JP6628555B2 - Electrophotographic photoreceptor, method of manufacturing electrophotographic photoreceptor, process cartridge and electrophotographic apparatus - Google Patents

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.

  Electrophotographic photoreceptors are required to have high abrasion resistance. Patent Literatures 1 and 2 disclose a cured product obtained by curing a charge transporting monomer having a polymerizable functional group on a surface layer of an electrophotographic photoreceptor, thereby reducing the abrasion resistance of the electrophotographic photoreceptor. Techniques for improving are described.

  An electrophotographic photoreceptor provided with a surface layer containing the cured product tends to be inferior in various electrical properties as compared with an electrophotographic photoreceptor without a surface layer. In particular, since the electrophotographic photoreceptor is likely to be exposed to light when replaced in a user's use environment, exposure memory is a problem in electrical characteristics.

JP 2000-066425 A JP 2010-156835 A

  An object of the present invention is to provide an electrophotographic photoreceptor having high abrasion resistance and suppressed exposure memory, and a method for manufacturing 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. Wherein the protective layer contains a cured product of a composition containing the following (A1) and (B1).
(A1): a charge-transporting monomer having at least one group represented by the formula (1) and at least one group represented by the formula (2) (B1): a group represented by the formula (2) Having two or more groups and having no group represented by the formula (1)

(In the formulas (1) and (2), R ¹ represents a substituted or unsubstituted alkylene group. X ¹ , Y ¹ , and Z ¹ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group. A group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group, and in the groups represented by formula (2) in (A1) and (B1), X ¹ , Y ¹ and Z ¹ may be different within the same molecule or between the 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 an electrophotograph 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. An electrophotographic photoconductor, wherein the protective layer contains a cured product of a composition containing the following (C1), (D1), and (E1).
(C1): Monomer having one or more groups represented by formula (1) and not having charge transporting property having one or more groups represented by formula (2) (D1): Formula (2) Having two or more groups represented by the formula (1) and having no group represented by the formula (1) and having no charge transporting property (E1): having at least one vinyl polymerizable functional group Charge transporting monomer.

(In the formulas (1) and (2), R ¹ represents a substituted or unsubstituted alkylene group. X ¹ , Y ¹ , and Z ¹ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group. A group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group, and in the groups represented by formula (2) in (C1) and (D1), X ¹ and Y of ¹ and Z ¹ may be different within the same molecule or between the 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 an electrophotograph 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. An electrophotographic photosensitive member, wherein the protective layer contains a cured product of a composition containing the following (A2) and (B2).
(A2): a charge-transporting monomer having at least one group represented by the formula (8) and having at least one group represented by the formula (2) (B2): a group represented by the formula (2) A charge-transporting monomer having two or more and having no group represented by the formula (8)

(In the formulas (8) and (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) a plurality of groups represented by the formula (2) and a group represented by the formula (8), which have 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 an electrophotograph 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. An electrophotographic photoconductor, wherein the protective layer contains a cured product of a composition containing the following (C2), (D2), and (E2).
(C2): a monomer having at least one group represented by the formula (8) and having no charge transporting property having at least one group represented by the formula (2) (D2): a formula (2) (E2) having two or more groups represented by the formula and having no group represented by the formula (8) and having no charge transporting property: having at least one vinyl polymerizable functional group Charge transporting monomer

(In the formulas (8) and (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) a plurality of groups represented by the formula (2) and a group represented by the formula (8), which have 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 an electrophotograph 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. 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 containing the following (A2) and (B2) A step of preparing a coating solution for a protective layer containing the composition or any one of the compositions containing the following (C2), (D2) and (E2), and a coating film of the coating solution for the protective layer And forming the protective layer by curing the composition in the coating film.
(A1): a charge-transporting monomer having at least one group represented by the formula (1) and at least one group represented by the formula (2) (B1): a group represented by the formula (2) Having two or more groups, and having no group represented by the formula (1), a charge transporting monomer (C1): having one or more groups represented by the formula (1), and (D1) having at least one group represented by formula (1): having at least two 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 at least one vinyl polymerizable functional group (A2): having at least one group represented by the formula (8), and A charge transporting monomer (B2) having one or more groups represented by the formula (2): having two or more groups represented by the formula (2), and A charge-transporting monomer (C2) having no group represented by the formula: charge-transporting monomer having at least one group represented by the formula (8) and having at least one group represented by the formula (2) Having no monomer.
(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 Transporting monomer having at least one functional group

(In the formulas (1) and (2), R ¹ represents a substituted or unsubstituted alkylene group. X ¹ , Y ¹ , and Z ¹ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group. 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 X ¹ , Y ¹ , and Z ^{1 of} a plurality of groups represented by formula (2) in (D2) may be different in 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 Represents 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 groups shown, X ⁴ , Y ⁴ , and Z ⁴ possessed by them may be different within the same molecule or between molecules.)

  Further, according to the present invention, the electrophotographic photosensitive member and at least one unit selected from the group consisting of a charging unit, a developing unit, a transfer unit and a cleaning unit are integrally supported, and are detachably attached to an electrophotographic apparatus main body. A certain process cartridge.

