter referred to as EO modification). Triacrylate, trimethylolpropylenepropyleneoxy-modified (hereinafter PO-modified) triacrylate, trimethylolpropane caprolactone-modified triacrylate, trimethylolpropane alkylene-modified trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, Glycerol epichlorohydrin modified (hereinafter ECH modified) tria Relate, glycerol EO modified triacrylate, glycerol PO modified triacrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol caprolactone modified hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkylated di Pentaerythritol pentaacrylate, alkylated dipentaerythritol tetraacrylate, alkylated dipentaerythritol triacrylate, dimethylolpropane tetraacrylate (DTMPTA), pentaerythritol ethoxytetraacrylate, phosphoric acid EO-modified triacrylate, 2, 2, 5, 5 , -Tetrahydroxymethylcyclopentanone tetraacrylate Etc. and the like, which can be used in combination either alone or in combination.

  The trifunctional or higher functional radical polymerizable monomer having no charge transport structure used in the present invention has a molecular weight relative to the number of functional groups in the monomer in order to form a dense crosslink in the crosslinkable charge transport layer. The ratio (molecular weight / functional group number) is preferably 250 or less. If this ratio is greater than 250, the cross-linked charge transport layer is soft and wear resistance is somewhat lowered. Therefore, among the monomers exemplified above, monomers having a modifying group such as EO 2, PO 3, and caprolactone are extremely It is not preferable to use a compound having a long modifying group alone. The component ratio of the radical polymerizable monomer having 3 or more radical polymerizable groups in the molecule is 20 to 80% by weight, preferably 30 to 70% by weight, based on the total amount of the cured coating composition. It depends on the proportion of radically polymerizable monomer having 3 or more radically polymerizable groups in the molecule in the solid content of the coating liquid. When the monomer component is less than 20% by weight, the three-dimensional crosslink density of the crosslinkable charge transport layer is small, and a drastic improvement in wear resistance is not achieved as compared with the case of using a conventional thermoplastic binder resin. On the other hand, if it exceeds 80% by weight, the content of the charge transporting compound is lowered, and the electrical characteristics are deteriorated. The electrical characteristics and abrasion resistance required differ depending on the process used, and the film thickness of the cross-linked charge transport layer of the photoreceptor varies accordingly. A range of 70% by weight is most preferred.

Next, the C component will be described.
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 Benzoin ether photopolymerization initiators such as ether, benzoin isopropyl ether, benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoylphenyl ether, acrylated benzophenone, Benzophenone-based photopolymerization initiators such as 1,4-benzoylbenzene, thioxanthone such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Examples of the photopolymerization initiator and other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethyl. Nzoylphenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9 , 10-phenanthrene, acridine compounds, triazine compounds, and imidazole compounds.

  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 polymerization initiators may be used alone or in combination of two or more. 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.

Next, a method for forming a cured coating composition will be described.
The cured coating composition used in the present invention, after preparing a coating solution containing at least component A or component A and B or component A and B and C, and coating the coating solution on the surface of the photoreceptor, It is formed by radical polymerization. In the case of component A, B and C, it is formed by carrying out light irradiation according to the absorption wavelength of the photopolymerization initiator and polymerizing.

  When the polymerizable monomer is a liquid, the coating liquid can be applied by dissolving other components in the liquid, but it is diluted with a solvent as required. 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. And ethers such as dichloromethane, dichloroethane, trichloroethane and chlorobenzene, aromatics such as benzene, toluene and xylene, 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.

  The component A is important for imparting the charge transport performance of the cured coating composition, and this component is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, based on the cured coating composition. If this component is less than 20% by weight, the charge transport performance cannot be sufficiently maintained, and deterioration of electrical characteristics such as a decrease in sensitivity and an increase in residual potential appear after repeated use. On the other hand, when the content exceeds 80% by weight, the content of the B component is lowered, and the crosslinking density is lowered, and the intended characteristics are hardly exhibited.

In addition to the A, B and C components, the coating liquid is monofunctional and bifunctional for the purpose of imparting functions such as viscosity adjustment during coating, stress relaxation of the cross-linked charge transport layer, lower surface energy, and reduced friction coefficient. A radical polymerizable monomer and a radical polymerizable oligomer can be used in combination. Known radical polymerizable monomers and oligomers can be used.
Examples of the monofunctional radical monomer include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, and cyclohexyl acrylate. , Isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, styrene monomer, and the like. Examples of the bifunctional radical polymerizable monomer include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1, Examples include 6-hexanediol dimethacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate bisphenol A-EO modified diacrylate, bisphenol F-EO modified diacrylate, neopentyl glycol diacrylate, and the like.

  Examples of the functional monomer include those substituted with a fluorine atom such as octafluoropentyl acrylate, 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl methacrylate, 2-perfluoroisononylethyl acrylate, No. 60503, JP-B-6-45770, siloxane repeating units: 20-70 acryloyl polydimethylsiloxane ethyl, methacryloyl polydimethylsiloxane ethyl, acryloyl polydimethylsiloxane propyl, acryloyl polydimethylsiloxane butyl, diacryloyl polydimethylsiloxane Examples include vinyl monomers having a polysiloxane group such as diethyl, acrylates and methacrylates.

