JP2017083750A - Electrophotographic photoreceptor, method for manufacturing electrophotographic photoreceptor, process cartridge, and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor with a high level of wear resistance and a suppressed exposure memory, a method for manufacturing the electrophotographic photoreceptor, and a process cartridge and an electrophotographic device having the electrophotographic photoreceptor.SOLUTION: The electrophotographic photoreceptor includes: a supporting body; an electric charge generation layer on the supporting body; an electric charge transporting layer on the electric charge generation layer; and a protective layer on the electric charge transporting layer, the protective layer containing a hardened material of a composition containing (A1) and (B1), (A1) being an electric charge transporting monomer having at least one specific substituent group and at least one group represented by a formula (2), and (B1) being an electric charge transporting monomer having at least two groups represented by the formula (2) and not having the specific substituent group.SELECTED DRAWING: None

Description

  The present invention relates to an electrophotographic photosensitive member, a method for manufacturing an electrophotographic photosensitive member, a process cartridge, and an electrophotographic apparatus.

  An electrophotographic photoreceptor is required to have high wear resistance. Patent Document 1 and Patent Document 2 contain a cured product obtained by curing a charge transporting monomer having a polymerizable functional group in the surface layer of an electrophotographic photosensitive member to improve the abrasion resistance of the electrophotographic photosensitive member. Techniques to improve are described.

  An electrophotographic photoreceptor provided with a surface layer containing the cured product tends to be inferior in various electrical characteristics as compared with an electrophotographic photoreceptor not provided with a surface layer. In particular, since an electrophotographic photosensitive member is highly likely to be exposed to light when it is replaced in a user's usage environment, exposure memory is a problem among the electrical characteristics.

JP 2000-066425 A JP 2010-156835 A

  An object of the present invention is to provide an electrophotographic photoreceptor having high wear resistance and suppressing exposure memory, and a method for producing the same.

  Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

（式（１）および式（２）中、Ｒ^１は、置換もしくは無置換のアルキレン基を示す。Ｘ¹、Ｙ¹、およびＺ¹は、それぞれ独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、アルコキシ基、ニトロ基、またはシアノ基を示す。（Ａ１）および（Ｂ１）が有する複数の式（２）で示される基において、それらの有するＸ^１、Ｙ^１、およびＺ^１が同一分子内あるいは分子間で異なっていても良い。） The present invention relates to an electrophotographic photoreceptor having a support, a charge generation layer formed on the support, a charge transport layer formed on the charge generation layer, and a protective layer formed on the charge transport layer. In the electrophotographic photoreceptor, the protective layer contains a cured product of a composition containing the following (A1) and (B1).
(A1): Charge transporting monomer (B1) having at least one group represented by formula (1) and at least one group represented by formula (2): Group represented by formula (2) Charge transporting monomer which has two or more and does not have the group represented by the formula (1)

(In Formula (1) and Formula (2), R ¹ represents a substituted or unsubstituted alkylene group. X ¹ , Y ¹ , and Z ¹ are each independently a hydrogen atom, substituted or unsubstituted alkyl, A group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group, in the groups represented by the formula (2) that (A1) and (B1) have, X ¹ , Y that they have ¹ and Z ¹ may be different within the same molecule or between molecules.)

（式（１）および式（２）中、Ｒ^１は、置換もしくは無置換のアルキレン基を示す。Ｘ¹、Ｙ¹、およびＺ¹は、それぞれ独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、アルコキシ基、ニトロ基、またはシアノ基を示す。（Ｃ１）および（Ｄ１）が有する複数の式（２）で示される基において、それらの有するＸ^１、Ｙ^１、およびＺ^１が同一分子内あるいは分子間で異なっていても良い。） The present invention also provides a support, a charge generation layer formed on the support, a charge transport layer formed on the charge generation layer, and a protective layer formed on the charge transport layer. An electrophotographic photoreceptor, wherein the protective layer contains a cured product of a composition containing the following (C1), (D1), and (E1).
(C1): Monomer having at least one group represented by formula (1) and having at least one group represented by formula (2) and having no charge transport property (D1): Formula (2) Monomer (E1) having at least two groups represented by the formula (1) and not having the group represented by the formula (1) and having at least one vinyl-based polymerizable functional group Charge transporting monomer.

(In Formula (1) and Formula (2), R ¹ represents a substituted or unsubstituted alkylene group. X ¹ , Y ¹ , and Z ¹ are each independently a hydrogen atom, substituted or unsubstituted alkyl, A group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group, in the groups represented by the formula (2) that (C1) and (D1) have, X ¹ , Y ¹ and Z ¹ may be different within the same molecule or between molecules.)

（式（８）および式（２）中、Ｒ^１は、置換もしくは無置換のアルキレン基を示す。Ｌはフッ素原子、塩素原子、臭素原子、ヨウ素原子を示す。Ｘ¹、Ｙ¹、Ｚ¹、Ｘ^４、Ｙ^４、およびＺ^４は、それぞれ独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、アルコキシ基、ニトロ基、またはシアノ基を示す。（Ａ２）および（Ｂ２）が有する複数の式（２）で示される基、および式（８）で示される基において、それらの有する、Ｘ^１、Ｙ^１、Ｚ^１、Ｘ⁴、Ｙ⁴、およびＺ⁴が同一分子内あるいは分子間で異なっていても良い。） The present invention also provides a support, a charge generation layer formed on the support, a charge transport layer formed on the charge generation layer, and a protective layer formed on the charge transport layer. An electrophotographic photoreceptor, wherein the protective layer contains a cured product of a composition containing the following (A2) and (B2).
(A2): Charge transporting monomer (B2) having at least one group represented by formula (8) and at least one group represented by formula (2): Group represented by formula (2) Charge transporting monomer having 2 or more and having no group represented by formula (8)

(In Formula (8) and Formula (2), R ¹ represents a substituted or unsubstituted alkylene group. L represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. X ¹ , Y ¹ , Z ¹ , X ⁴ , Y ⁴ , and Z ⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group (A2). And (B2) have a plurality of groups represented by the formula (2) and a group represented by the formula (8), X ¹ , Y ¹ , Z ¹ , X ⁴ , Y ⁴ , and Z ⁴ May be different within the same molecule or between molecules.)

（式（８）および式（２）中、Ｒ^１は、置換もしくは無置換のアルキレン基を示す。Ｌはフッ素原子、塩素原子、臭素原子、ヨウ素原子を示す。Ｘ¹、Ｙ¹、Ｚ¹、Ｘ^４、Ｙ^４、およびＺ^４は、それぞれ独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、アルコキシ基、ニトロ基、またはシアノ基を示す。（Ｃ２）および（Ｄ２）が有する複数の式（２）で示される基、および式（８）で示される基において、それらの有する、Ｘ^１、Ｙ^１、Ｚ^１、Ｘ⁴、Ｙ⁴、およびＺ⁴が同一分子内あるいは分子間で異なっていても良い。） The present invention also provides a support, a charge generation layer formed on the support, a charge transport layer formed on the charge generation layer, and a protective layer formed on the charge transport layer. An electrophotographic photoreceptor, wherein the protective layer contains a cured product of a composition containing the following (C2), (D2), and (E2).
(C2): Monomer having at least one group represented by formula (8) and having at least one group represented by formula (2) and having no charge transport property (D2): Formula (2) A monomer (E2) having at least two groups represented by formula (8) and not having the group represented by the formula (8) and having at least one vinyl-based polymerizable functional group Charge transporting monomer

(In Formula (8) and Formula (2), R ¹ represents a substituted or unsubstituted alkylene group. L represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. X ¹ , Y ¹ , Z ¹ , X ⁴ , Y ⁴ , and Z ⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group (C2). And (D2) have a plurality of groups represented by the formula (2) and a group represented by the formula (8), X ¹ , Y ¹ , Z ¹ , X ⁴ , Y ⁴ , and Z ⁴ May be different within the same molecule or between molecules.)

（式（１）および式（２）中、Ｒ^１は、置換もしくは無置換のアルキレン基を示す。Ｘ¹、Ｙ¹、およびＺ¹は、それぞれ独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、アルコキシ基、ニトロ基、またはシアノ基を示す。（Ａ１）、（Ｂ１）、（Ｃ１）、（Ｄ１）、（Ａ２）、（Ｂ２）、（Ｃ２）、および（Ｄ２）が有する複数の式（２）で示される基において、それらの有するＸ^１、Ｙ^１、およびＺ^１が同一分子内あるいは分子間で異なっていても良い。）

（式（８）中、Ｒ^１は、置換もしくは無置換のアルキレン基を示す。Ｌはフッ素原子、塩素原子、臭素原子、ヨウ素原子を示す。Ｘ^４、Ｙ^４、およびＺ^４は、それぞれ独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、アルコキシ基、ニトロ基、またはシアノ基を示す。（Ａ２）、および（Ｃ２）が有する複数の式（８）で示される基において、それらの有する、Ｘ⁴、Ｙ⁴、およびＺ⁴が同一分子内あるいは分子間で異なっていても良い。） The present invention also provides a support, a charge generation layer formed on the support, a charge transport layer formed on the charge generation layer, and a protective layer formed on the charge transport layer. A method for producing a photoreceptor, comprising a composition containing the following (A1) and (B1), a composition containing the following (C1), (D1), and (E1), and the following (A2) and (B2) A step of preparing a protective layer coating solution containing the composition or any one of the following compositions (C2), (D2), and (E2), and a coating film of the protective layer coating solution And forming the protective layer by curing the composition in the coating film.
(A1): Charge transporting monomer (B1) having at least one group represented by formula (1) and at least one group represented by formula (2): Group represented by formula (2) A charge transporting monomer (C1) having at least one group represented by formula (1) and having at least one group represented by formula (1) Monomer (D1) having at least one group represented by formula (2) having no charge transporting property: having two or more groups represented by formula (2) and having a group represented by formula (1) A monomer having no charge transporting property (E1): a charge transporting monomer having one or more vinyl-based polymerizable functional groups (A2): having at least one group represented by formula (8), and Charge transporting monomer (B2) having one or more groups represented by the formula (2): Two or more groups represented by the formula (2), and the formula (8) Charge transporting monomer (C2) having no group represented by formula (8): having one or more groups represented by formula (8) and having one or more groups represented by formula (2) Monomers that do not have
(D2): a monomer having two or more groups represented by the formula (2) and not having a group represented by the formula (8) and having no charge transporting property (E2): vinyl-based polymerization Charge transporting monomer having at least one functional group

(In Formula (1) and Formula (2), R ¹ represents a substituted or unsubstituted alkylene group. X ¹ , Y ¹ , and Z ¹ are each independently a hydrogen atom, substituted or unsubstituted alkyl, A group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group, (A1), (B1), (C1), (D1), (A2), (B2), (C2), And in the groups represented by the plurality of formulas (2) possessed by (D2), X ¹ , Y ¹ and Z ¹ possessed by them may be different within the same molecule or between molecules.