  Further, the present invention is an electrophotographic apparatus having the above electrophotographic photosensitive member, and a charging unit, an exposing unit, a developing unit and a transferring unit.

  ADVANTAGE OF THE INVENTION According to this invention, the abrasion resistance is high, and the electrophotographic photosensitive member with which exposure memory was suppressed, and its manufacturing method can be provided. Further, according to the present invention, it is possible to provide a process cartridge and an electrophotographic apparatus having such an electrophotographic photosensitive member.

FIG. 3 is a diagram illustrating an example of a layer configuration of an electrophotographic photosensitive member. FIG. 2 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 photoreceptor 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 photoreceptor 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): a charge-transporting monomer having at least one group represented by the formula (1) and at least one group represented by the formula (2) (B1): a group represented by the formula (2) Having two or more groups, and having no group represented by the formula (1), a charge transporting monomer (C1): having one or more groups represented by the formula (1), and (D1) having at least one group represented by formula (1): having at least two 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 at least one vinyl polymerizable functional group (A2): having at least one group represented by the formula (8), and A charge transporting monomer (B2) having one or more groups represented by the formula (2): having two or more groups represented by the formula (2), and A charge-transporting monomer (C2) having no group represented by the formula: charge-transporting monomer having at least one group represented by the formula (8) and having at least one group represented by the formula (2) (D2) having no group represented by the formula (2): 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 at least one vinyl polymerizable functional group

(In the formulas (1) and (2), R ¹ represents a substituted or unsubstituted alkylene group. X ¹ , Y ¹ , and Z ¹ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group. 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 X ¹ , Y ¹ , and Z ^{1 of} a plurality of groups represented by formula (2) in (D2) may be different in 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 Represents 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) in (C2) In the group represented by, X ⁴ , Y ⁴ and Z ⁴ possessed by them 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 indicate the same general formula.

The electrophotographic photoreceptor of the present invention has high abrasion resistance and has reduced exposure memory. A 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 that does not participate in curing, and further, the alkylene group (R ¹ ) of the monomer has It is the same. The specific polymerizable functional group is a group represented by the formula (2), and the monomer having two or more specific polymerizable functional groups is represented by (B1), (D1), (B2), or (D2). is there. Further, the specific substituent not involved in the curing is a group represented by the formula (1) or a group represented by the formula (8), and the monomer having the 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 the stagnation of charges 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 does not mix with the constituent material of the charge transport layer immediately below. It is presumed that the level is not continuous at the interface, and the charge tends to stay. Therefore, if a material that does not participate in curing is mixed with the protective layer in order to appropriately mix the material of the protective layer with the material of the charge transport layer, the film strength decreases and the abrasion resistance decreases due to the inhibition of curing, possibly due to the inhibition of curing. I will. The inventors of the present invention mix a monomer having two or more specific polymerizable functional groups and a monomer having a specific substituent that does not participate in curing with the configuration of the present invention, without impairing abrasion resistance, It has been found that the intended effect of suppressing memory can be obtained. In particular, it is presumed that the same alkylene group (R ¹ ) of these monomers contributes to the inhibition of curing inhibition. As a result, it is considered that the substituents not involved in curing contribute to mixing with the material of the charge transport layer immediately below while maintaining abrasion resistance, thereby suppressing exposure memory.

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

  The above (A1), (B1), (A2) and (B2) represent a charge transporting structure and a predetermined number of groups represented by the formula (1), groups represented by the formula (2), And a monomer having the 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 the groups represented by the formula (1), the groups represented by the formula (2), and the groups represented by the formula (8) are bonded monomers 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) include, for example, a vinyl polymerizable functional group to 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. 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 of the charge transporting monomer (E1) is preferably a functional group having the same structure as that of the formula (2) of (C1) and (D1). The polymerizable functional group of the charge transporting monomer (E2) is preferably a functional group having the same structure as that of the formula (2) of (C2) and (D2).

  Further, the monomer having no charge transporting property contained in each of the above-described compositions is a monomer in 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). It is a monomer having a group represented by the following formula, a group represented by the formula (2), and a group represented by the formula (8). That is, (C1), (D1), (C2) and (D2) are a predetermined number of groups represented by the formula (1), groups represented by the formula (2), and groups represented by the 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。） It is preferable that the charge transporting monomers (A1) and (B1) are monomers represented by the formula (3).

(In the 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 divalent. 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 Wherein, when r is 1, Ar ¹³ represents a group represented by the formula (6), a group represented by the formula (7), or a substituted or unsubstituted arylene group. However, when r is 0, at least one of Ar ^{11 to} Ar ¹³ is a group represented by the formula (4), and at least one is a group represented by the formula (5); 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 is a group represented by the formula (5) Or a group represented by the 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. 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 formula (5), and at least two of Ar ^{11 to} Ar ¹⁴ when r is 1 A group represented by (5) or a group represented by formula (7).