  Examples of the radical polymerizable oligomer include epoxy acrylate, urethane acrylate, and polyester acrylate oligomers. However, when a large amount of monofunctional and bifunctional radically polymerizable monomers and radically polymerizable oligomers are contained, the three-dimensional cross-linking density of the cured coating composition is substantially reduced, leading to deterioration of properties. For this reason, the content of these monomers and oligomers is limited to 50 parts by weight or less, preferably 30 parts by weight or less with respect to 100 parts by weight of component A.

  Furthermore, the coating liquid 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 necessary. 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

After application of the coating solution, a drying step is optionally performed and curing is performed by light irradiation or the like.
For UV irradiation, UV light sources such as high-pressure mercury lamps and metal halide lamps that mainly emit 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. It is. Irradiation light amount is 50 mW / cm ² or more, preferably 2000 mW / cm ² or less, it takes time for the curing reaction is less than 50 mW / cm ^2. If it is higher than 2000 mW / cm ^2, the progress of the reaction becomes non-uniform, and local flaws are generated on the surface of the cross-linked charge transport layer, or many unreacted residues and reaction termination ends are generated. In addition, internal stress increases due to rapid crosslinking, which causes cracks and film peeling. Further, nitrogen substitution may be performed at the time of light irradiation to prevent polymerization inhibition due to oxygen. Further, the light irradiation may be performed continuously, or may be performed intermittently in a plurality of times.

  Electron beam irradiation can also be used as a similar means of light irradiation. However, those using light energy are preferred because of easy reaction rate control and simple apparatus.

The greater the amount of light irradiation, the higher the gel fraction of the cured coating composition and the more insoluble and infusible state. In order to achieve the object of the present invention, the gel fraction is preferably 95% or more. The gel fraction can be observed by immersing the cured coating composition in a highly soluble organic solvent such as tetrahydrofuran for 5 days and measuring the weight loss.
Gel fraction (%) = 100 × (weight of cured coating composition after immersion drying / initial weight of cured coating composition)
In order to form a cured coating composition having a gel fraction of 95% or more, it is desirable to irradiate an integrated irradiation energy of 10 J / cm ² or more.
Further, it is desirable to cure the gel fraction to 97% or more. By increasing the gel fraction, it is possible to further prevent stabs such as silica. In this case, it is desirable to irradiate accumulated irradiation energy of 20 J / cm ² or more.
After being cured by light irradiation, annealing is performed at 80 ° C. to 150 ° C. and used as an electrophotographic photoreceptor. The annealing time is about 1 minute to 60 minutes.

Next, the configuration of the electrophotographic photosensitive member will be described.
The electrophotographic photoreceptor of the present invention has the above-mentioned cured coating composition on the surface, and there is no limitation on the structure thereof, but the general formulas (2) and (3) listed as preferred radical polymerizable monomers for the component A It is preferable that the compound is formed on the surface of a negatively charged organic photoreceptor because of its hole transportability.

  As a typical configuration of the negatively charged organic photoreceptor, a charge generation layer and a charge transport layer are sequentially laminated on a conductive support, and the cured coating composition can be applied to the charge transport layer. However, in this case, since the film thickness of the charge transport layer is limited by the curing conditions, a photoconductor structure in which a crosslinkable charge transport layer is further laminated on the charge transport layer is formed, and the cured coating composition is formed on the crosslinkable charge transport layer. Is most preferably applied.

Hereinafter, the present invention will be described according to the optimum layer structure.
FIG. 1 is a cross-sectional view showing one embodiment. On a conductive support (31), a charge generation layer (35) having a charge generation function, a charge transport layer (37) having a charge transport material function, and The photoconductor has a laminated structure in which a cross-linked charge transport layer (39) is laminated.

<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.

  Further, 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, polytetrafluoroethylene-based fluororesin on a suitable cylindrical substrate. Those provided with a conductive layer can be used favorably as the conductive support (31) of the present invention.

<About photosensitive 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 a carbazole skeleton, azo pigments having a triphenylamine skeleton, azo pigments having a 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 , JP 09-268226 A, JP 09-272735 A, JP 09-302084 A, JP 09-302085 A, JP 09-328539 A, etc. Is 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. A charge transport material having a charge transport function and a binder resin are dissolved or dispersed in an appropriate solvent, and this is coated on the charge generation layer (35) and dried. To form. 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 cross-linked charge transport 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 appropriately 20 to 300 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by 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 charge transport layer, the same solvent as that used 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 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 0 with respect to 100 parts by weight of the binder resin. About 30 parts by weight is appropriate.

  Leveling agents that can be used in combination with the charge transport layer include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain. The amount used is a binder resin. About 0 to 1 part by weight is appropriate for 100 parts by weight. The thickness of the charge transport layer is suitably about 5 to 40 μm, preferably about 10 to 30 μm. On the charge transport layer thus formed, the above-described curable coating liquid is applied, and if necessary, dried, and then a curing reaction is initiated by the external energy of light irradiation to form a crosslinkable charge transport layer. The

<About the intermediate layer>
In the photoreceptor of the present invention, an intermediate layer is provided between the charge transport layer and the cross-linked charge transport layer for the purpose of suppressing charge transport layer component mixing into the cross-linked charge transport layer or improving adhesion between the two layers. It is possible. For this reason, as the intermediate layer, those which are insoluble or hardly soluble in the cross-linked charge transport layer coating solution are suitable, and generally a binder resin is 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>
Further, in the present invention, in order to improve environmental resistance, in particular, for the purpose of preventing a decrease in sensitivity and an increase in residual potential, a cross-linked charge transport layer, a charge transport layer, a charge generation layer, an undercoat layer, an intermediate layer An antioxidant can be added to each 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, oils and fats, 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.