(In Formula (8), R ¹ represents a substituted or unsubstituted alkylene group. L represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. X ⁴ , Y ⁴ , and Z ⁴ are each independently selected. Are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group, wherein (A2) and (C2) have a plurality of formulas (8) In the group shown, X ⁴ , Y ⁴ and Z ⁴ which they have may be different within the same molecule or between molecules.)

  Further, the present invention integrally supports the electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means, and is detachable from the main body of the electrophotographic apparatus. A process cartridge.

  The present invention also provides an electrophotographic apparatus having the above electrophotographic photosensitive member, and a charging unit, an exposure unit, a developing unit, and a transfer unit.

  According to the present invention, it is possible to provide an electrophotographic photosensitive member with high wear resistance and suppressed exposure memory, and a method for manufacturing the same. In addition, according to the present invention, a process cartridge and an electrophotographic apparatus having such an electrophotographic photosensitive member can be provided.

It is a figure which shows an example of the layer structure of an electrophotographic photoreceptor. 1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member.

（式（１）および式（２）中、Ｒ^１は、置換もしくは無置換のアルキレン基を示す。Ｘ¹、Ｙ¹、およびＺ¹は、それぞれ独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、アルコキシ基、ニトロ基、またはシアノ基を示す。（Ａ１）、（Ｂ１）、（Ｃ１）、（Ｄ１）、（Ａ２）、（Ｂ２）、（Ｃ２）、および（Ｄ２）が有する複数の式（２）で示される基において、それらの有するＸ^１、Ｙ^１、およびＺ^１が同一分子内あるいは分子間で異なっていても良い。）

（式（８）中、Ｒ^１は、置換もしくは無置換のアルキレン基を示す。Ｌはフッ素原子、塩素原子、臭素原子、ヨウ素原子を示す。Ｘ^４、Ｙ^４、およびＺ^４は、それぞれ独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、アルコキシ基、ニトロ基、またはシアノ基を示す。（Ａ２）、および、（Ｃ２）が有する複数の式（８）で示される基において、それらの有するＸ⁴、Ｙ⁴、およびＺ⁴が同一分子内あるいは分子間で異なっていても良い。）
なお、（Ｂ１）と（Ｂ２）、（Ｄ１）と（Ｄ２）、および（Ｅ１）と（Ｅ２）は、便宜上、異なる記号で表記しているが、本質的には、同じ一般式を指す。 The electrophotographic photosensitive member of the present invention comprises a support, a charge generation layer formed on the support, a charge transport layer formed on the charge generation layer, and a protective layer formed on the charge transport layer. An electrophotographic photosensitive member having a protective layer comprising a composition containing the following (A1) and (B1), a composition containing (C1), (D1) and (E1), (A2) and (B2) Or a cured product of the composition containing (C2), (D2), and (E2).
(A1): Charge transporting monomer (B1) having at least one group represented by formula (1) and at least one group represented by formula (2): Group represented by formula (2) A charge transporting monomer (C1) having at least one group represented by formula (1) and having at least one group represented by formula (1) Monomer (D1) having at least one group represented by formula (2) having no charge transporting property: having two or more groups represented by formula (2) and having a group represented by formula (1) A monomer having no charge transporting property (E1): a charge transporting monomer having one or more vinyl-based polymerizable functional groups (A2): having at least one group represented by formula (8), and Charge transporting monomer (B2) having one or more groups represented by the formula (2): Two or more groups represented by the formula (2), and the formula (8) Charge transporting monomer (C2) having no group represented by formula (8): having one or more groups represented by formula (8) and having one or more groups represented by formula (2) Monomer (D2) not having: A monomer (E2) having two or more groups represented by the formula (2) and having no group represented by the formula (8) and having no charge transporting property : Charge transporting monomer having one or more vinyl-based polymerizable functional groups

(In Formula (1) and Formula (2), R ¹ represents a substituted or unsubstituted alkylene group. X ¹ , Y ¹ , and Z ¹ are each independently a hydrogen atom, substituted or unsubstituted alkyl, A group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group, (A1), (B1), (C1), (D1), (A2), (B2), (C2), And in the groups represented by the plurality of formulas (2) possessed by (D2), X ¹ , Y ¹ and Z ¹ possessed by them may be different within the same molecule or between molecules.

(In Formula (8), R ¹ represents a substituted or unsubstituted alkylene group. L represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. X ⁴ , Y ⁴ , and Z ⁴ are each independently selected. Are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group (A2) and a plurality of formulas (8) possessed by (C2) In the group represented by the formula (1), X ⁴ , Y ⁴ and Z ⁴ which they have may be different within the same molecule or between molecules.)
Note that (B1) and (B2), (D1) and (D2), and (E1) and (E2) are represented by different symbols for convenience, but essentially refer to the same general formula.

The electrophotographic photosensitive member of the present invention has high wear resistance and suppressed exposure memory. The feature of the present invention is to use a monomer having two or more specific polymerizable functional groups and a monomer having a specific substituent not involved in curing, and further, an alkylene group (R ¹ ) of these monomers is It is the same. The specific polymerizable functional group is a group represented by the formula (2), and monomers having two or more specific polymerizable functional groups are (B1), (D1), (B2), and (D2). is there. The specific substituent not involved in the curing is a group represented by the formula (1) and a group represented by the formula (8), and a monomer having a specific substituent not involved in the curing is (A1), (C1), (A2), and (C2).

One of the causes of the exposure memory is considered to be charge accumulation at the layer interface. When a protective layer containing a cured product of a composition containing a monomer having two or more polymerizable functional groups is provided on the charge transport layer, the cured product is not mixed with the constituent material of the charge transport layer immediately below. It is presumed that the levels are not continuous at the interface and the charges are likely to stay. Therefore, in order to properly mix the material of the protective layer with the material of the charge transport layer, mixing a substance that does not participate in the curing with the protective layer may result in a decrease in film strength and a decrease in wear resistance because of inhibition of curing. End up. In the configuration of the present invention in which a monomer having two or more specific polymerizable functional groups and a monomer having a specific substituent not involved in curing are mixed, the exposure is performed without impairing wear resistance. It has been found that the intended effect of suppressing memory is obtained. In particular, it is speculated that the same alkylene group (R ¹ ) of these monomers contributes to inhibition of curing inhibition. As a result, it is considered that the substituents that do not participate in the curing while maintaining the wear resistance contribute to the mixing with the material of the charge transport layer immediately below, thereby suppressing the exposure memory.

  The charge transporting monomer contained in each composition is a monomer having a charge transporting structure. Examples of the charge transport structure include a triarylamine structure, a hydrazone structure, a stilbene structure, and a carbazole derivative.

  The above (A1), (B1), (A2), and (B2) are a charge transporting structure, a predetermined number of groups represented by the formula (1), a group represented by the formula (2), and a formula ( And a monomer having a group represented by 8). (A1), (B1), (A2), and (B2) are, for example, a charge transporting structure or a structure in which a plurality of charge transporting structures are bonded directly or via a hydrocarbon group, an oxygen atom, or the like. A predetermined number of groups represented by the formula (1), groups represented by the formula (2), and groups represented by the formula (8) are monomers bonded directly or via an aromatic group or the like.

  The above (E1) and (E2) are monomers having a charge transporting structure and a vinyl polymerizable functional group. The above (E1) and (E2) are, for example, a chargeable transporting structure or a structure in which a plurality of charge transporting structures are bonded directly or via a hydrocarbon group, an oxygen atom, etc. Is a monomer bonded directly or via an aromatic group or the like. Examples of the vinyl polymerizable functional group include an acryloyloxy group and a methacryloyloxy group. The polymerizable functional group possessed by the charge transporting monomer (E1) is preferably a functional group having the same structure as the formula (2) possessed by (C1) and (D1). Further, the polymerizable functional group possessed by the charge transporting monomer (E2) is preferably a functional group having the same structure as the formula (2) possessed by (C2) and (D2).

  Moreover, the monomer which does not have the charge transport property which said each composition contains is a monomer by which charge transport is not observed. The above (C1), (D1), (C2) and (D2) are, for example, a structure having no charge transporting property such as a saturated hydrocarbon structure or an alkyl ether structure, and a predetermined number of formulas (1). A monomer having a group represented by formula (2) and a group represented by formula (8). That is, (C1), (D1), (C2), and (D2) are a predetermined number of groups represented by Formula (1), groups represented by Formula (2), and groups represented by Formula (8). Is a monomer bonded to a structure having no charge transporting property.