(In the formulas (4) and (5), Ar ² and Ar ³ each independently represent a substituted or unsubstituted arylene group. In the formulas (6) and (7), Ar ⁴ and Ar ⁴ ) ^{In the} formulas (4) to (7), R ¹ represents a substituted or unsubstituted alkylene group, and each independently represents a substituted or unsubstituted trivalent aromatic group. And in formula (7), X ² , X ³ , Y ² , Y ³ , Z ² , and Z ³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, And represents an alkoxy group, a nitro group, or a cyano group, and in the groups represented by the formula (5) and the group represented by the formula (7) in (A1) and (B1), X ² and X ^{3 , 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。） In addition, 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 divalent. 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, when r is 0, at least one of Ar ^{61 to} Ar ⁶³ is a group represented by the formula (10), and at least one is a group represented by the formula (5); 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 is a group represented by the formula (5) Or a group represented by the 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。式（１０）、および（１１）中、Ｌはフッ素原子、塩素原子、臭素原子、または、ヨウ素原子を示す。）
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; 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 A group represented by (5) or a group represented by formula (7).

(In the formulas (10) and (5), Ar ⁷ and Ar ³ each independently represent a substituted or unsubstituted arylene group. In the formulas (11) and (7), Ar ⁸ and Ar 3) ^{In the} formulas (10), (11), (5), and (7), R ¹ represents a substituted or unsubstituted trivalent aromatic group. In formulas (10), (11), (5), and (7), X ² , X ³ , X ⁵ , X ⁶ , Y ² , Y ³ , Y ⁵ , and 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. A2) and (B2) have a plurality of groups represented by the formula (10), a group represented by the formula (11), and a group represented by the formula (5) And 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 in the same molecule or between the molecules.In the formulas (10) and (11), L represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. )
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.

  Hereinafter, each formula will be further described.

In the formulas (1), (2), (4) to (8), (10), and (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 the formulas (2), (5), (7), (8), (10), and (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 of 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. Each of X ^{1 to} X ⁶ , Y ^{1 to} Y ⁶ , and Z ^{1 to} Z ⁶ is preferably a hydrogen atom or a methyl group.

When there are a plurality of X ^{1 to} X ⁶ , Y ^{1 to} Y ⁶ , and Z ^{1 to} Z ⁶ , they may be the same or different. That is, as described above, (A1), (B1), (C1), (D1), (A2), (B2), (C2), and (D2) have a plurality of equations (2) and ( 5) In the groups represented by the formulas (7), (8), (10), and (11), X ^{1 to} X ⁶ , Y ^{1 to} Y ⁶ , and Z ^{1 to} Z ⁶ possessed by them. May be the same or different within the same molecule or between the 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 of 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 Formulas (4) to (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 of 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 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.

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

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

  The above (C1) or (C2) is obtained by using a compound having no charge transporting structure having a plurality of hydroxy groups in place of the dihydroxy compound of 4 in the synthesis method of the above (A1) or (A2). Can be synthesized.

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

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

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

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

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

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

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

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

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

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

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

  The monomers (A1), (C1), (A2) and (C2) each having a specific substituent not involved in curing are contained in an amount of 0.1% by mass based on the total mass of the monomer components contained in the composition. % Or less and preferably 30% by mass or less. More preferably, the content is 1% by mass or more and 10% by mass or less.

  In addition, the monomers (B1), (D1), (B2), and (D2) having two or more specific polymerizable functional groups are 40% by weight based on the total mass of the monomer components contained in the composition. It is preferable to contain it in an amount of not less than mass% and not more than 99.9 mass%.

  The charge transporting monomers (E1) and (E2) having one or more vinyl polymerizable functional groups are contained in an amount of 45% by mass or more and 55% by mass or less based on the total mass of the monomer components contained in the composition. It is preferred that the content be contained at not more than mass%.

The protective layer can contain various additives. Examples of the additive include a deterioration inhibitor such as an antioxidant and an ultraviolet absorber, and a lubricant such as polytetrafluoroethylene (PTFE) particles and carbon fluoride. Further, a polymerization control agent such as a polymerization reaction initiator and a polymerization reaction terminator, a leveling agent such as silicone oil, a surfactant, 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 photoreceptor of the present invention includes a composition containing the above (A1) and (B1), a composition containing the above (C1), (D1) and (E1), and the above (A2) and (B2) ) Or a coating liquid for a protective layer containing any one of the above-mentioned compositions (C2), (D2) and (E2). 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, a protective layer coating solution 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 solution for the protective layer may contain the above-mentioned various additives and solvents in addition to any one of the above-mentioned compositions.
Examples of the solvent used for the protective layer coating solution 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 and dioxane. Ether solvents, halogen solvents such as 1,1,2,2,3,3,4-heptafluorocyclopentane, dichloromethane, dichloroethane and chlorobenzene, aromatic solvents such as benzene, toluene and xylene, methyl cellosolve and ethyl A cellosolve-based solvent such as cellosolve is exemplified. These solvents may be used alone or in combination of two or more.

  When applying the protective layer coating solution, for example, an application 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, and a beam coating method can be used.