(Crosslinked charge transport layer)
The film thickness of the crosslinked charge transport layer of the present invention is preferably 1 μm or more and 10 μm or less, more preferably 3 μm or more and 10 μm or less. If it is thicker than 10 μm, cracks and film peeling tend to occur, and radical polymerization due to photocleavage of the photoinitiator hardly occurs in the deep part, so that it becomes difficult to form a film having a high crosslinking density. On the other hand, the radical polymerization reaction is prone to oxygen inhibition, that is, the surface in contact with the air is not easily cross-linked or non-uniform due to the effect of radical trapping by oxygen. This effect is noticeable when the surface layer is 1 μm or less, and the cross-linked charge transport layer having a thickness of less than this thickness is liable to cause a decrease in wear resistance or uneven wear. In addition, mixing of the lower layer charge transport layer component occurs during the application of the crosslinkable charge transport layer. If the coating thickness of the crosslinkable charge transport layer is thin, contaminants spread throughout the layer, which inhibits the curing reaction and lowers the crosslink density. For these reasons, the crosslinked charge transport layer of the present invention can form a high-density crosslinked body with a film thickness of 1 μm or more, thereby preventing white spots. In addition, a decrease in film thickness due to wear in repeated use tends to cause local chargeability and sensitivity fluctuations, and it is desirable that the film thickness of the cross-linked charge transport layer be 3 μm or more from the viewpoint of extending the life.

<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 multilayer photoreceptor having a cross-linked charge transport layer on the surface, which has very high wear resistance and scratch resistance and is less likely to cause cracks or film peeling. An image forming method and an image forming apparatus including a process of charging, image exposure, and development of a photosensitive member, and a process of transferring a toner image onto an image carrier (transfer paper), fixing, and cleaning of the surface of the photosensitive member. 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. 2 is a schematic diagram illustrating an example of an image forming apparatus. A charging charger (3) is used as a means for charging the photoconductor on average. 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 structure of the present invention is particularly 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. Therefore, 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. If this is developed with toner of negative (positive) polarity (detection fine particles), a positive image can be obtained, and if developed with toner of positive (negative) polarity, a negative image can be obtained. 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. 3, the surface of the photoconductor (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 is a laminate type photoconductor having a cross-linked charge transport layer on its surface that has very high wear resistance and scratch resistance and is unlikely to cause cracks or film peeling, and at least one of charging, developing, transferring, cleaning, and neutralizing means. The present invention provides a process cartridge for an image forming apparatus in which the two 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.

<Synthesis example 1 of component A used in the present invention>
(Preparation of 4,4′-dimethyltriphenylamine)
Into a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, put 18.63 g of aniline (manufactured by Tokyo Chemicals), 89.39 g of p-iodotoluene, 66.34 g of potassium carbonate, 1.27 g of copper powder, and a nitrogen stream. The reaction was carried out at 210 ° C. for 25 hours. After cooling, the reaction solution was diluted with 200 ml of cyclohexane, subjected to adsorption treatment with activated clay and silica gel, and then concentrated to obtain 29.82 g of target crystals. (Melting point 109 ° C)

(Preparation of 4-bromo-4 ′, 4 ″ -dimethyltriphenylamine)
Into a reaction vessel equipped with a stirrer, a thermometer and a dropping funnel, 14.53 g of 4,4′-dimethyltriphenylamine and 30 ml of dioxane were placed, and 9.34 g of bromine was slowly dropped into 50 ml of dioxane at room temperature under a nitrogen stream. The prepared liquid was slowly dropped at room temperature, and the reaction was further performed at the same temperature for 1 hour. Thereafter, 50 ml of toluene and 100 ml of water were added, and the organic layer was taken out.
After washing with a sodium hydrogen carbonate solution and water, it was subjected to adsorption treatment with silica gel and concentrated to obtain the desired crystal. (Yield 15.78 g, melting point 102.0-103.0 ° C.)

(Preparation of 4-methoxy-4′-N, N-di-p-tolylaminobiphenyl)
In a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, 4.66 g of 4-bromo-4 ′, 4 ″ -dimethyltriphenylamine, 2.04 g of 4-methoxyphenylboronic acid, 26 ml of toluene, 2N After adding 26 ml of potassium carbonate aqueous solution and 13 ml of ethanol and performing deaeration treatment with ultrasonic waves under a nitrogen stream, 0.6 g of tetrakistriphenylphosphine palladium was added and reacted at 70 ° C. for 6 hours. Thereafter, the extracted organic layer was washed with water and concentrated to obtain a coarse product. It was purified by column chromatography using silica gel, and further recrystallized and purified with a mixed solvent of hexane / toluene to obtain the desired product. (Yield 4.28 g, melting point 142.0-142.5 ° C.)