（式（３）中、ｒは、０または１である。ｒが０のとき、−Ａｒ¹⁴は無く、Ａｒ¹³は１価の基である。ｒが１のとき、Ａｒ¹³は２価の基である。） The charge transporting monomers (A1) and (B1) are preferably monomers represented by the formula (3).

(In Formula (3), r is 0 or 1. When r is 0, there is no —Ar ¹⁴ and Ar ¹³ is a monovalent group. When r is 1, Ar ¹³ is a divalent group. Group.)

In the charge transporting monomer (A1),
Ar ¹¹ , Ar ¹² , Ar ¹⁴ , and Ar ¹³ when r is 0 are each independently a group represented by the formula (4), a group represented by the formula (5), or a substituted or unsubstituted aryl group Ar ¹³ when r is 1 represents a group represented by the formula (6), a group represented by the formula (7), or a substituted or unsubstituted arylene group. However, at least one of Ar ^{11 to} Ar ¹³ when r is 0 is a group represented by the formula (4), and at least one is a group represented by the formula (5), and r is 1 At least one of Ar ^{11 to} Ar ¹⁴ is a group represented by the formula (4) or a group represented by the formula (6), and at least one group represented by the formula (5) Or a group represented by formula (7).

（式（４）および式（５）中、Ａｒ²、およびＡｒ³は、それぞれ独立に、置換もしくは無置換のアリーレン基を示す。式（６）および式（７）中、Ａｒ⁴、およびＡｒ⁵は、それぞれ独立に、置換もしくは無置換の３価の芳香族基を示す。式（４）〜式（７）中、Ｒ^１は、置換もしくは無置換のアルキレン基を示す。式（５）および式（７）中、Ｘ²、Ｘ³、Ｙ²、Ｙ³、Ｚ²、およびＺ³は、それぞれ独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、アルコキシ基、ニトロ基、シアノ基を示す。（Ａ１）および（Ｂ１）が有する複数の式（５）で示される基、および式（７）で示される基において、それらの有するＸ²、Ｘ³、Ｙ²、Ｙ³、Ｚ²、およびＺ³が同一分子内あるいは分子間で異なっていても良い。） In the charge transporting monomer (B1),
Ar ¹¹ , Ar ¹² , Ar ¹⁴ , and Ar ¹³ when r is 0 each independently represent a group represented by the formula (5) or a substituted or unsubstituted aryl group, and when r is 1 Ar ¹³ represents a group represented by the formula (7) or a substituted or unsubstituted arylene group. However, at least two of Ar ^{11 to} Ar ¹³ when r is 0 are groups represented by the formula (5), and at least two of Ar ^{11 to} Ar ¹⁴ when r is 1 are represented by the formula It is a group represented by (5) or a group represented by formula (7).

(In formula (4) and formula (5), Ar ² and Ar ³ each independently represent a substituted or unsubstituted arylene group. In formula (6) and formula (7), Ar ⁴ and Ar 3 ⁵ independently represents a substituted or unsubstituted trivalent aromatic group, and in Formulas (4) to (7), R ¹ represents a substituted or unsubstituted alkylene group, Formula (5) And in formula (7), X ² , X ³ , Y ² , Y ³ , Z ² and Z ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, alkoxy group, a nitro group, a cyano group. (A1) and (B1) groups represented by the plurality of formula (5) with the, and the group represented by the formula (7), X ^2, X ³ having the them ^{, Y 2, Y 3, Z} 2, and Z ³ are different between the same intramolecular or molecular It may have.)

（式（９）中、ｒは、０または１である。ｒが０のとき、−Ａｒ⁶⁴は無く、Ａｒ⁶³は１価の基である。ｒが１のとき、Ａｒ⁶³は２価の基である。） The charge transporting monomers (A2) and (B2) are preferably monomers represented by the formula (9).

(In the formula (9), r is 0 or 1. When r is 0, there is no —Ar ⁶⁴ and Ar ⁶³ is a monovalent group. When r is 1, Ar ⁶³ is a divalent group. Group.)

In the charge transporting monomer (A2),
Ar ⁶¹ , Ar ⁶² , Ar ⁶⁴ , and Ar ⁶³ when r is 0 are each independently a group represented by the formula (10), a group represented by the formula (5), or a substituted or unsubstituted aryl group And when r is 1, Ar ⁶³ represents a group represented by the formula (11), a group represented by the formula (7), or a substituted or unsubstituted arylene group. However, at least one of Ar ^{61 to} Ar ⁶³ when r is 0 is a group represented by the formula (10), and at least one is a group represented by the formula (5), and r is 1 At least one of Ar ^{61 to} Ar ⁶⁴ is a group represented by the formula (10) or a group represented by the formula (11), and at least one group represented by the formula (5) Or a group represented by formula (7).

（式（１０）および式（５）中、Ａｒ⁷、およびＡｒ³は、それぞれ独立に、置換もしくは無置換のアリーレン基を示す。式（１１）および式（７）中、Ａｒ⁸、およびＡｒ⁵は、それぞれ独立に、置換もしくは無置換の３価の芳香族基を示す。式（１０）、式（１１）、式（５）、および（７）中、Ｒ^１は、置換もしくは無置換のアルキレン基を示す。式（１０）、式（１１）、式（５）、および（７）中、Ｘ²、Ｘ³、Ｘ⁵、Ｘ⁶、Ｙ²、Ｙ³、Ｙ⁵、Ｙ⁶、Ｚ²、Ｚ³、Ｚ⁵、およびＺ⁶は、それぞれ独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、アルコキシ基、ニトロ基、シアノ基を示す。（Ａ２）および（Ｂ２）が有する複数の式（１０）で示される基、式（１１）で示される基、式（５）で示される基、および式（７）で示される基において、それらの有するＸ²、Ｘ³、Ｘ⁵、Ｘ⁶、Ｙ²、Ｙ³、Ｙ⁵、Ｙ⁶、Ｚ²、Ｚ³、Ｚ⁵、およびＺ⁶が同一分子内または分子間で異なっていても良い。）
なお、式（３）で示されるモノマーおよび式（９）で示されるモノマーは、いずれも電荷輸送性構造として、トリアリールアミン構造を有するモノマーである。 In the charge transporting monomer (B2),
Ar ⁶¹ , Ar ⁶² , Ar ⁶⁴ , and Ar ⁶³ when r is 0 each independently represent a group represented by the formula (5) or a substituted or unsubstituted aryl group, and when r is 1 Ar ⁶³ represents a group represented by the formula (7) or a substituted or unsubstituted arylene group. However, at least two of Ar ^{61 to} Ar ⁶³ when r is 0 are groups represented by the formula (5), and at least two of Ar ^{61 to} Ar ⁶⁴ when r is 1 are represented by the formula It is a group represented by (5) or a group represented by formula (7).

(In Formula (10) and Formula (5), Ar ⁷ and Ar ³ each independently represent a substituted or unsubstituted arylene group. In Formula (11) and Formula (7), Ar ⁸ and Ar ⁵ each independently represents a substituted or unsubstituted trivalent aromatic group, wherein R ¹ is substituted or unsubstituted in formula (10), formula (11), formula (5), and (7); In formula (10), formula (11), formula (5), and (7), X ² , X ³ , X ⁵ , X ⁶ , Y ² , Y ³ , Y ⁵ , Y ⁶ , Z ² , Z ³ , Z ⁵ , and Z ⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group. A group represented by formula (10), a group represented by formula (11), a formula (5), ) And the group represented by formula (7), X ² , X ³ , X ⁵ , X ⁶ , Y ² , Y ³ , Y ⁵ , Y ⁶ , Z ² , Z ³ , Z ⁵ and Z ⁶ may be different within the same molecule or between molecules.)
The monomer represented by the formula (3) and the monomer represented by the formula (9) are both monomers having a triarylamine structure as a charge transporting structure.

  Each formula will be further described below.

In Formula (1), Formula (2), Formula (4) to Formula (8), Formula (10), and Formula (11), R ¹ represents a substituted or unsubstituted alkylene group. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonanylene group, and a decylene group. Examples of the substituent of the substituted alkylene group include a methyl group, an ethyl group, a propyl group, a trimethylsilyl group, a trifluoromethyl group, and a fluorine atom.

In formula (2), formula (5), formula (7), formula (8), formula (10), and formula (11), X ^{1 to} X ⁶ , Y ^{1 to} Y ⁶ , and Z ^{1 to} Z ⁶ Is as described above. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonanyl group, and a decyl group. Examples of the substituent of the substituted alkyl group include a methyl group, an ethyl group, a propyl group, and a phenyl group. Examples of the aryl group include a phenyl group, a biphenyl group, a fluorenyl group, a 9,9′-dimethylfluorenyl group, and a naphthyl group. Examples of the substituent for the substituted aryl group include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group, a nitro group, and a cyano group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. X ^{1 to} X ⁶ , Y ^{1 to} Y ⁶ , and Z ^{1 to} Z ⁶ are each preferably a hydrogen atom or a methyl group.

In ^the case ^{X 1 ~X 6, Y 1 ~Y} 6 and ^{that Z} 1 to Z ^6, is present in plural may each be the same or different. That is, as described above, (A1), (B1), (C1), (D1), (A2), (B2), (C2), and (D2) have a plurality of expressions (2), ( 5), groups represented by formula (7), formula (8), formula (10), and formula (11), X ^{1 to} X ⁶ , Y ^{1 to} Y ⁶ , and Z ^{1 to} Z ^{6 that they have} May be the same or different within the same molecule or between molecules.