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

  In the case of performing polymerization using an electron beam, a polymerization initiator is not required, so that a decrease in electrophotographic characteristics due to the remaining polymerization initiator can be avoided. Further, since the polymerization reaction is performed in a short time and efficiently, the productivity is also increased. When irradiating with 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 that deterioration of material properties due to the electron beam can be suppressed without impairing polymerization efficiency. The electron beam absorption dose on the surface of the coating film of the protective layer coating liquid is preferably 5 kGy or more and 50 kGy or less, more preferably 1 kGy or more and 10 kGy or less.

  When the composition is cured (polymerized) using an electron beam, the composition may be irradiated with an electron beam in an inert gas atmosphere and then heated in an inert gas atmosphere in order to suppress the polymerization inhibitory effect of oxygen. preferable. Examples of the inert gas include nitrogen, argon, and helium.

Next, the overall configuration of the electrophotographic photosensitive member of the present invention will be described.
The electrophotographic photoreceptor 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 configuration of the 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 an undercoat layer described later may be provided between the support and the photosensitive layer (charge generation layer, charge transport layer).

The support used for the electrophotographic photoreceptor is preferably a conductive one (conductive support). For example, a support made of a metal or alloy such as aluminum, an aluminum alloy, and stainless steel can be used. In the case of a support made of aluminum or an aluminum alloy, an ED tube, an EI tube, or a support obtained by cutting, electrolytic complex polishing, or wet or dry honing thereof may 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 over a metal support or a resin support and used as the support.
The surface of the support may be subjected to a cutting treatment, a roughening treatment, an alumite treatment, or the like.
In addition, a support formed by impregnating conductive particles such as carbon black, tin oxide particles, titanium oxide particles, and silver particles with a resin or the like, or a support made of a 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 applying a conductive layer coating solution obtained by dispersing conductive particles together with a binder resin and a solvent to form a coating film, and 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. And the like.

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

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

  The thickness of the conductive layer is preferably from 0.2 μm to 40 μm, more preferably from 5 μm to 40 μm.

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 liquid 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, methyl cellulose, ethyl cellulose, polyamide, polyimide, polyamide imide, polyamic acid, melamine resin, epoxy resin, and polyurethane.

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

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

  The thickness of the undercoat layer is preferably from 0.05 μm to 40 μm, more preferably from 0.4 μm to 20 μm.

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

  Examples of the charge generating substance used in the electrophotographic photoreceptor include, for example, pyrylium, thiapyrylium dye, phthalocyanine compound, anthantrone pigment, dibenzpyrenequinone pigment, pyranthrone pigment, azo pigment, indigo pigment, quinacridone pigment, and quinocyanine pigment. Can be Among these, gallium phthalocyanine is preferred. Further, from the viewpoint of high sensitivity, hydroxygallium phthalocyanine is preferable, and among them, strong peaks at a Bragg angle 2θ of 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° in CuKα characteristic X-ray diffraction. A hydroxygallium phthalocyanine crystal having

  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, butyral resin is preferred. One of these resins may be used alone, or two or more of them may be used in combination or as a copolymer.

  The charge generation layer is formed by applying a coating solution for a charge generation layer obtained by dispersing a charge generation substance together with a binder resin and a solvent to form a coating film, and drying the obtained coating film. Can be. Further, the charge generation layer may be a deposited film of a charge generation substance.

  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 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 for the coating solution for the charge generation layer 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.

  Further, if necessary, various sensitizers, antioxidants, ultraviolet absorbers, and plasticizers can be added to the charge generation layer.

  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, forming a coating film, and drying the obtained coating film. Can be.

  Examples of the charge transport material used for the charge transport layer include a triarylamine compound, a hydrazone compound, a stilbene compound, a pyrazoline compound, an oxazole compound, a thiazole compound, and a triarylmethane compound.

  As the binder resin used for the charge transport layer, for example, polyvinyl butyral, polyarylate, polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide, polyamide, polyvinyl pyridine, cellulose resin, urethane resin, epoxy resin , Agarose resin, cellulose resin, casein, polyvinyl alcohol, and polyvinylpyrrolidone. One of these resins may be used alone, or two or more of them may be used in combination or as a copolymer.

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

  The ratio of the charge transport material is preferably 30% by mass or more and 70% by mass or less based on the total mass of the charge transport layer.

  Examples of the solvent used in the coating solution for the charge transport layer 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 photoreceptor in the invention is as described above, and includes a composition containing (A1) and (B1), a composition containing (C1), (D1) and (E1), (A2) and It contains a composition containing (B2) or a cured product of a composition containing (C2), (D2) and (E2). In addition, as described above, the protective layer contains a composition containing (A1) and (B1), a composition containing (C1), (D1) and (E1), and a composition containing (A2) and (B2). Or a coating film of a coating liquid 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 around an axis 2 at a predetermined peripheral speed (process speed) in a direction indicated by an arrow. In the rotation process, the surface (peripheral surface) of the electrophotographic photosensitive member 1 is positively or negatively charged by the charging means (primary charging means) 3. Next, the surface of the electrophotographic photosensitive member 1 is irradiated with exposure light (image exposure light) 4 output from an exposure unit (image exposure unit) (not shown). The exposure light 4 is intensity-modulated according to a time-series electric digital image signal of target image information. 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 photosensitive member 1.
Next, the electrostatic latent image formed on the surface of the electrophotographic photoreceptor 1 is developed (regular development or reversal development) with the toner contained in the developing means 5 to form a toner image. The toner image formed on the surface of the electrophotographic photosensitive member 1 is transferred to a transfer material 7 by a transfer unit 6. Here, when the transfer material 7 is paper, it is taken out from a paper feed 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 that of the retained charge of the toner is applied to the transfer unit 6 from a bias power supply (not shown). Further, 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 to which the toner image has been transferred is separated from the surface of the electrophotographic photoreceptor 1, conveyed to a fixing unit 8, and subjected to a fixing process of the toner image, so that the image is formed as an image forming product (print, copy). Printed out of the photo device.