(Preparation of 4-hydroxy-4′-N, N-di-p-tolylaminobiphenyl)
Into a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, 15.2 g of 4-methoxy-4′-N, N-di-p-tolylaminobiphenyl and 60 ml of methylene chloride were added, and tribromide under ice-cooling. 26 ml of a methylene chloride solution of boron was added dropwise, and the reaction was further performed at the same temperature for 4 hours. Thereafter, the reaction solution was poured into ice water, extracted by adding methylene chloride, washed with an aqueous sodium bicarbonate solution and water, and concentrated to obtain the desired product. (Yield 14.7 g, amorphous)
<Results of mass spectrometry>
The mass (m / z) value per unit charge obtained by ionization by the atmospheric pressure chemical ionization method was 366, which coincided with the value of molecular weight + 1 (proton addition).

(Preparation of 2-hydroxy-3- (4- (4′-N, N-di-p-tolylamino) biphenyloxy) propyl methacrylate)
In a reaction vessel equipped with a stirrer, thermometer, condenser, and dropping funnel, 6.0 g of 4-hydroxy-4′-N, N-di-p-tolylaminobiphenyl, 1.8 g of benzyltriethylammonium chloride, 40 ml of tetrahydrofuran And a solution of glycidyl methacrylate 3.3 ml / tetrahydrofuran 10 ml was added dropwise at room temperature under a nitrogen stream. Then, it heated and refluxed for 40 hours.
After completion of the reaction, the reaction mixture was diluted with ethyl acetate, passed through silica gel, and the solvent was distilled off to obtain 8 g of a crude product. Furthermore, the target product was obtained by column chromatography using silica gel (solvent: hexane / ethyl acetate (2/1)). (Yield 1.5 g, colorless crystals) IR measurement data is shown in FIG.
In addition, a mixture with 2-hydroxymethyl-2- (4- (4′-N, N-di-p-tolylamino) biphenyloxy) ethyl methacrylate, which is a structural analog that is a reaction byproduct, was obtained. (Yield 3.5 g, colorless crystals) IR measurement data is shown in FIG.
<Results of mass spectrometry>
The mass (m / z) value per unit charge obtained by ionization by the atmospheric pressure chemical ionization method was 508, which was consistent with the value of molecular weight + 1 (proton addition).

(Synthesis of Exemplified Compound 2)
In a reaction vessel equipped with a stirrer, a thermometer and a dropping funnel, 5.2 g of 2-hydroxy-3- (4- (4′-N, N-di-p-tolylamino) biphenyloxy) propyl methacrylate, 50 ml of tetrahydrofuran, 2 g of triethylamine was added, and a mixed solution of 1.9 g of acryloyl chloride and 5 ml of tetrahydrofuran was added dropwise at 15 ° C. under a nitrogen stream. Then, it was made to react at room temperature for 5 hours. After completion of the reaction, the mixture was diluted with 100 ml of toluene and washed with water to obtain an organic layer. The concentrated product was obtained by column chromatography using silica gel (solvent: hexane / ethyl acetate (3/1)). (Yield 3.1 g, colorless oil)
IR measurement data is shown in FIG.
<Results of mass spectrometry>
The mass (m / z) value per unit charge obtained by ionization by the atmospheric pressure chemical ionization method was 562, which was consistent with the value of molecular weight + 1 (proton addition).

As described above, other specific examples can be synthesized in the same manner by changing 4,4′-dimethyltriphenylamine to various aniline derivatives.
Further, other specific examples can be synthesized in the same manner from the methoxy compound corresponding to 4-methoxy-4′-N, N-di-p-tolylaminobiphenyl.

<Synthesis example 2 of component A used in the present invention>
Synthesis of mixture of exemplary compound 2 and compound represented by general formula (13) below

2-Hydroxy-3- (4- (4′-N, N-di-p-tolylamino) biphenyloxy) propyl methacrylate obtained above and 2-hydroxymethyl-2 which is a structural analog that is a reaction byproduct Using 3 g of a mixture with-(4- (4′-N, N-di-p-tolylamino) biphenyloxy) ethyl methacrylate, the same procedure as in the synthesis of Exemplified Compound 2 was performed to obtain the desired mixture. (Yield 2.86 g, colorless oil)
IR data of the mixed composition is shown in FIG.
<Results of mass spectrometry>
Mass per unit charge obtained by positive ionization by atmospheric pressure chemical ionization method (
m / z) value was 562, which coincided with the value of molecular weight + 1 (proton addition).

<Synthesis example 3 of component A used in the present invention>
Synthesis of the compound represented by the following formula (14) Preparation of 1,2-dihydroxy-3- (4- (4′-N, N-di-p-tolylamino) biphenyloxy) propane)
In a reaction vessel equipped with a stirrer, thermometer, condenser, and dropping funnel, 5.0 g of 4-hydroxy-4′-N, N-di-p-tolylaminobiphenyl, 1.8 g of sodium hydroxide and 8 g of water A solution of 1.9 ml of glycidyl methacrylate / 10 ml of tetrahydrofuran was added dropwise at room temperature under a nitrogen stream. Then, it was made to react at 50 degreeC for 10 hours.
After completion of the reaction, the reaction mixture was diluted with ethyl acetate and washed with water, and then the solvent was distilled off to obtain 7 g of a coarse product. Furthermore, the target compound represented by the following general formula (15) was obtained by column chromatography using silica gel (solvent: ethyl acetate). (Yield 4g, colorless crystals)