Ar ^{11 to} Ar ¹⁴ in the formula (3) and Ar ^{61 to} Ar ⁶⁴ in the formula (9) are as described above. Examples of the aryl group include a phenyl group, a biphenylyl group, a fluorenyl group, a 9,9′-dimethylfluorenyl group, and a naphthyl group. Examples of the substituent of the substituted aryl group include a methyl group, for example, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, a nitro group, and a cyano group. Examples of the arylene group include a phenylene group, a biphenylylene group, a fluorenylene group, a 9,9′-dimethylfluorenylene group, and a naphthylene group. Examples of the substituent for the substituted arylene group include a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, a nitro group, and a cyano group.

Ar ^{2 to} Ar ⁵ , Ar ⁷ , and Ar ⁸ in Formula (4) to Formula (7), Formula (10), and Formula (11) are as described above. Examples of the arylene group include a phenylene group, a biphenylylene group, a fluorenylene group, a 9,9′-dimethylfluorenylene group, and a naphthylene group. Examples of the substituent for the substituted arylene group include a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, a nitro group, and a cyano group. Examples of the trivalent aromatic group include groups represented by the formulas (12) to (15). Examples of the substituent of the substituted trivalent aromatic group include a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, a nitro group, and a cyano group.

  Said (B1) or (B2) can be created by the synthesis method described in Patent Document 1 or Patent Document 2, for example.

  Said (A1) or (A2) can be created as follows, for example. Using the method described in (Synthesis Example 1) in paragraph [0087] of Patent Document 1, the dihydroxy compound 4 described in the reaction formula of [Outside 26] in paragraph [0087] is synthesized. This is reacted with acetic acid or a 3-chloropropionic acid derivative. Next, a compound obtained by condensation reaction of only one hydroxy group of the dihydroxy compound is separated by column purification, and an objective compound can be prepared by reacting an acrylic acid derivative or an acryloyl chloride derivative.

  The above (C1) or (C2) is obtained by using, in the synthesis method of (A1) or (A2), a compound having a plurality of hydroxy groups and not having a charge transporting structure instead of the dihydroxy compound of 4. Can be synthesized.

  The above (D1), (D2), (E1) or (E2) can be prepared in the same manner as the above (B1) or (B2).

  Examples of (A1) include the following exemplary compounds (A1) -1 to (A1) -29.

  Examples of (A2) include the following exemplary compounds (A2) -1 to (A2) -37.

Examples of (B1) include the following exemplary compounds (B1) -1 to (B1) -24.

Examples of (B2) include the following exemplary compounds (B2) -1 to (B2) -24.

Examples of (C1) include the following exemplary compounds (C1) -1 to (C1) -6.

Examples of (C2) include the following exemplary compounds (C2) -1 to (C2) -6.

Examples of (D1) include the following exemplary compounds (D1) -1 to (D1) -6.

Examples of (D2) include the following exemplary compounds (D2) -1 to (D2) -6.

Examples of (E1) include the following exemplary compound (E1) -1.

Examples of (E2) include the following exemplary compound (E2) -1.

  The above-mentioned monomers (A1), (C1), (A2), and (C2) having specific substituents not involved in curing are 0.1 mass relative to the total mass of monomer components contained in the composition. % To 30% by mass or less is preferable. More preferably, they are 1 mass% or more and 10 mass% or less.

  In addition, the monomers (B1), (D1), (B2), and (D2) having two or more specific polymerizable functional groups described above are 40% relative to the total mass of monomer components contained in the composition. It is preferable to make it contain by the mass% or more and 99.9 mass% or less.

  The charge transporting monomers (E1) and (E2) having one or more vinyl-based polymerizable functional groups are 45% by mass or more and 55% by mass or more based on the total mass of the monomer components contained in the composition. It is preferable to contain it by the mass% or less.

The protective layer can contain various additives. Examples of the additive include deterioration preventing agents such as antioxidants and ultraviolet absorbers, and lubricants such as polytetrafluoroethylene (PTFE) particles and carbon fluoride. Further, polymerization control agents such as polymerization reaction initiators and polymerization reaction terminators, leveling agents such as silicone oil, surfactants, and the like are also included.
The thickness of the protective layer is preferably 2 μm or more and 20 μm or less.

  The protective layer of the electrophotographic photosensitive member of the present invention includes a composition containing the above (A1) and (B1), a composition containing the above (C1), (D1) and (E1), the above (A2) and (B2). ), Or a coating film of a coating solution for protective layer containing any one of the compositions containing (C2), (D2), and (E2), and the composition in the coating film It can be formed by curing an object. In the present invention, the protective layer has a cured product of only one of the above compositions. Therefore, the protective layer coating liquid containing a plurality of the above compositions (for example, a composition containing (A1) and (B1) and a composition containing (C1), (D1) and (E1)). It does not have a cured product of the coating film of the protective layer coating solution.

The coating liquid for protective layer may contain the above various additives and solvents in addition to any one of the above compositions.
Solvents used in the coating solution for the protective layer include alcohol solvents such as methanol, ethanol and propanol, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, tetrahydrofuran, dioxane and the like. Ether solvents, 1,1,2,2,3,3,4-heptafluorocyclopentane, halogen solvents such as dichloromethane, dichloroethane, chlorobenzene, aromatic solvents such as benzene, toluene, xylene, methyl cellosolve, ethyl Examples include cellosolve solvents such as cellosolve. These solvents may be used alone or in combination of two or more.

  When applying the coating liquid for the protective layer, for example, a coating method such as a dip coating method (dipping method), a spray coating method, a spinner coating method, a bead coating method, a blade coating method, or a beam coating method can be used.

  The composition can be cured using heat, light (such as ultraviolet rays), or radiation (such as electron beams). Among these, polymerization using radiation is preferable, and polymerization using an electron beam is more preferable among radiations.

  When the polymerization is carried out using an electron beam, a polymerization initiator is not necessary, so that deterioration of electrophotographic characteristics due to the remaining polymerization initiator can be avoided. Further, since the polymerization reaction is efficient in a short time, productivity is also increased. When irradiating an electron beam, examples of the accelerator include a scanning type, an electro curtain type, a broad beam type, a pulse type, and a laminar type.

  When an electron beam is used, the acceleration voltage of the electron beam is preferably 120 kV or less from the viewpoint of suppressing material property deterioration due to the electron beam without impairing the polymerization efficiency. Further, the electron beam absorbed dose on the surface of the coating film of the protective layer coating solution is preferably 5 kGy or more and 50 kGy or less, and more preferably 1 kGy or more and 10 kGy or less.

  In addition, when the above composition is cured (polymerized) using an electron beam, it may be heated in an inert gas atmosphere after being irradiated with an electron beam in an inert gas atmosphere for the purpose of suppressing the polymerization inhibitory action by oxygen. preferable. Examples of the inert gas include nitrogen, argon, and helium.

Next, the overall configuration of the electrophotographic photoreceptor of the present invention will be described.
The electrophotographic photosensitive member of the present invention comprises a support, a charge generation layer formed on the support, a charge transport layer formed on the charge generation layer, and a protective layer formed on the charge transport layer. Have.

  FIG. 1 is a diagram illustrating an example of a layer structure of an electrophotographic photosensitive member. In FIG. 1, the electrophotographic photosensitive member has a support 101, a charge generation layer 102, a charge transport layer 103, and a protective layer 104 in this order, and the protective layer 104 is a surface layer of the electrophotographic photosensitive member. If necessary, a conductive layer or undercoat layer described later may be provided between the support and the photosensitive layer (charge generation layer, charge transport layer).

As the support used in the electrophotographic photosensitive member, a conductive one (conductive support) is preferable. For example, a support made of a metal such as aluminum, an aluminum alloy, or stainless steel or an alloy can be used. In the case of a support made of aluminum or aluminum alloy, an ED tube, an EI tube, or a support obtained by cutting, electrolytic composite polishing, wet or dry honing treatment of these can also be used. Alternatively, a thin film of a conductive material such as aluminum, an aluminum alloy, or an indium oxide-tin oxide alloy may be formed on a metal support or resin support, and used as a support.
The surface of the support may be subjected to cutting treatment, roughening treatment, alumite treatment, or the like.
A support formed by impregnating a resin or the like with conductive particles such as carbon black, tin oxide particles, titanium oxide particles, or silver particles, or a support made of conductive resin can also be used.

A conductive layer containing conductive particles and a binder resin may be provided between the support and the charge generation layer or the undercoat layer described below.
The conductive layer is formed by coating a conductive layer coating solution obtained by dispersing conductive particles together with a binder resin and a solvent to form a coating film, and then drying and / or curing the obtained coating film. can do.

  Examples of the conductive particles used in the conductive layer include carbon black, acetylene black, metal particles such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, and metal oxides such as tin oxide and ITO. Particles.

  Examples of the binder resin used for the conductive layer include acrylic resin, alkyd resin, epoxy resin, phenol resin, butyral resin, polyacetal, polyurethane, polyester, polycarbonate, and melamine resin.

  Examples of the solvent used in the conductive layer coating solution include ether solvents, alcohol solvents, ketone solvents, and aromatic hydrocarbon solvents.

  The thickness of the conductive layer is preferably 0.2 μm or more and 40 μm or less, and more preferably 5 μm or more and 40 μm or less.

An undercoat layer may be provided between the support or the conductive layer and the charge generation layer.
The undercoat layer can be formed by applying a coating solution for an undercoat layer containing a resin to form a coating film, and drying or curing the obtained coating film.