  The surface of the electrophotographic photoreceptor 1 after the transfer of the toner image is cleaned by the cleaning unit 9 to remove extraneous matters such as transfer residual toner. The transfer residual toner can also be collected by a developing unit or the like. Further, if necessary, the surface of the electrophotographic photoreceptor 1 is subjected to static elimination treatment by irradiation with pre-exposure light 10 from a pre-exposure unit (not shown), and is thereafter 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, among the components selected from the electrophotographic photoreceptor 1, the charging unit 3, the developing unit 5, the transfer unit 6, the cleaning unit 9, and the like, a plurality of components may be housed in a container to form a process cartridge. Further, the process cartridge may be configured to be detachable from the main body of the electrophotographic apparatus. For example, the electrophotographic photosensitive member 1 and at least one unit selected from the group consisting of a charging unit 3, a developing unit 5, a transfer unit 6 and a cleaning unit 9 are integrally supported to form a cartridge. The process cartridge 11 can be detachably attached to the main body of the electrophotographic apparatus using the guide means 12 such as a rail of the main body of the electrophotographic apparatus.

  Hereinafter, a specific example will be described in more detail. In the examples, “parts” means “parts by mass”. Further, the electrophotographic photosensitive member is also simply referred to as “photosensitive member” hereinafter.

(Synthesis Example 1: Synthesis of Exemplified Compound (A1) -2))
Using the method described in paragraph [0087] of Patent Document 1 (Synthesis Example 1), the dihydroxy compound (4) described in the reaction formula of [Formula 26] in paragraph [0087] (the following reaction formula) Compound 1 was synthesized. 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 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 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 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 30 g of Exemplified Compound (A1) -2.

(Synthesis Example 2: Synthesis of Exemplified Compound (A2) -2))
Using the method described in paragraph [0087] of Patent Document 1 (Synthesis Example 1), the dihydroxy compound (4) described in the reaction formula of [Formula 26] in paragraph [0087] (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 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 30 g of Exemplified Compound (A2) -2.

(Production Example 1 of Electrophotographic Photoreceptor)
-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 as a support.
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. 0.8 parts of a silane coupling agent (compound name: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) was added thereto, and the mixture was added for 6 hours. Stirred. Thereafter, toluene was distilled off under reduced pressure, and the resultant was dried by heating at 140 ° C. for 6 hours to obtain surface-treated zinc oxide particles.
Next, as a polyol resin, 15 parts of butyral resin (trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.) and 15 parts of blocked isocyanate (trade name: Sumidur 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.) were added to the 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 the mixture was added to glass having a diameter of 0.8 mm. The particles were dispersed in a sand mill using beads at 23 ± 3 ° C. for 3 hours. After dispersion, 0.01 part of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Silicone Co., Ltd.), cross-linked polymethyl methacrylate (PMMA) particles (trade name: TECHPOLYMER SSX-103, manufactured by Sekisui Plastics Co., Ltd.) 5.6 parts of an average primary particle size of 3.1 μm) and stirred to prepare a coating liquid for an undercoat layer.
This undercoat layer coating solution was applied onto the above-mentioned support by dip coating, and the obtained 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。 Next, the following four substances were placed in a sand mill using glass beads of 1 mm in diameter and dispersed for 4 hours, and then 700 parts of ethyl acetate was added to prepare a coating liquid for a charge generation layer. .
Crystalline hydroxygallium phthalocyanine crystal (charge generating substance) having strong peaks at 7.4 ° and 28.2 ° at Bragg angles 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction (20 parts) Calixarene compound represented by the formula (s): 0.2 part

・ Polyvinyl butyral (trade name: S-REC BX-1, manufactured by Sekisui Chemical Co., Ltd.)
··· 10 parts · Cyclohexanone ··· 600 parts This charge generation layer coating solution is dip-coated on the undercoat layer, and the obtained coating film is dried at 80 ° C. for 15 minutes to obtain a film thickness of 0.18 μm. 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, the following five substances were dissolved in a mixed solvent of 600 parts of xylene and 200 parts of dimethoxymethane to prepare a coating solution for a charge transport layer.
-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-By the following structural formula (v) Compound shown (charge-transporting substance): 10 partsPolycarbonate resin (trade name: Iupilon Z400, bisphenol Z-type polycarbonate manufactured by Mitsubishi Engineering-Plastics Co., Ltd.) 100 parts: Structural formula (w) shown below Polycarbonate (viscosity average molecular weight Mv: 20,000)
... 0.02 parts

(In the structural formula (W), 0.95 and 0.05 are a molar ratio (copolymerization ratio) of two structural units.)
This charge transport layer coating solution was applied onto the charge generation layer by dip coating, and the obtained coating film was dried at 110 ° C. for 30 minutes to form a charge transport layer having a thickness of 18 μm.