（１、２−ジヒドロキシ−３−（４−（４’−Ｎ，Ｎ−ジ−ｐ−トリルアミノ）ビフェニルオキシ）プロパンの調製）
かき混ぜ装置、温度計、冷却管、滴下漏斗をつけた反応容器に、４−ヒドロキシ−４’−Ｎ，Ｎ−ジ−ｐ−トリルアミノビフェニル５．０ｇ、水酸化ナトリウム１．８ｇと水８ｇからなる水溶液、テトラヒドロフラン３０ｍｌを入れ、窒素気流下室温でグリシジルメタクリレート１．９ｍｌ／テトラヒドロフラン１０ｍｌの溶液を滴下した。その後、５０℃で１０時間反応させた。
反応終了後、酢酸エチルで希釈し、水洗してから溶媒を留去して粗収物７ｇを得た。さらに、シリカゲルを用いたカラムクロマトグラフ（溶媒：酢酸エチル）により下記一般式（１５）で表わされる目的物を得た。（収量４ｇ、無色結晶）

(Preparation of 1,2-dihydroxy-3- (4- (4′-N, N-di-p-tolylamino) biphenyloxy) propane)
In a reaction vessel equipped with a stirrer, thermometer, condenser, and dropping funnel, 5.0 g of 4-hydroxy-4′-N, N-di-p-tolylaminobiphenyl, 1.8 g of sodium hydroxide and 8 g of water A solution of 1.9 ml of glycidyl methacrylate / 10 ml of tetrahydrofuran was added dropwise at room temperature under a nitrogen stream. Then, it was made to react at 50 degreeC for 10 hours.
After completion of the reaction, the reaction mixture was diluted with ethyl acetate and washed with water, and then the solvent was distilled off to obtain 7 g of a coarse product. Furthermore, the target compound represented by the following general formula (15) was obtained by column chromatography using silica gel (solvent: ethyl acetate). (Yield 4g, colorless crystals)

The identification information (IR measurement data) of this material is shown in FIG.
<Results of mass spectrometry>
The mass (m / z) value per unit charge obtained by ionization by the atmospheric pressure chemical ionization method and positive was 440, which coincided with the value of molecular weight + 1 (proton addition). Melting point: 146-147 ° C.

(Synthesis of General Formula (14))
In a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, 4.6 g of 1,2-dihydroxy-3- (4- (4′-N, N-di-p-tolylamino) biphenyloxy) propane, 20 ml of tetrahydrofuran. Then, 5 g of triethylamine was added, and a mixed solution of 3.5 g of acryloyl chloride and 5 ml of tetrahydrofuran was added dropwise at 15 ° C. under a nitrogen stream. Then, it was made to react at room temperature for 5 hours. After completion of the reaction, the mixture was diluted with 100 ml of toluene and washed with water to obtain an organic layer. The concentrated solution was purified by column chromatography using silica gel (solvent: hexane / ethyl acetate (3/1)) to obtain the desired product. (Yield 4.6g)
IR measurement data is shown in FIG.
<Results of mass spectrometry>
Mass per unit charge obtained by positive ionization by atmospheric pressure chemical ionization method (
m / z) value was 548, which coincided with the value of molecular weight + 1 (proton addition).

<Synthesis example 4 of component A used in the present invention>

Preparation of diethyl 4-methoxybenzylphosphonate 4-Methoxybenzyl chloride and triethyl phosphite were reacted at 150 ° C. for 5 hours.
Thereafter, excess triethyl phosphite and by-product ethyl chloride were removed by distillation under reduced pressure to obtain diethyl 4-methoxybenzylphosphonate.
<Results of mass spectrometry>
The mass (m / z) value per unit charge obtained by positive ionization by the atmospheric pressure chemical ionization method was 259, which coincided with the value of molecular weight + 1 (proton addition).

Preparation of 4-methoxy-4 ′-(di-p-tolylamino) stilbene equimolar diethyl 4-methoxybenzylphosphonate and 4- (di-p-tolylamino) benzaldehyde are dissolved in N, N-dimethylformamide and cooled with water. Tert-butoxypotassium was added little by little with stirring. After stirring at room temperature for 5 hours, water was added to make it acidic, and a crude product of the desired product was obtained. Further, purification by column chromatography on silica gel yielded the desired 4-methoxy-4 ′-(di-p-tolylamino) stilbene.
<Results of mass spectrometry>
The mass (m / z) value per unit charge obtained by ionization by the atmospheric pressure chemical ionization method was 406, which was equal to the value of molecular weight + 1 (proton addition). Melting point: 157-157.5 ° C.

Preparation of 4-hydroxy-4 '-(di-p-tolylamino) stilbene 4-methoxy-4'-(di-p-tolylamino) stilbene and double equivalent sodium ethanethiolate dissolved in N, N-dimethylformamide And allowed to react at 130 ° C. for 5 hours. Then, it was cooled and poured into water, neutralized with hydrochloric acid, and the target product was extracted with ethyl acetate. The extract was washed with water, dried and evaporated to give a crude product. Further, the product was purified by column chromatography on silica gel to obtain the desired product 4-hydroxy-4 ′-(di-p-tolylamino) stilbene.
<Results of mass spectrometry>
The mass (m / z) value per unit charge obtained by ionization by the atmospheric pressure chemical ionization method was 392, which coincided with the value of molecular weight + 1 (proton addition). Melting point: 152-155 ° C.