  Examples of the resin used for the undercoat layer include polyacrylic acid, methylcellulose, ethylcellulose, polyamide, polyimide, polyamideimide, polyamic acid, melamine resin, epoxy resin, and polyurethane.

  The undercoat layer may contain the above-described conductive particles, semiconductive particles, electron transporting material, and electron accepting material.

  Examples of the solvent used in the coating solution for the undercoat layer include ether solvents, alcohol solvents, ketone solvents, aromatic hydrocarbon solvents, and the like.

  The thickness of the undercoat layer is preferably 0.05 μm or more and 40 μm or less, and more preferably 0.4 μm or more and 20 μm or less.

  A charge generation layer is formed on the support, the conductive layer, or the undercoat layer.

  Examples of the charge generating material used in the electrophotographic photosensitive member include pyrylium, thiapyrylium dyes, phthalocyanine compounds, anthanthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, azo pigments, indigo pigments, quinacridone pigments, and quinocyanine pigments. It is done. Among these, gallium phthalocyanine is preferable. Furthermore, from the viewpoint of high sensitivity, hydroxygallium phthalocyanine is preferable, and among them, strong peaks at the Bragg angle 2θ of 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° in CuKα characteristic X-ray diffraction Hydroxygallium phthalocyanine crystals having the following are preferred.

  Examples of the binder resin used for the charge generation layer include polycarbonate, polyester, butyral resin, polyvinyl acetal, acrylic resin, vinyl acetate resin, and urea resin. Among these, a butyral resin is preferable. These resin may use only 1 type and may use 2 or more types together as a mixture or a copolymer.

  The charge generation layer is formed by applying a charge generation layer coating solution obtained by dispersing a charge generation material together with a binder resin and a solvent to form a coating film, and then drying the obtained coating film. Can do. The charge generation layer may be a vapor generation film of a charge generation material.

  In the charge generation layer, the ratio of the charge generation material to the binder resin is preferably 0.3 parts by mass or more and 4 parts by mass or less for the binder resin with respect to 1 part by mass of the charge generation material.

  Examples of the dispersion treatment method include a method using a homogenizer, an ultrasonic wave, a ball mill, a sand mill, an attritor, and a roll mill.

  Examples of the solvent used in the charge generation layer coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

  The thickness of the charge generation layer is preferably from 0.01 μm to 5 μm, and more preferably from 0.1 μm to 1 μm.

  In addition, various sensitizers, antioxidants, ultraviolet absorbers, and plasticizers can be added to the charge generation layer as necessary.

  The charge transport layer is formed by applying a charge transport layer coating solution obtained by dissolving a charge transport material and a binder resin in a solvent to form a coating film, and then drying the obtained coating film. Can do.

  Examples of the charge transport material used in the charge transport layer include triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, and triarylmethane compounds.

  Examples of the binder resin used for the charge transport layer include polyvinyl butyral, polyarylate, polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide, polyamide, polyvinyl pyridine, cellulose resin, urethane resin, and epoxy resin. , Agarose resin, cellulose resin, casein, polyvinyl alcohol, and polyvinylpyrrolidone. These resin may use only 1 type and may use 2 or more types together as a mixture or a copolymer.

  In the present invention, such a material for the charge transport layer and the cured product of the composition contained in the protective layer are mixed well due to the influence of substituents not involved in the curing of the monomer contained in the composition. It is estimated that the exposure memory is suppressed because it can be matched.

  The ratio of the charge transport material is preferably 30% by mass to 70% by mass with respect to the total mass of the charge transport layer.

  Examples of the solvent used in the charge transport layer coating solution include ether solvents, alcohol solvents, ketone solvents, and aromatic hydrocarbon solvents. The thickness of the charge transport layer is preferably 5 μm or more and 40 μm or less.

  The protective layer of the electrophotographic photosensitive member in the present invention is as described above, a composition containing (A1) and (B1), a composition containing (C1), (D1) and (E1), (A2) and The composition containing (B2) or the cured product of the composition containing (C2), (D2), and (E2) is contained. Further, as described above, the protective layer is a composition containing (A1) and (B1), a composition containing (C1), (D1) and (E1), and a composition containing (A2) and (B2). Or forming a coating film of a coating solution for a protective layer containing any one of the compositions containing (C2), (D2), and (E2), and curing the composition in the coating film Can be formed.

Next, FIG. 2 shows an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having an electrophotographic photosensitive member.
In FIG. 2, a cylindrical electrophotographic photosensitive member 1 is driven to rotate at a predetermined peripheral speed (process speed) in the direction of an arrow about an axis 2. The surface (circumferential surface) of the electrophotographic photosensitive member 1 is positively or negatively charged by a charging unit (primary charging unit) 3 during the rotation process. Next, the surface of the electrophotographic photoreceptor 1 is irradiated with exposure light (image exposure light) 4 output from an exposure means (image exposure means) (not shown). The exposure light 4 is intensity-modulated corresponding to the time-series electric digital image signal of the target image information. Examples of exposure means include slit exposure and laser beam scanning exposure. Thus, an electrostatic latent image corresponding to the target image information is formed on the surface of the electrophotographic photoreceptor 1.
The electrostatic latent image formed on the surface of the electrophotographic photoreceptor 1 is then developed (regular development or reversal development) with toner stored in the developing means 5 to form a toner image. The toner image formed on the surface of the electrophotographic photoreceptor 1 is transferred to the transfer material 7 by the transfer means 6. Here, when the transfer material 7 is paper, it is taken out from a paper feeding unit (not shown) in synchronization with the rotation of the electrophotographic photosensitive member 1 and fed between the electrophotographic photosensitive member 1 and the transfer means 6. Is done. Further, a bias voltage having a polarity opposite to the charge held in the toner is applied to the transfer means 6 from a bias power source (not shown). The transfer means may be an intermediate transfer type transfer means having a primary transfer member, an intermediate transfer member, and a secondary transfer member.
The transfer material 7 onto which the toner image has been transferred is separated from the surface of the electrophotographic photosensitive member 1, transported to a fixing unit 8, and subjected to a fixing process of the toner image, whereby an electronic image forming product (print, copy) is obtained. Printed out of the photographic device.

  The surface of the electrophotographic photoreceptor 1 after the transfer of the toner image is cleaned by a cleaning unit 9 to remove deposits such as transfer residual toner. The transfer residual toner can also be collected by a developing means or the like. Further, if necessary, the surface of the electrophotographic photosensitive member 1 is subjected to charge removal treatment by irradiation with pre-exposure light 10 from a pre-exposure unit (not shown), and then repeatedly used for image formation. When the charging unit 3 is a contact charging unit using a charging roller or the like, the pre-exposure unit is not always necessary.

  In the present invention, a plurality of components selected from the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, the transfer unit 6, the cleaning unit 9, and the like may be housed in a container to form a process cartridge. Further, the process cartridge may be detachable from the main body of the electrophotographic apparatus. For example, the electrophotographic photoreceptor 1 and at least one means selected from the group consisting of charging means 3, developing means 5, transfer means 6 and cleaning means 9 are integrally supported to form a cartridge. Then, the process cartridge 11 can be detachably attached to the main body of the electrophotographic apparatus using guide means 12 such as a rail of the main body of the electrophotographic apparatus.

  Hereinafter, specific examples will be given and described in more detail. In the examples, “part” means “part by mass”. In addition, the electrophotographic photoreceptor is hereinafter simply referred to as “photoreceptor”.

(Synthesis Example 1: Synthesis of Exemplary Compound (A1) -2))
Using the method of (Synthesis Example 1) described in paragraph [0087] of Patent Document 1, the dihydroxy compound of 4 described in [Outside 26] of paragraph [0087] (of the following reaction formula) Compound 1) was synthesized. To the 1 L flask, 80 g of the obtained dihydroxy compound, 80 g of acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 5 g of p-toluenesulfonic acid (PTS) and 200 ml of toluene were added and stirred at room temperature for 24 hours. After completion of the reaction, the obtained oil was separated and purified by silica gel column chromatography to obtain 40 g of compound 2 of the following reaction formula. Next, 40 g of the obtained compound 2, 40 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.5 g of p-toluenesulfonic acid (PTS) and 100 ml of toluene were added and stirred at room temperature for 24 hours. After completion of the reaction, the obtained oil was separated and purified by silica gel column chromatography to obtain 30 g of exemplary compound (A1) -2.

(Synthesis Example 2: Synthesis of Exemplary Compound (A2) -2))
Using the method of (Synthesis Example 1) described in paragraph [0087] of Patent Document 1, the dihydroxy compound of 4 described in [Outside 26] of paragraph [0087] (of the following reaction formula) Compound 1) was synthesized. 80 g of the obtained dihydroxy compound, 80 g of 3-chloropropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 5 g of p-toluenesulfonic acid (PTS) and 200 ml of toluene were added to a 1 L flask, and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, the obtained oil was separated and purified by silica gel column chromatography to obtain 35 g of compound 3 of the following reaction formula. Next, 35 g of the obtained compound 3, 35 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.5 g of p-toluenesulfonic acid (PTS) and 100 ml of toluene were added and stirred at room temperature for 24 hours. After completion of the reaction, the obtained oil was separated and purified by silica gel column chromatography to obtain 30 g of exemplary compound (A2) -2.