-Protective layer A mixed solvent of 100 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeorola H, manufactured by Nippon Zeon Co., Ltd.) / 100 parts of 1-propanol was mixed with polyflon. The solution was filtered through a filter (trade name: PF-040, manufactured by Advantech Toyo Co., Ltd.). As described below, two kinds of monomer compounds were added to this mixed solvent so that the total amount was 100 parts. This was filtered through a polyflon filter (trade name: PF-020, manufactured by Advantech Toyo Co., Ltd.) to prepare a coating solution for the second charge transport layer (protective layer).
-Exemplified compound (A1) -2 ... 5 parts-Exemplified compound (B1)-2 ... 95 parts This coating liquid for the second charge transport layer is dip-coated on the charge transport layer to obtain a coating film. Was dried in air at 50 ° C. for 6 minutes. Thereafter, the coating film was irradiated with an electron beam for 1.6 seconds in nitrogen under the conditions of an acceleration voltage of 70 kV and an absorbed dose of 8000 Gy while rotating the support (irradiation target) at 200 rpm.
Subsequently, the temperature was raised from 25 ° C. to 120 ° C. in nitrogen over 30 seconds, and the coating film was heated. The oxygen concentration in the atmosphere during electron beam irradiation and subsequent heating was 15 ppm. Next, a 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 photosensitive member was prepared as described above.

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

-Protective layer First, a lubricant dispersion was prepared in 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: Zeorola 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 dispersing machine (trade name: Microfluidizer M-110EH, manufactured by Microfluidics, Inc.), and subjected to a dispersion treatment four times at a pressure of 600 kgf / cm ² . This was filtered through 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: Zeola H, manufactured by Zeon Corporation) / 70 parts of 1-propanol was added to polyflon. The solution was filtered through a filter (trade name: PF-040, manufactured by Advantech Toyo Co., Ltd.). As described below, two kinds of monomer compounds were added to the mixed solvent so that the total amount became 70 parts. This was filtered through a polyflon filter (trade name: PF-020, manufactured by Advantech Toyo Co., Ltd.) to obtain a monomer solution.
-Exemplified compound (A1) -2 ... 3.5 parts-Exemplified compound (B1) -2 ... 66.5 parts The obtained lubricant dispersion and monomer solution are mixed to form a second charge transport layer. A coating solution for (protective layer) was prepared.

The coating solution for the second charge transport layer was applied onto the charge transport layer by dip coating, and the obtained coating film was dried at 50 ° C. for 6 minutes in the air. Thereafter, the coating film was irradiated with an electron beam for 1.6 seconds in nitrogen under the conditions of an acceleration voltage of 70 kV and an absorbed dose of 8000 Gy while rotating the support (irradiation target) at 200 rpm. Subsequently, the temperature was raised from 25 ° C. to 120 ° C. in nitrogen over 30 seconds, and the coating film was heated. The oxygen concentration in the atmosphere during electron beam irradiation and subsequent heating was 15 ppm. Next, a 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 photosensitive member was prepared as described above.

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

(Production Example 4 of Electrophotographic Photoreceptor)
-Protective layer A mixed solvent of 100 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeorola H, manufactured by Nippon Zeon Co., Ltd.) / 100 parts of 1-propanol was mixed with polyflon. The solution was filtered through a filter (trade name: PF-040, manufactured by Advantech Toyo Co., Ltd.). As described below, three kinds of monomer compounds were added to this mixed solvent so that the total amount was 100 parts. This was filtered through a polyflon filter (trade name: PF-020, manufactured by Advantech Toyo Co., Ltd.) to prepare a coating solution for the second charge transport layer (protective layer).
-Exemplified compound (C1) -1 ... 5 parts-Exemplified compound (D1) -1 ... 45 parts Exemplified compound (E1) -1 ... 50 parts The coating liquid for the second charge transport layer is charged. Dip coating was performed on the transport layer, and the obtained coating film was dried at 50 ° C. for 6 minutes in the air. Thereafter, the coating film was irradiated with an electron beam for 1.6 seconds in nitrogen under the conditions of an acceleration voltage of 70 kV and an absorbed dose of 8000 Gy while rotating the support (irradiation target) at 200 rpm.
Subsequently, the temperature was raised from 25 ° C. to 120 ° C. in nitrogen over 30 seconds, and the coating film was heated. The oxygen concentration in the atmosphere during electron beam irradiation and subsequent heating was 15 ppm. Next, a 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 photosensitive member was prepared as described above.