Preparation of 1,2-dihydroxy-3- [4 ′-(di-p-tolylamino) stilben-4-yloxy] propane A reaction vessel equipped with a stirrer, thermometer, condenser, and dropping funnel was charged with 4-hydroxy- After putting 11.75 g of 4 ′-(di-p-tolylamino) stilbene, 4.35 g of glycidyl methacrylate and 8 ml of toluene, the temperature was raised to 90 ° C., 0.16 g of triethylamine was added, and the mixture was heated and stirred at 95 ° C. for 8 hours. Thereafter, 16 ml of toluene and 20 ml of a 10% aqueous sodium hydroxide solution were added, and the mixture was further heated and stirred at 95 ° C. for 8 hours.
After completion of the reaction, the reaction mixture was diluted with ethyl acetate, washed with acid and washed with water, and then the solvent was distilled off to obtain 19 g of a crude product. Furthermore, the target product of the following general formula (17) was obtained by column chromatography using silica gel (solvent: ethyl acetate). (Yield 9.85 g, yellow crystals, melting point 127-128.7 ° C.)

IR measurement data is shown in FIG.
<Results of mass spectrometry>
Mass per unit charge obtained by positive ionization by atmospheric pressure chemical ionization method (
m / z) value was 466, which coincided with the value of molecular weight + 1 (proton addition).

(Synthesis of compound of general formula (16))
In a reaction vessel equipped with a stirrer, thermometer and dropping funnel, 1.0 g of 1,2-dihydroxy-3- [4 ′-(di-p-tolylamino) stilben-4-yloxy] propane, N, N-dimethyl 10 ml of acetamide was added, and 1.09 g of 3-chloropropanoic acid chloride was added dropwise at 3 ° C. under a nitrogen stream. Then, it was made to react at room temperature for 8 hours. Next, 1.74 g of triethylamine was added, and the mixture was further reacted at 60 ° C. for 4 hours. After completion, the mixture was extracted with methylene chloride and washed with water to obtain an organic layer. The concentrated solution was purified by column chromatography using silica gel (solvent: hexane / ethyl acetate (2/1)) to obtain the desired product. (Yield 1.1 g, yellow oil) IR measurement data is shown in FIG.
<Results of mass spectrometry>
The mass (m / z) value per unit charge obtained by ionization by the atmospheric pressure chemical ionization method was 574, which was consistent with the value of molecular weight + 1 (proton addition).
As described above, 4-methoxybenzylphosphonic acid diethyl or its derivatives and various benzaldehyde derivatives are reacted to synthesize 4-methoxystilbene derivatives, and then the other specific examples are synthesized by carrying out in the same manner as described above. be able to.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to a following example. Note that “parts” used in the examples all represent parts by weight.
<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 an 18 μm charge transport layer were formed. On this charge transport layer, a coating solution for a crosslinkable charge transport layer having the following composition is spray-coated, and after naturally drying for 20 minutes, a metal halide lamp: 160 W / cm 2, irradiation distance: 110 mm, irradiation intensity: 750 mW / cm ² Irradiation time: Light irradiation was performed under the condition of 240 seconds to cure the coating film. Furthermore, drying was performed at 130 ° C. for 20 minutes, and a 5.0 μm cross-linked charge transport layer was provided to obtain an electrophotographic photoreceptor of the present invention.

[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]
2.5 parts of bisazo pigment of the following structural formula (I)

ポリビニルブチラール（ＸＹＨＬ、ＵＣＣ製） ０．５部
シクロヘキサノン ２００部
メチルエチルケトン ８０部

Polyvinyl butyral (XYHL, manufactured by UCC) 0.5 part Cyclohexanone 200 parts Methyl ethyl ketone 80 parts

[Coating liquid for charge transport layer]
10 parts of bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals)
7 parts of a low molecular charge transport material (D-1) having the following structural formula (II)

テトラヒドロフラン １００部
１％シリコーンオイルのテトラヒドロフラン溶液 ０．２部
（ＫＦ５０−１００ＣＳ、信越化学工業製）

Tetrahydrofuran 100 parts 1% silicone oil tetrahydrofuran solution 0.2 parts (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Coating liquid for cross-linked charge transport layer]
A component 10 parts (Exemplary Compound No. 2)
B component 10 parts Trimethylolpropane triacrylate (KAYARAD TMPTA, Nippon Kayaku)
Molecular weight: 296, number of functional groups: trifunctional, molecular weight / number of functional groups = 99
Component C 1 part 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
Solvent tetrahydrofuran 100 parts

<Example 2>
The component A of Example 1 was replaced with Exemplified Compound No. An electrophotographic photosensitive member was produced in the same manner except that the mixture of 2 and the general formula (13) was used.

<Example 3>
An electrophotographic photosensitive member was produced in the same manner except that the component A in Example 1 was replaced by the general formula (14).

<Example 4>
An electrophotographic photoreceptor was prepared in the same manner as in Example 3 except that the thickness of the cross-linked charge transport layer was 1 μm.

<Example 5>
An electrophotographic photosensitive member was prepared in the same manner as in Example 3 except that the thickness of the cross-linked charge transport layer was 2 μm.

<Example 6>
An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the thickness of the cross-linked charge transport layer was 7 μm.

<Example 7>
An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the thickness of the cross-linked charge transport layer was 10 μm.

