JP7336355B2 - Electrophotographic photoreceptor, electrophotographic apparatus and process cartridge - Google Patents

Description

The present invention relates to an electrophotographic photoreceptor, an electrophotographic apparatus having the electrophotographic photoreceptor, and a process cartridge having the electrophotographic photoreceptor.

Abrasion resistance and chemical stability are required for the surface layer of the electrophotographic photoreceptor, since stress is repeatedly applied by a series of electrophotographic processes such as charging, exposure, development, transfer, and cleaning. As means for improving abrasion resistance, there is a method of incorporating a curable resin into the surface layer of the electrophotographic photoreceptor. However, when a surface layer with high wear resistance is provided, the surface layer becomes less likely to wear, so the removal of the chemically deteriorated surface layer due to wear does not proceed, and chemical deterioration etc. accumulates in the surface layer. easier to do.

On the other hand, charging means in an electrophotographic apparatus includes methods such as charging with discharge, triboelectric charging, and injection charging. Among them, the charging method with discharge is widely used because of its excellent charging uniformity. there is However, in the charging method involving discharge, active gas (nitrogen oxide, ozone) is generated and adheres to the surface of the electrophotographic photoreceptor, chemically degrading the electrophotographic photoreceptor, resulting in so-called image unevenness. It produces band-like image defects. Image unevenness is a phenomenon in which a band-like density difference occurs in an output image, and is one of image defects due to memory under the charging device. Under-charger memory refers to a phenomenon in which a portion of the electrophotographic photosensitive member facing the charger deteriorates during the rest of the electrophotographic apparatus for several hours after the end of the electrophotographic process. As a result, when an image is formed again after the pause, the image density of the portion of the output image corresponding to the position of the charger changes compared to the surrounding area, resulting in image unevenness.

In particular, in recent years, as the speed of the electrophotographic process has increased and the output of the charger has been improved to shorten the time required for the charging process, the generation of active gas has increased. It is

Patent Document 1 describes that the occurrence of image unevenness and blurring can be suppressed by including a specific additive in an electrophotographic photoreceptor. Japanese Patent Laid-Open No. 2002-200002 describes a technique for improving image deletion by incorporating a charge transport material having a specific polymerizable functional group into an electrophotographic photoreceptor. Patent Literature 3 describes a method for improving image blurring and the like by incorporating a tertiary amine compound having a specific polymerizable functional group into a photosensitive layer of an electrophotographic photoreceptor.

Patent Document 4 describes a technique for suppressing image defects by incorporating a specific secondary amine compound in the photosensitive layer of an electrophotographic photoreceptor.

JP 2014-199391 A JP 2017-146416 A JP 2007-293247 A JP-A-2004-125907

The techniques described in Patent Documents 1 to 3 are techniques for mitigating adverse effects caused by exposure of the hole-transporting compound to the aforementioned active gas. In the technique described in Patent Document 4, a secondary amine is added, but it is added to the charge generation layer, not to the surface layer having charge transport properties. All of these prior arts have room for improvement in suppressing image defects.

In order to more effectively suppress image defects, not only the adverse effects caused by the exposure of the hole-transporting compound to the aforementioned active gas should be mitigated, but also the effect of the active gas on the hole-transporting compound itself should be reduced. Technology is in demand.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an electrophotographic photoreceptor that has high potential stability and suppresses the occurrence of image unevenness during repeated use.
Another object of the present invention is to provide an electrophotographic apparatus having the electrophotographic photoreceptor and a process cartridge having the electrophotographic photoreceptor.
Still another object of the present invention is to provide a method for producing the above electrophotographic photoreceptor.

（式（１）中、Ｒ^１およびＲ^２は、それぞれ独立に、炭素数１以上８以下のアルキル基を示す。Ｒ^３およびＲ^４は、それぞれ独立に、水素原子、または、炭素数４以下のアルキル基を示す。Ｒ^５は、炭素数２以上６以下のアルキレン基を示す。Ｒ^６は、水素原子、または、メチル基を示す。） An electrophotographic photoreceptor according to one aspect of the present invention is an electrophotographic photoreceptor having a support and a photosensitive layer on the support, wherein the surface layer of the electrophotographic photoreceptor comprises at least bifunctional or higher acryloyl containing a polymer of a composition containing a triarylamine-based hole-transporting compound having an oxy group or a methacryloyloxy group and a compound represented by the following general formula (1); The content of the compound represented by formula (1) is 0.1% by mass or more and 1.0% by mass or less relative to the triarylamine-based hole-transporting compound in the composition. and

(In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or 4 or less carbon atoms. represents an alkyl group of R ⁵ represents an alkylene group having 2 to 6 carbon atoms, and R ⁶ represents a hydrogen atom or a methyl group.)

Further, an electrophotographic apparatus according to another aspect of the present invention has the above electrophotographic photosensitive member, charging means, exposure means, developing means and transfer means.

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

Further, a method for producing an electrophotographic photoreceptor according to still another aspect of the present invention is a method for producing an electrophotographic photoreceptor having a support and a photosensitive layer on the support, the production method comprising at least Forming a coating film of a surface layer coating liquid containing a triarylamine-based hole-transporting compound having a bifunctional or higher acryloyloxy group or methacryloyloxy group and a compound represented by the general formula (1) a step (i) and a step (ii) of polymerizing the coating film to form a surface layer of the electrophotographic photoreceptor; content of the compound is 0.1% by mass or more and 1.0% by mass or less with respect to the triarylamine-based hole-transporting compound in the surface layer coating liquid. .