(Production Example 1 of electrophotographic photosensitive member)
-Support As a support, a cylindrical aluminum cylinder having a diameter of 29.92 mm, a length of 357.5 mm, and a thickness of 0.7 mm was used.
-Undercoat layer Next, 100 parts of zinc oxide particles (specific surface area: 19 m ² / g, powder resistance: 4.7 × 10 ⁶ Ω · cm) as a metal oxide were stirred and mixed with 500 parts of toluene. To this, 0.8 part of a silane coupling agent (compound name: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) is added for 6 hours. Stir. Thereafter, toluene was distilled off under reduced pressure, followed by heating and drying at 140 ° C. for 6 hours to obtain surface-treated zinc oxide particles.
Next, 15 parts of butyral resin (trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.) and 15 parts of blocked isocyanate (trade name: Sumijoule 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.) as a polyol resin are mixed solution. Dissolved. The mixed solution is a mixture of 73.5 parts of methyl ethyl ketone and 73.5 parts of 1-butanol.
To this solution, 80.8 parts of the surface-treated zinc oxide particles and 0.4 part of 2,3,4-trihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and this was added to a glass having a diameter of 0.8 mm. Dispersion was performed in a sand mill apparatus using beads in an atmosphere of 23 ± 3 ° C. for 3 hours. After dispersion, 0.01 parts of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Silicone), crosslinked polymethyl methacrylate (PMMA) particles (trade name: TECHPOLYMER SSX-103, manufactured by Sekisui Plastics Co., Ltd.) The average primary particle size of 3.1 μm) was added and stirred to prepare a coating solution for the undercoat layer.
This undercoat layer coating solution was applied onto the support by dip coating, and the resulting coating film was dried at 160 ° C. for 40 minutes to form an undercoat layer having a thickness of 18 μm.

・ポリビニルブチラール（商品名：エスレックＢＸ−１、積水化学工業（株）製）
・・・１０部
・シクロヘキサノン ・・・６００部
この電荷発生層用塗布液を下引き層上に浸漬塗布し、得られた塗膜を１５分間８０℃で乾燥させることによって、膜厚０．１８μｍの電荷発生層を形成した。 -Electricity generation layer Next, the following four substances were placed in a sand mill using glass beads having a diameter of 1 mm, dispersed for 4 hours, and then 700 parts of ethyl acetate was added to prepare a charge generation layer coating solution. .
-Crystal form hydroxygallium phthalocyanine crystal (charge generating material) with strong peaks at 7.4 ° and 28.2 ° with Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction. Calixarene compound represented by formula (s): 0.2 part

・ Polyvinyl butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.)
・ ・ ・ 10 parts ・ Cyclohexanone ・ ・ ・ 600 parts This coating solution for charge generation layer is dip coated on the undercoat layer, and the resulting coating film is dried at 80 ° C. for 15 minutes to obtain a film thickness of 0.18 μm. The charge generation layer was formed.

（構造式（Ｗ）中、０．９５および０．０５は、２つの構造単位のモル比（共重合比）である。）
この電荷輸送層用塗布液を電荷発生層上に浸漬塗布し、得られた塗膜を３０分間１１０℃で乾燥させることによって、膜厚１８μｍの電荷輸送層を形成した。 Next, a coating solution for a charge transport layer was prepared by dissolving the following five substances in a mixed solvent of 600 parts of xylene and 200 parts of dimethoxymethane.
・ Compound represented by the following structural formula (t) (charge transporting substance) 30 parts ・ Compound represented by the following structural formula (u) (charge transporting substance) 60 parts ・ In the following structural formula (v) Compound shown (charge transport material): 10 parts Polycarbonate resin (trade name: Iupilon Z400, manufactured by Mitsubishi Engineering Plastics Co., Ltd., bisphenol Z type polycarbonate): 100 parts Structural formula (w) (Viscosity average molecular weight Mv: 20000)
... 0.02 parts

(In the structural formula (W), 0.95 and 0.05 are molar ratios (copolymerization ratios) of two structural units.)
The charge transport layer coating solution was dip coated on the charge generation layer, and the resulting coating film was dried at 110 ° C. for 30 minutes to form a charge transport layer having a thickness of 18 μm.

Protective layer 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.) 100 parts / 1-propanol 100 parts mixed solvent, polyfluorone The mixture was filtered with a filter (trade name: PF-040, manufactured by Advantech Toyo Co., Ltd.). Two kinds of monomer compounds were added to this mixed solvent so that it might become a total of 100 parts as follows. By filtering this with a polyflon filter (trade name: PF-020, manufactured by Advantech Toyo Co., Ltd.), a coating solution for a second charge transport layer (protective layer) was prepared.
Exemplified compound (A1) -2 ... 5 parts Exemplified compound (B1) -2 ... 95 parts This coating solution obtained by dip-coating the coating solution for the second charge transport layer on the charge transport layer Was dried at 50 ° C. for 6 minutes in air. Thereafter, in nitrogen, the coating film was irradiated with an electron beam for 1.6 seconds under the conditions of an acceleration voltage of 70 kV and an absorbed dose of 8000 Gy while rotating the support (object to be irradiated) at 200 rpm.
Subsequently, the temperature was raised from 25 ° C. to 120 ° C. over 30 seconds in nitrogen, and the coating film was heated. The oxygen concentration in the atmosphere during electron beam irradiation and subsequent heating was 15 ppm. Next, the second charge transport layer (protective layer) having a thickness of 5 μm was formed by performing a heat treatment at 100 ° C. for 30 minutes in the air.
An electrophotographic photoreceptor was prepared as described above.

(Production example 2 of electrophotographic photosensitive member)
An electrophotographic photoreceptor was prepared in the same manner as in Production Example 1 of the electrophotographic photoreceptor except that the protective layer was changed as follows.

-Protective layer First, a lubricant dispersion was prepared by the following procedure.
1.5 parts of a fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) as a dispersant was dissolved in the following mixed solvent.
・ 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeorora H, manufactured by Nippon Zeon Co., Ltd.) ・ ・ ・ 30 parts ・ 1-propanol ・ ・ ・ 30 parts 30 parts of polytetrafluoroethylene particles (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) as a lubricant were added. This was put into a high-pressure disperser (trade name: Microfluidizer M-110EH, manufactured by Microfluidics, USA), and subjected to dispersion treatment four times at a pressure of 600 kgf / cm ² . This was filtered with a polyflon filter (trade name: PF-040, manufactured by Advantech Toyo Co., Ltd.) to obtain a lubricant dispersion.
Next, a mixed solvent of 70 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.) / 1 70 parts of 1-propanol was added to polyflon. The mixture was filtered with a filter (trade name: PF-040, manufactured by Advantech Toyo Co., Ltd.). Two kinds of monomer compounds were added to this mixed solvent so that it might become a total of 70 parts as follows. The monomer solution was obtained by filtering this with a polyfluorone filter (trade name: PF-020, manufactured by Advantech Toyo Co., Ltd.).
-Exemplified compound (A1) -2 ... 3.5 parts-Exemplified compound (B1) -2 ... 66.5 parts The obtained lubricant dispersion and the monomer solution are mixed to obtain a second charge transport layer. A coating solution for (protective layer) was prepared.

The coating solution for the second charge transport layer was dip-coated on the charge transport layer, and the obtained coating film was dried at 50 ° C. for 6 minutes in the air. Thereafter, in nitrogen, the coating film was irradiated with an electron beam for 1.6 seconds under the conditions of an acceleration voltage of 70 kV and an absorbed dose of 8000 Gy while rotating the support (object to be irradiated) at 200 rpm. Subsequently, the temperature was raised from 25 ° C. to 120 ° C. over 30 seconds in nitrogen, and the coating film was heated. The oxygen concentration in the atmosphere during electron beam irradiation and subsequent heating was 15 ppm. Next, the second charge transport layer (protective layer) having a thickness of 5 μm was formed by performing a heat treatment at 100 ° C. for 30 minutes in the air.
An electrophotographic photoreceptor was prepared as described above.

(Production Example 3 of Electrophotographic Photoreceptor)
An electrophotographic photoreceptor was prepared in the same manner as in Production Example 1 of the electrophotographic photoreceptor except that the protective layer was changed as follows.
-Protective layer After 1 part of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) is dissolved in 100 parts of n-propanol, the total is 100 parts as follows. Two monomer compounds were added as described above.
-Exemplified compound (A1) -2 ... 5 parts-Exemplified compound (B1) -2 ... 95 parts 1,1,2,2,3,3,4-Heptafluorocyclopentane 100 parts, 4- A coating solution for the second charge transport layer (protective layer) was prepared by adding 0.01 part of methoxyphenol.
This coating solution for protective layer was dip coated on the charge transport layer to form a coating film, and the resulting coating film was heat-treated at 50 ° C. for 5 minutes. Then, using a metal halide lamp, the coating film was irradiated with ultraviolet rays for 20 seconds under the condition of irradiation intensity: 500 mW / cm ² , and heat-treated for 30 minutes under the condition that the coating film reached 130 ° C. A two-charge transport layer (protective layer) was formed.

(Production Example 4 of electrophotographic photoreceptor)
Protective layer 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.) 100 parts / 1-propanol 100 parts mixed solvent, polyfluorone The mixture was filtered with a filter (trade name: PF-040, manufactured by Advantech Toyo Co., Ltd.). Three kinds of monomer compounds were added to this mixed solvent so that it might become a total of 100 parts as follows. By filtering this with a polyflon filter (trade name: PF-020, manufactured by Advantech Toyo Co., Ltd.), a coating solution for a second charge transport layer (protective layer) was prepared.
Exemplified compound (C1) -1 ... 5 parts Exemplified compound (D1) -1 ... 45 parts Exemplified compound (E1) -1 ... 50 parts Charge the coating solution for the second charge transport layer. It was dip-coated on the transport layer, and the resulting coating film was dried at 50 ° C. for 6 minutes in the air. Thereafter, in nitrogen, the coating film was irradiated with an electron beam for 1.6 seconds under the conditions of an acceleration voltage of 70 kV and an absorbed dose of 8000 Gy while rotating the support (object to be irradiated) at 200 rpm.
Subsequently, the temperature was raised from 25 ° C. to 120 ° C. over 30 seconds in nitrogen, and the coating film was heated. The oxygen concentration in the atmosphere during electron beam irradiation and subsequent heating was 15 ppm. Next, the second charge transport layer (protective layer) having a thickness of 5 μm was formed by performing a heat treatment at 100 ° C. for 30 minutes in the air.
An electrophotographic photoreceptor was prepared as described above.