<Example 8>
An electrophotographic photosensitive member was produced in the same manner as in Example 3, except that the thickness of the cross-linked charge transport layer was 12 μm.

<Example 9>
An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the component A was replaced by the general formula (16).

<Examples 10 to 14>
Exemplified Compound Nos. Obtained in the same manner as in Synthesis Example 3 and Synthesis Example 4. 3, a compound obtained by changing the methacryloxy group to an acryloxy group, Exemplified Compound No. 3 No. 9, a compound obtained by changing the methacryloxy group to an acryloxy group, Exemplified Compound No. 9 No. 38, a compound obtained by changing the methacryloxy group of 38 to an acrylicoxy group 11, No. of additional exemplified compounds. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 28 was the A component.

<Comparative Example 1>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the component A was replaced by the general formula (18).

<Comparative example 2>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the component A was replaced by the following general formula (19).

<Comparative Example 3>
An electrophotographic photosensitive member was produced in the same manner except that the component A in Example 1 was replaced by the following general formula (20).

<Comparative example 4>
An electrophotographic photosensitive member was produced in the same manner except that the component A in Example 1 was replaced with the compound represented by the following general formula (21).

<Comparative Example 5>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the component A was replaced by the following general formula (22).

<Comparative Example 6>
An electrophotographic photosensitive member was produced in the same manner except that the component A in Example 1 was replaced by the following general formula (23).

<Comparative Example 7>
An electrophotographic photosensitive member was produced in the same manner except that the component A in Example 1 was replaced by the following general formula (24).

<Comparative Example 8>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the component A was replaced by the following general formula (25).

  With respect to the electrophotographic photoreceptors of Examples 1 to 9 and Comparative Examples 1 to 8 produced as described above, the appearance was visually observed to determine the presence or absence of cracks and film peeling. Moreover, the gel fraction of each crosslinkable charge transport layer was determined. The gel fraction was determined by applying a crosslinked charge transport layer coating solution directly onto an aluminum support in the same manner as in each Example and Comparative Example, and irradiating and drying the membrane under the same conditions in a tetrahydrofuran solution at 25 ° C. It was immersed for 5 days and determined from the weight residual ratio of the gel. The results are shown in Table 13.

  Next, in Examples 1-9 and Comparative Examples 1-8, except for the photoconductor of Comparative Example 5 in which cracks occurred during the formation of the cross-linked charge transport layer, these photoconductors and silica external additives prepared in the same manner Using the contained toner, a paper passing test of 100,000 sheets of A4 size was performed. 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. Then, measure the total film thickness after the initial and 50,000 copies, calculate the amount of wear from the difference, observe the image after 50,000 copies, and the number of white spots per unit area from the solid image area I counted. Further, in order to check the residual potential accumulation property, the initial portion and the exposure portion potential (VL) after 50,000 copies were measured. The results are shown in Table 14.

  As described above, the electrophotographic photoreceptor of the present invention is excellent in wear resistance among organic photoreceptors having excellent wear resistance, and on the other hand, image output with few defects is possible. In particular, white spots caused by the sticking of silica hardly occur, and the image has sufficient image stability even when used for a long time.

  It is clear that the primary factor of these is due to the specific A component used in the present application in comparison with the comparative example, and an electrophotographic film having a cured coating composition obtained by radical polymerization of the A component of the present application on the surface. It represents that the photoreceptor has excellent characteristics.

  In particular, the combination of Component A and Component B of the present application provides a highly durable photoreceptor that is smooth and extremely wear-resistant as shown in the examples, has low residual charge accumulation, and has few image defects such as white spots. Show. The examples also show that a cured coating composition of the composition photocured in the presence of a photopolymerization initiator is effective.

  Also, good characteristics are maintained in the range of the cross-linked charge transport layer in the range of 1 to 10 μm. When the thickness is less than 1 μm, there is almost no margin for the amount of wear after copying 50,000 sheets. In the case of exceeding the range, the gel fraction is decreased and the residual potential accumulation property is deteriorated, which indicates that the above range is preferable.

  Further, under the curing conditions of the examples, it was determined that the gel fraction data was substantially insoluble in the organic solvent, and excellent abrasion resistance and image stability were achieved under the conditions. Show.

  Moreover, when A component represented by General formula (4) and General formula (5) is used, it has the highest abrasion resistance and the outstanding electric potential stability, and also there are few generation | occurrence | production of a white spot.

1 is an example of a cross-sectional view of an electrophotographic photosensitive member of the present 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 spectrum of General formula (15) in this invention. It is the figure which showed IR spectrum of 2-hydroxy-3- (4- (4'-N, N-di-p-tolylamino) biphenyloxy) propyl methacrylate in the present invention. It is the figure which showed IR spectrum of the exemplary compound 2 in this invention. It is the figure which showed IR spectrum of the mixed composition of the exemplary compound 2 and general formula (13) in this invention. It is the figure which showed IR spectrum of General formula (14) in this invention. It is the figure which showed IR spectrum of General formula (17) in this invention. It is the figure which showed an example of IR spectrum of General formula (16) in this invention. 2-hydroxy-3- (4- (4'-N, N-di-p-tolylamino) biphenyloxy) propyl methacrylate and 2-hydroxymethyl-2- (4- (4'-N, N-) in the present invention It is the figure which showed IR spectrum of the mixture with di-p-tolylamino) biphenyloxy) ethyl methacrylate.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Static elimination lamp 3 Charger charger 4 Eraser 5 Image exposure part 6 Developing unit 7 Charger before transfer 8 Registration roller 9 Transfer paper 10 Transfer charger 11 Separation charger 12 Separation claw 13 Charger before cleaning 14 Fur brush 15 Cleaning blade 31 Conductivity Support 33 Photosensitive layer 35 Charge generation layer 37 Charge transport layer 39 Crosslinkable charge transport layer 101 Photosensitive drum 102 Charging device 103 Exposure device 104 Development device 105 Transfer body 106 Transfer device 107 Cleaning blade