(Evaluation of wear resistance)
Using a cartridge having an electrophotographic photosensitive member of iR-ADV C5255 manufactured by Canon Inc. and a jig, the amount of abrasion of the cleaning blade due to sliding was examined. As the jig, a jig having a motor for supporting the cartridge and rotating the electrophotographic photosensitive member was used. Under a normal temperature and normal humidity environment of a temperature of 23 ° C. and a humidity of 50% RH, the prepared electrophotographic photosensitive member was mounted on the cartridge, and the rotation speed of the electrophotographic photosensitive member was set at 250 mm / sec, and a test was performed for 6 hours. 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 evenly 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 between the total film thickness before and after the test was determined as the shaved amount (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. The following evaluations were all performed in a normal temperature and normal humidity environment at a temperature of 23 ° C. and a humidity of 50% RH. Light irradiation was performed for 5 minutes using an illuminometer, adjusting the distance between the electrophotographic photosensitive member and the white fluorescent lamp so that the irradiation light amount was 1500 (lx). The surface potential before and after the irradiation was measured using a black station of iR-ADV C5255 manufactured by Canon Inc. Instead of the developing device of the black station, a surface electrometer (trade name: model 344, manufactured by Trek Japan Co., Ltd.) was mounted, and a cartridge having the prepared electrophotographic photosensitive member was installed. In the electrophotographic photoreceptor before light irradiation of the white fluorescent lamp, the developing position potential (charging potential) when operating with the image exposure turned off is -500 V, and the developing position when operating with the image exposure turned on. The charging voltage of the primary charger and the amount of image exposure were adjusted so that the potential (potential after image exposure) was -150V. After the light irradiation of the white fluorescent lamp, the potential after the image exposure was measured with the same setting as before the irradiation. The absolute value of the difference between the potentials after image exposure before and after irradiation with a white fluorescent lamp was determined as an exposure memory (V).

(Examples 1 to 25)
In each of the examples, one of the methods of Production Examples 1 to 3 of the electrophotographic photosensitive member was selected to prepare an electrophotographic photosensitive member. At this time, the above two kinds of monomer compounds to be added to the coating solution for the second charge transport layer (protective layer) were changed to the compounds and parts shown in Table 1. (Indicated in the column of Compound 1 and Compound 2 in Table 1.) Two electrophotographic photoreceptors were prepared for each example, one for the evaluation of the abrasion resistance test described above, and one for the electrophotographic photoreceptor. The exposure memory was evaluated. Table 1 shows the results.

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

(Comparative Example 1)
An electrophotographic photoreceptor was manufactured in the same manner as in Example 1, except that the following compound (F) was used instead of Exemplified Compound (A1) -2 to prepare a coating solution for a protective layer. Table 3 shows the compounds, parts, and evaluation results.

(Comparative Example 2)
An electrophotographic photosensitive member was manufactured in the same manner as in Example 1, except that the following compound (G) was used in place of the exemplary compound (A1) -2 to prepare a coating solution for a protective layer. Table 3 shows the compounds, parts, and evaluation results.

(Comparative Example 3)
A protective layer coating solution was prepared in the same manner as in Example 1 except that the following compound (H) was used instead of the exemplified compound (A1) -2 and the following compound (I) was used instead of the exemplified compound (B1) -2. In the same manner as in Example 1, an electrophotographic photosensitive member was manufactured. Table 3 shows the compounds, parts, and evaluation results.

(Comparative Example 4)
Electrophotography was carried out in the same manner as in Example 1, except that Exemplified Compound (A1) -2 was not used and Exemplified Compound (B1) -2 was changed to 100 parts to prepare a coating solution for a protective layer. A photoreceptor was manufactured. Table 3 shows the compounds, parts, and evaluation results.

(Comparative Example 5)
Electrophotography was carried out in the same manner as in Example 1, except that Exemplified Compound (A1) -6 was not used and Exemplified Compound (B1) -6 was changed to 100 parts to prepare a coating solution for a protective layer. A photoreceptor was manufactured. Table 3 shows the compounds, parts, and evaluation results.

(Comparative Example 6)
Electrophotography was performed in the same manner as in Example 1 except that Exemplified Compound (A1) -25 was not used and Exemplified Compound (B1) -20 was changed to 100 parts to prepare a coating solution for a protective layer. A photoreceptor was manufactured. Table 3 shows the compounds, parts, and evaluation results.

(Comparative Example 7)
Electrophotography was carried out in the same manner as in Example 1, except that Exemplified Compound (A1) -29 was not used and Exemplified Compound (B1) -24 was changed to 100 parts to prepare a coating solution for a protective layer. A photoreceptor was manufactured. Table 3 shows the compounds, parts, and evaluation results.

(Comparative Example 8)
Electrophotography was carried out in the same manner as in Example 1 except that Example Compound (A1) -2 was not used and Example Compound (B1) -2 was changed to 70 parts to prepare a coating solution for a protective layer. A photoreceptor was manufactured. Table 3 shows the compounds, parts, and evaluation results.

  According to the embodiment, in the electrophotographic photoreceptor according to the present invention, the shaving amount is less than the measurement limit (0.1 μm), the exposure memory is less than 40 V, the abrasion resistance is high, and the exposure memory is suppressed. It can be said that this is an electrophotographic photosensitive member.