(Evaluation of wear resistance)
Using an iR-ADV C5255 electrophotographic photosensitive member manufactured by Canon Inc. and a jig, the amount of wear due to rubbing of the cleaning blade was examined. As the jig, a jig having a motor for supporting the cartridge and rotating the electrophotographic photosensitive member was used. The electrophotographic photosensitive member prepared in the cartridge was mounted in a normal temperature and normal humidity environment at a temperature of 23 ° C. and a humidity of 50% RH, and the rotation speed of the electrophotographic photosensitive member was 250 mm / sec. The film thickness before and after the test was measured with an eddy current film thickness meter (Fischerscope, manufactured by Fisher Instruments). Six points were measured uniformly in the generatrix direction of the cylindrical electrophotographic photosensitive member, and the average value of the six points was adopted as the total film thickness of the organic layer. The difference in total film thickness before and after the test was determined as the amount of scraping (μm).

(Evaluation of exposure memory)
The prepared electrophotographic photosensitive member was irradiated with light from a white fluorescent lamp, and the surface potential before and after the irradiation was measured to evaluate the exposure memory. All of the following evaluations were performed in a normal temperature and humidity environment with a temperature of 23 ° C. and a humidity of 50% RH. Light irradiation was performed for 5 minutes using an illuminometer and adjusting the distance between the electrophotographic photosensitive member and the white fluorescent lamp so that the amount of irradiation light was 1500 (lx). The surface potential before and after irradiation was measured using a black station of iR-ADV C5255 manufactured by Canon Inc. Instead of the black station developer, a surface potential meter (trade name: model 344, manufactured by Trek Japan Co., Ltd.) was attached, and a cartridge having the prepared electrophotographic photosensitive member was installed. The development position potential when the image exposure is turned off on the electrophotographic photosensitive member before being irradiated with light from the white fluorescent lamp is −500 V, and the development position when the image exposure is turned on. The charging voltage of the primary charger and the amount of image exposure light were adjusted so that the potential (potential after image exposure) was −150V. The potential after image exposure was measured with the same setting as before irradiation even after irradiation with white fluorescent light. The absolute value of the difference in potential after image exposure before and after irradiation with the white fluorescent lamp was determined as exposure memory (V).

(Examples 1 to 25)
In each Example, one of the methods of Production Examples 1 to 3 of an electrophotographic photosensitive member was selected to prepare an electrophotographic photosensitive member. At this time, the two types of monomer compounds added to the coating solution for the second charge transport layer (protective layer) were changed to the compounds and parts shown in Table 1. (In Table 1, shown in the columns of Compound 1 and Compound 2.) Two electrophotographic photoreceptors were prepared for each example, one for the above-mentioned wear resistance test and the other for the above-mentioned abrasion resistance test. The exposure memory was evaluated. The results are shown in Table 1.

(Examples 26 to 28)
In each Example, an electrophotographic photosensitive member was prepared using the method of Production Example 4 of an electrophotographic photosensitive member. At this time, the above-described three monomer compounds added to the coating solution for the second charge transport layer (protective layer) were changed to the compounds shown in Table 2 and the number of parts. (Shown in the column of Compound 1, Compound 2, and Compound 3 in Table 2.) Two electrophotographic photoreceptors were prepared for each example, and one was evaluated for the above abrasion resistance test. Evaluated the above exposure memory. The results are shown in Table 2.

(Comparative Example 1)
In Example 1, an electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the coating liquid for protective layer was prepared using the following compound (F) instead of the exemplified compound (A1) -2. Table 3 shows the compounds, the number of parts, and the evaluation results.

(Comparative Example 2)
In Example 1, an electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the coating liquid for protective layer was prepared using the following compound (G) instead of the exemplified compound (A1) -2. Table 3 shows the compounds, the number of parts, and the evaluation results.

(Comparative Example 3)
In Example 1, the following compound (H) was used in place of the exemplified compound (A1) -2, and a protective layer coating solution was prepared using the following compound (I) in place of the exemplified compound (B1) -2. Produced an electrophotographic photoreceptor in the same manner as in Example 1. Table 3 shows the compounds, the number of parts, and the evaluation results.

(Comparative Example 4)
In Example 1, electrophotography was carried out in the same manner as in Example 1, except that the exemplified compound (A1) -2 was not used and the protective compound coating solution was prepared by changing the exemplified compound (B1) -2 to 100 parts. A photoreceptor was manufactured. Table 3 shows the compounds, the number of parts, and the evaluation results.

(Comparative Example 5)
In Example 5, Exemplified Compound (A1) -6 was not used, and Exemplified Compound (B1) -6 was changed to 100 parts to prepare a coating solution for protective layer. A photoreceptor was manufactured. Table 3 shows the compounds, the number of parts, and the evaluation results.

(Comparative Example 6)
In Example 9, electrophotography was carried out in the same manner as in Example 1 except that the exemplified compound (A1) -25 was not used and the example compound (B1) -20 was changed to 100 parts to prepare a protective layer coating solution. A photoreceptor was manufactured. Table 3 shows the compounds, the number of parts, and the evaluation results.

(Comparative Example 7)
In Example 10, Exemplified Compound (A1) -29 was not used, and Exemplified Compound (B1) -24 was changed to 100 parts to prepare a coating solution for protective layer. A photoreceptor was manufactured. Table 3 shows the compounds, the number of parts, and the evaluation results.

(Comparative Example 8)
In Example 14, Exemplified Compound (A1) -2 was not used, and the same procedure as in Example 1 was carried out except that the coating solution for protective layer was prepared by changing Exemplified Compound (B1) -2 to 70 parts. A photoreceptor was manufactured. Table 3 shows the compounds, the number of parts, and the evaluation results.

  According to the examples, the electrophotographic photosensitive member according to the present invention has a scraping amount of not more than a measurement limit (0.1 μm), an exposure memory of less than 40V, high wear resistance, and the exposure memory is suppressed. It can be said that this is an electrophotographic photoreceptor.

  In Comparative Example 1 and Comparative Example 2, as a result of adding a substance not involved in curing in place of (A1) to the protective layer coating solution, the amount of abrasion increased and the wear resistance was impaired.

As a result of using a charge transporting monomer having a structure without R ^{1 in} Comparative Example 3, the amount of abrasion increased and the wear resistance was impaired. About this, since the freedom degree of the functional group site | part of a monomer is low, it is guessed that hardening became inadequate.

  In Comparative Examples 4 to 8, as a result of not using a monomer having a specific substituent (group represented by the formula (1)) that does not participate in curing, the amount of abrasion is less than the measurement limit, but the exposure memory is It was 50V or more. These electrophotographic photoreceptors are electrophotographic photoreceptors that have sufficient abrasion resistance but remain subject to exposure memory.

DESCRIPTION OF SYMBOLS 101 Support body 102 Charge generation layer 103 Charge transport layer 104 Protective layer 1 Electrophotographic photosensitive member 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means

Claims (11)

An electrophotographic photosensitive member having a support, a charge generation layer formed on the support, a charge transport layer formed on the charge generation layer, and a protective layer formed on the charge transport layer, The electrophotographic photoreceptor, wherein the protective layer contains a cured product of a composition containing the following (A1) and (B1).
(A1): Charge transporting monomer (B1) having at least one group represented by formula (1) and at least one group represented by formula (2): Group represented by formula (2) Charge transporting monomer which has two or more and does not have the group represented by the formula (1)

(In Formula (1) and Formula (2), R ¹ represents a substituted or unsubstituted alkylene group. X ¹ , Y ¹ , and Z ¹ are each independently a hydrogen atom, substituted or unsubstituted alkyl, A group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group, in the groups represented by the formula (2) that (A1) and (B1) have, X ¹ , Y that they have ¹ and Z ¹ may be different within the same molecule or between molecules.) 2. The electrophotographic photosensitive member according to claim 1, wherein (A1) and (B1) are charge transporting monomers represented by the formula (3).