Claims (16)

An electrophotographic photosensitive member having a cured coating composition obtained by radical polymerization of at least the following component A on the surface.
(A: a radical polymerizable monomer in which an aliphatic group having two radical polymerizable groups and a charge transporting group not containing a radical polymerizable group are linked by a single bond) An electrophotographic photosensitive member having a cured coating composition obtained by radical polymerization of at least the following components A and B on the surface.
(A: a radical polymerizable monomer in which an aliphatic group having two radical polymerizable groups and a charge transporting group not containing a radical polymerizable group are linked by a single bond)
(B: radical polymerizable monomer having three or more radical polymerizable groups in the molecule) An electrophotographic photosensitive member having a cured coating composition obtained by radical polymerization of at least the following components A, B and C on the surface.
(A: a radical polymerizable monomer in which an aliphatic group having two radical polymerizable groups and a charge transporting group not containing a radical polymerizable group are linked by a single bond)
(B: radical polymerizable monomer having three or more radical polymerizable groups in the molecule)
(C: photopolymerization initiator) 4. The electrophotographic photoreceptor according to claim 1, wherein the radically polymerizable group of the component A and / or the component B is an acryloyloxy group and / or a methacryloyloxy group. The electrophotographic photosensitive member according to claim 1, wherein the aliphatic group having two radical polymerizable groups of the component A is represented by the following general formula (1).

(In the formula, Ra and Rb each represent a hydrogen atom or a methyl group.) 6. The electrophotographic photoreceptor according to claim 1, wherein the component A is a radical polymerizable monomer represented by the following general formula (2).

(In the formula, Ra and Rb each represent a hydrogen atom or a methyl group, and Rc and Rd each represents an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted alkoxy group, An aryl group that may have a substituent is represented, Ar ₁ and Ar ₂ represent an aryl group that may have a substituent, and i and j represent an integer of 0 to 4. Rc and Rd May combine to form a cyclic hydrocarbon ring having 5 to 8 carbon atoms together with the biphenyl ring.) The electrophotographic photoreceptor according to claim 1, wherein the component A is a radical polymerizable monomer represented by the following general formula (3).

(In the formula, Ra and Rb each represent a hydrogen atom or a methyl group, and Rc, Rd, Re, and Rf each have a C 1-6 alkyl group that may have a substituent or a substituent. Represents a good alkoxy group or an aryl group which may have a substituent, i and j represent an integer of 0 to 4 and k represents an integer of 0 to 5. Rc and Rd are bonded to form a biphenyl ring. And a cyclic hydrocarbon ring having 5 to 8 carbon atoms may be formed.) The electrophotographic photoreceptor according to claim 1, wherein the component A is a radical polymerizable monomer represented by the following general formula (4).

(In the formula, Ra and Rb represent a hydrogen atom or a methyl group, and Rc and Rd each represent an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted alkoxy group, and a substituted group. An aryl group which may have a group is represented, Ar ₁ and Ar ₂ represent an aryl group which may have a substituent, and i and j represent an integer of 0 to 4.) The electrophotographic photoreceptor according to claim 1, wherein the component A is a radical polymerizable monomer represented by the following general formula (5).

(In the formula, Ra and Rb represent a hydrogen atom or a methyl group, and Rc, Rd, Re, and Rf may have a C 1-6 alkyl group or substituent which may have a substituent. An alkoxy group and an aryl group which may have a substituent are represented, i and j represent an integer of 0 to 4, k represents an integer of 0 to 5. 10. The cured coating according to claim 1, wherein at least a charge generation layer, a charge transport layer, and a crosslinked charge transport layer are sequentially laminated on a conductive support, wherein the crosslinked charge transport layer is a cured coating according to claim 1. An electrophotographic photoreceptor comprising a composition. The electrophotographic photosensitive member according to claim 10, wherein the cross-linked charge transport layer has a thickness of 1 μm or more and 10 μm or less. 12. The electrophotographic photosensitive member according to claim 8, wherein the crosslinkable charge transport layer is insoluble in an organic solvent. The ratio of the molecular weight to the number of radically polymerizable functional groups of the B component of the cured coating composition used for the crosslinkable charge transport layer (molecular weight / functional group number) is 250 or less. An electrophotographic photoreceptor according to any one of the above. An image forming method, wherein at least charging, image exposure, development, and transfer are repeated using the electrophotographic photosensitive member according to claim 1. An image forming apparatus comprising the electrophotographic photosensitive member according to claim 1. An electrophotographic photosensitive member according to any one of claims 1 to 13, and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, a cleaning means, and a charge eliminating means, A process cartridge for an image forming apparatus, wherein the process cartridge is removable from a main body of the forming apparatus.

Images