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

In Comparative Example 3, results of using the charge transporting monomer R ¹ is not structured, the wear amount is increased, abrasion resistance had been compromised. In this regard, it is presumed that curing was insufficient due to the low degree of freedom of the functional group site of the monomer.

  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 scraping amount was below the measurement limit, but the exposure memory was It was 50 V or more. These electrophotographic photoreceptors had sufficient abrasion resistance, but still had problems of exposure memory.

REFERENCE SIGNS LIST 101 support 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 Guidance means

Claims (11)

An electrophotographic photoreceptor 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. An electrophotographic photosensitive member, wherein the protective layer contains a cured product of a composition containing the following (A1) and (B1).
(A1): a charge-transporting monomer having at least one group represented by the formula (1) and at least one group represented by the formula (2) (B1): a group represented by the formula (2) Having two or more groups and having no group represented by the formula (1)

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

(In the 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 divalent. 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 Wherein, when r is 1, Ar ¹³ represents a group represented by the formula (6), a group represented by the formula (7), or a substituted or unsubstituted arylene group. However, when r is 0, at least one of Ar ^{11 to} Ar ¹³ is a group represented by the formula (4), and at least one is a group represented by the formula (5); 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 is a group represented by the formula (5) Or a group represented by the 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. 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 formula (5), and at least two of Ar ^{11 to} Ar ¹⁴ when r is 1 A group represented by (5) or a group represented by formula (7). )

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

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

(In the formulas (8) and (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) a plurality of groups represented by the formula (2) and a group represented by the formula (8), which have 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 photoconductor 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 divalent. 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, when r is 0, at least one of Ar ^{61 to} Ar ⁶³ is a group represented by the formula (10), and at least one is a group represented by the formula (5); 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 is a group represented by the formula (5) Or a group represented by the 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; 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 A group represented by (5) or a group represented by formula (7). )

(In the formulas (10) and (5), Ar ⁷ and Ar ³ each independently represent a substituted or unsubstituted arylene group. In the formulas (11) and (7), Ar ⁸ and Ar 3) ^{In the} formulas (10), (11), (5), and (7), R ¹ represents a substituted or unsubstituted trivalent aromatic group. In formulas (10), (11), (5), and (7), X ² , X ³ , X ⁵ , X ⁶ , Y ² , Y ³ , Y ⁵ , and 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. A2) and (B2) have a plurality of groups represented by the formula (10), a group represented by the formula (11), and a group represented by the formula (5) And 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.
In the formulas (10) and (11), L represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. ) An electrophotographic photoreceptor 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. An electrophotographic photosensitive member, wherein the protective layer contains a cured product of a composition containing the following (C2), (D2), and (E2).
(C2): a monomer having at least one group represented by the formula (8) and having no charge transporting property having at least one group represented by the formula (2) (D2): a formula (2) (E2) having two or more groups represented by the formula and having no group represented by the formula (8) and having no charge transporting property: having at least one vinyl polymerizable functional group Charge transporting monomer

(In the formulas (8) and (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) a plurality of groups represented by the formula (2) and a group represented by the formula (8), which have 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 claim 1, 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 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 A composition containing the following (A1) and (B1), a composition containing the following (C1), (D1), and (E1), a composition containing the following (A2) and (B2), or the following ( C2), a step of preparing a coating solution for a protective layer containing any one of the compositions comprising (D2) and (E2), and forming a coating film of the coating solution for a protective layer, A method for producing an electrophotographic photosensitive member, comprising a step of forming the protective layer by curing the composition in a film.
(A1): a charge-transporting monomer having at least one group represented by the formula (1) and at least one group represented by the formula (2) (B1): a group represented by the formula (2) Having two or more groups, and having no group represented by the formula (1), a charge transporting monomer (C1): having one or more groups represented by the formula (1), and (D1) having at least one group represented by formula (1): having at least two 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 at least one vinyl polymerizable functional group (A2): having at least one group represented by the formula (8), and A charge transporting monomer (B2) having one or more groups represented by the formula (2): having two or more groups represented by the formula (2), and A charge-transporting monomer (C2) having no group represented by the formula: charge-transporting monomer having at least one group represented by the formula (8) and having at least one group represented by the formula (2) (D2) having no group represented by the formula (2): 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 at least one vinyl polymerizable functional group

(In the formulas (1) and (2), R ¹ represents a substituted or unsubstituted alkylene group. X ¹ , Y ¹ , and Z ¹ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group. 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 X ¹ , Y ¹ , and Z ^{1 of} a plurality of groups represented by formula (2) in (D2) may be different in 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 Represents 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 groups shown, X ⁴ , Y ⁴ , and Z ⁴ possessed by them may be different within the same molecule or between molecules.)   The method according to claim 8, wherein the composition is cured by irradiating the coating film of the coating liquid for the protective layer with an electron beam.   An electrophotographic apparatus comprising: an electrophotographic photosensitive member according to claim 1 and at least one unit selected from the group consisting of a charging unit, a developing unit, a transferring unit, and a cleaning unit; A process cartridge which is detachable from an apparatus main body.   An electrophotographic apparatus comprising: the electrophotographic photosensitive member according to claim 1; and a charging unit, an exposing unit, a developing unit, and a transferring unit.

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