(In Formula (3), r is 0 or 1. When r is 0, there is no —Ar ¹⁴ and Ar ¹³ is a monovalent group. When r is 1, Ar ¹³ is a divalent group. It is a group.
In the charge transporting monomer (A1),
Ar ¹¹ , Ar ¹² , Ar ¹⁴ , and Ar ¹³ when r is 0 are each independently a group represented by the formula (4), a group represented by the formula (5), or a substituted or unsubstituted aryl group Ar ¹³ when r is 1 represents a group represented by the formula (6), a group represented by the formula (7), or a substituted or unsubstituted arylene group. However, at least one of Ar ^{11 to} Ar ¹³ when r is 0 is a group represented by the formula (4), and at least one is a group represented by the formula (5), and r is 1 At least one of Ar ^{11 to} Ar ¹⁴ is a group represented by the formula (4) or a group represented by the formula (6), and at least one group represented by the formula (5) Or a group represented by formula (7).
In the charge transporting monomer (B1),
Ar ¹¹ , Ar ¹² , Ar ¹⁴ , and Ar ¹³ when r is 0 each independently represent a group represented by the formula (5) or a substituted or unsubstituted aryl group, and when r is 1 Ar ¹³ represents a group represented by the formula (7) or a substituted or unsubstituted arylene group. However, at least two of Ar ^{11 to} Ar ¹³ when r is 0 are groups represented by the formula (5), and at least two of Ar ^{11 to} Ar ¹⁴ when r is 1 are represented by the formula It is a group represented by (5) or a group represented by formula (7). )

(In formula (4) and formula (5), Ar ² and Ar ³ each independently represent a substituted or unsubstituted arylene group. In formula (6) and formula (7), Ar ⁴ and Ar 3 ⁵ independently represents a substituted or unsubstituted trivalent aromatic group, and in Formulas (4) to (7), R ¹ represents a substituted or unsubstituted alkylene group, Formula (5) And in formula (7), X ² , X ³ , Y ² , Y ³ , Z ² and Z ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, alkoxy group, a nitro group, a cyano group. (A1) and (B1) groups represented by the plurality of formula (5) with the, and the group represented by the formula (7), X ^2, X ³ having the them ^{, Y 2, Y 3, Z} 2, and Z ³ are different between the same intramolecular or molecular It may have.) An electrophotographic photosensitive member having a support, a charge generation layer formed on the support, a charge transport layer formed on the charge generation layer, and a protective layer formed on the charge transport layer, The electrophotographic photoreceptor, wherein the protective layer contains a cured product of a composition containing the following (C1), (D1), and (E1).
(C1): Monomer having at least one group represented by formula (1) and having at least one group represented by formula (2) and having no charge transport property (D1): Formula (2) Monomer (E1) having at least two groups represented by the formula (1) and not having the group represented by the formula (1) and having at least one vinyl-based polymerizable functional group Charge transporting monomer

(In Formula (1) and Formula (2), R ¹ represents a substituted or unsubstituted alkylene group. X ¹ , Y ¹ , and Z ¹ are each independently a hydrogen atom, substituted or unsubstituted alkyl, A group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group, in the groups represented by the formula (2) that (C1) and (D1) have, X ¹ , Y ¹ and Z ¹ may be different within the same molecule or between molecules.) An electrophotographic photosensitive member having a support, a charge generation layer formed on the support, a charge transport layer formed on the charge generation layer, and a protective layer formed on the charge transport layer, The electrophotographic photoreceptor, wherein the protective layer contains a cured product of a composition containing the following (A2) and (B2).
(A2): Charge transporting monomer (B2) having at least one group represented by formula (8) and at least one group represented by formula (2): Group represented by formula (2) Charge transporting monomer having 2 or more and having no group represented by formula (8)

(In Formula (8) and Formula (2), R ¹ represents a substituted or unsubstituted alkylene group. L represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. X ¹ , Y ¹ , Z ¹ , X ⁴ , Y ⁴ , and Z ⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group (A2). And (B2) have a plurality of groups represented by the formula (2) and a group represented by the formula (8), X ¹ , Y ¹ , Z ¹ , X ⁴ , Y ⁴ , and Z ⁴ May be different within the same molecule or between molecules.) 5. The electrophotographic photosensitive member according to claim 4, wherein (A2) and (B2) are charge transporting monomers represented by the formula (9).

(In the formula (9), r is 0 or 1. When r is 0, there is no —Ar ⁶⁴ and Ar ⁶³ is a monovalent group. When r is 1, Ar ⁶³ is a divalent group. It is a group.
In the charge transporting monomer (A2),
Ar ⁶¹ , Ar ⁶² , Ar ⁶⁴ , and Ar ⁶³ when r is 0 are each independently a group represented by the formula (10), a group represented by the formula (5), or a substituted or unsubstituted aryl group And when r is 1, Ar ⁶³ represents a group represented by the formula (11), a group represented by the formula (7), or a substituted or unsubstituted arylene group. However, at least one of Ar ^{61 to} Ar ⁶³ when r is 0 is a group represented by the formula (10), and at least one is a group represented by the formula (5), and r is 1 At least one of Ar ^{61 to} Ar ⁶⁴ is a group represented by the formula (10) or a group represented by the formula (11), and at least one group represented by the formula (5) Or a group represented by formula (7).
In the charge transporting monomer (B2),
Ar ⁶¹ , Ar ⁶² , Ar ⁶⁴ , and Ar ⁶³ when r is 0 each independently represent a group represented by the formula (5) or a substituted or unsubstituted aryl group, and when r is 1 Ar ⁶³ represents a group represented by the formula (7) or a substituted or unsubstituted arylene group. However, at least two of Ar ^{61 to} Ar ⁶³ when r is 0 are groups represented by the formula (5), and at least two of Ar ^{61 to} Ar ⁶⁴ when r is 1 are represented by the formula It is a group represented by (5) or a group represented by formula (7). )

(In Formula (10) and Formula (5), Ar ⁷ and Ar ³ each independently represent a substituted or unsubstituted arylene group. In Formula (11) and Formula (7), Ar ⁸ and Ar ⁵ each independently represents a substituted or unsubstituted trivalent aromatic group, wherein R ¹ is substituted or unsubstituted in formula (10), formula (11), formula (5), and (7); In formula (10), formula (11), formula (5), and (7), X ² , X ³ , X ⁵ , X ⁶ , Y ² , Y ³ , Y ⁵ , Y ⁶ , Z ² , Z ³ , Z ⁵ , and Z ⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group. A group represented by formula (10), a group represented by formula (11), a formula (5), ) And the group represented by formula (7), X ² , X ³ , X ⁵ , X ⁶ , Y ² , Y ³ , Y ⁵ , Y ⁶ , Z ² , Z ³ , Z ⁵ and Z ⁶ may be different within the same molecule or between molecules.) An electrophotographic photosensitive member having a support, a charge generation layer formed on the support, a charge transport layer formed on the charge generation layer, and a protective layer formed on the charge transport layer, The electrophotographic photoreceptor, wherein the protective layer contains a cured product of a composition comprising the following (C2), (D2), and (E2).
(C2): Monomer having at least one group represented by formula (8) and having at least one group represented by formula (2) and having no charge transport property (D2): Formula (2) A monomer (E2) having at least two groups represented by formula (8) and not having the group represented by the formula (8) and having at least one vinyl-based polymerizable functional group Charge transporting monomer

(In Formula (8) and Formula (2), R ¹ represents a substituted or unsubstituted alkylene group. L represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. X ¹ , Y ¹ , Z ¹ , X ⁴ , Y ⁴ , and Z ⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group (C2). And (D2) have a plurality of groups represented by the formula (2) and a group represented by the formula (8), X ¹ , Y ¹ , Z ¹ , X ⁴ , Y ⁴ , and Z ⁴ May be different within the same molecule or between molecules.) The electrophotographic photoreceptor according to any one of claims 1 to 6, wherein R ¹ is an ethylene group, a propylene group, a butylene group, a pentylene group, or a hexylene group. A method for producing an electrophotographic photosensitive member comprising a support, a charge generation layer formed on the support, a charge transport layer formed on the charge generation layer, and a protective layer formed on the charge transport layer A composition comprising the following (A1) and (B1), a composition comprising the following (C1), (D1) and (E1), a composition comprising the following (A2) and (B2), or the following ( C2), (D2), and a step of preparing a protective layer coating solution containing any one of the compositions containing (E2), and forming a coating film of the protective layer coating solution. A method for producing an electrophotographic photosensitive member, comprising the step of forming the protective layer by curing the composition in a film.
(A1): Charge transporting monomer (B1) having at least one group represented by formula (1) and at least one group represented by formula (2): Group represented by formula (2) A charge transporting monomer (C1) having at least one group represented by formula (1) and having at least one group represented by formula (1) Monomer (D1) having at least one group represented by formula (2) having no charge transporting property: having two or more groups represented by formula (2) and having a group represented by formula (1) A monomer having no charge transporting property (E1): a charge transporting monomer having one or more vinyl-based polymerizable functional groups (A2): having at least one group represented by formula (8), and Charge transporting monomer (B2) having one or more groups represented by the formula (2): Two or more groups represented by the formula (2), and the formula (8) Charge transporting monomer (C2) having no group represented by formula (8): having one or more groups represented by formula (8) and having one or more groups represented by formula (2) Monomer (D2) not having: A monomer (E2) having two or more groups represented by the formula (2) and having no group represented by the formula (8) and having no charge transporting property : Charge transporting monomer having one or more vinyl-based polymerizable functional groups

(In Formula (1) and Formula (2), R ¹ represents a substituted or unsubstituted alkylene group. X ¹ , Y ¹ , and Z ¹ are each independently a hydrogen atom, substituted or unsubstituted alkyl, A group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group, (A1), (B1), (C1), (D1), (A2), (B2), (C2), And in the groups represented by the plurality of formulas (2) possessed by (D2), X ¹ , Y ¹ and Z ¹ possessed by them may be different within the same molecule or between molecules.

(In Formula (8), R ¹ represents a substituted or unsubstituted alkylene group. L represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. X ⁴ , Y ⁴ , and Z ⁴ are each independently selected. Are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group, wherein (A2) and (C2) have a plurality of formulas (8) In the group shown, X ⁴ , Y ⁴ and Z ⁴ which they have may be different within the same molecule or between molecules.)   The method for producing an electrophotographic photosensitive member according to claim 8, wherein the composition is cured by irradiating the coating film of the coating solution for the protective layer with an electron beam.   An electrophotographic photosensitive member according to any one of claims 1 to 7, and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means, are integrally supported, and electrophotographic A process cartridge which is detachable from the apparatus main body.   An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, and a charging unit, an exposure unit, a developing unit, and a transfer unit.

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