According to the present invention, an electrophotographic photoreceptor is provided that has high potential stability and suppresses the occurrence of image unevenness during repeated use. Also provided are an electrophotographic apparatus having the electrophotographic photoreceptor, a process cartridge having the electrophotographic photoreceptor, and a method for manufacturing the electrophotographic photoreceptor.

1 is a schematic diagram showing an example of a process cartridge having an electrophotographic photosensitive member; FIG. 1 is a schematic diagram showing an example of an electrophotographic apparatus having an electrophotographic photoreceptor; FIG. 1 is a schematic diagram showing an example of an apparatus for processing a surface of an electrophotographic photosensitive member by pressure contact shape transfer processing; FIG. FIG. 2 is a schematic diagram showing an example of a stamper mold for crimping;

The present invention relates to an electrophotographic photoreceptor in which the surface layer of the electrophotographic photoreceptor contains a polymer of a hole transport compound having a polymerizable functional group and further contains a secondary amine compound having a specific aminofluorene structure.

Generally, arylamine compounds having excellent hole-transporting properties are widely used as hole-transporting compounds used in electrophotographic photoreceptors.

The hole-transporting property of arylamine compounds is considered to be expressed by the amine structure exhibiting electron-donating properties, forming a molecular orbital with an aryl group or the like around the nitrogen atom, and causing oxidation-reduction.

On the other hand, it is believed that the arylamine site is in a state of being susceptible to chemical reactions, etc., since the transfer of charge is actively performed through repeated electrophotographic processes. In particular, it is considered that the film is susceptible to changes such as oxidation due to the action of the discharge energy in the charging process and the action of ozone and oxidizing substances generated by the discharge phenomenon. As a result, it is speculated that a chemical change at the arylamine site is induced. In particular, active gases such as nitrogen oxides and ozone generated by the discharge phenomenon in the charging process adhere to the surface of the electrophotographic photoreceptor and deteriorate the electrophotographic photoreceptor, thereby causing band-like image defects called so-called image unevenness. thought to occur.

In order to effectively suppress the occurrence of image unevenness, the inventors of the present invention have searched for a substance that suppresses the action of the active gas that degrades the surface of the electrophotographic photosensitive member. As a result, the present inventors have found a substance that suppresses the occurrence of image defects such as image unevenness without impairing the potential stability of an electrophotographic photoreceptor, resulting in the present invention.

（式（１）中、Ｒ^１およびＲ^２は、それぞれ独立に、炭素数１以上８以下のアルキル基を示す。Ｒ^３およびＲ^４は、それぞれ独立に、水素原子、または、炭素数４以下のアルキル基を示す。Ｒ^５は、炭素数２以上６以下のアルキレン基を示す。Ｒ^６は、水素原子、または、メチル基を示す。） That is, the electrophotographic photoreceptor according to the present invention is an electrophotographic photoreceptor having a support and a photosensitive layer, wherein the surface layer of the electrophotographic photoreceptor contains at least a bifunctional or more functional acryloyloxy group or methacryloyloxy group. and a polymer of a composition containing a compound represented by the following general formula (1).

(In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or 4 or less carbon atoms. represents an alkyl group of R ⁵ represents an alkylene group having 2 to 6 carbon atoms, and R ⁶ represents a hydrogen atom or a methyl group.)

The content of the compound represented by the general formula (1) in the composition is 0.1 % by mass or more and 1.0% with respect to the triarylamine-based hole-transporting compound in the composition. % by mass or less. The content of the compound represented by the general formula (1) in the composition is 0.5% by mass or more and 1.0 % by mass with respect to the triarylamine-based hole-transporting compound in the composition. It is preferable to contain in the following ratios.

The amine compound represented by the general formula (1) has the following characteristics. That is, the amine compound represented by the general formula (1) has a basic aromatic secondary amine structure in order to suppress the deterioration of the electrophotographic photosensitive member surface by active gases such as nitrogen oxides and ozone. have
Commonly used secondary amines such as diphenylamine, which have a small molecular weight and a strong basicity, have an acid scavenging effect, but have the problem of lowering the potential stability of electrophotographic photoreceptors even when added in small amounts.

On the other hand, the amine compound represented by the general formula (1) has an aromatic secondary amine structure, but has a specific alkyl-substituted fluorene structure in one aromatic group, and the molecule It has an alkyl group with a specific number of carbon atoms at a specific position within.

Furthermore, the amine compound represented by general formula (1) has a polymerizable functional group such as an acryloyloxy group. As a result, the amine compound represented by general formula (1) has improved compatibility with triarylamine-based hole-transporting compounds having a bifunctional or higher acryloyloxy group or methacryloyloxy group. Further, the amine compound represented by the general formula (1) is polymerized and cured together with a triarylamine-based hole-transporting compound having a bifunctional or more acryloyloxy group or methacryloyloxy group, and is fixed in the surface layer. .

Since the amine compound represented by the general formula (1) has the above characteristics, deterioration of the active gas is suppressed while suppressing a decrease in the potential stability of the electrophotographic photosensitive member due to the addition of the compound having a secondary amine structure. We believe that the effect can be effectively suppressed.

Although the mechanism by which the above effects are expressed has not been completely elucidated, the amine compound represented by the general formula (1) has a fluorene structure with an extended conjugated system bound to a secondary amine. Furthermore, it has steric hindrance by having an alkyl group at a specific site. Therefore, it has the effect of moderately lowering the basicity of the nitrogen atoms constituting the amine, and is considered not to be a strong hole trap.

Essential requirements for the amine compound represented by the general formula (1) are described below for each partial structure of the general formula (1). The amine compound represented by the general formula (1) has R ¹ and R ² , which bind to the 9-position of the so-called fluorene structure as alkyl groups having 1 to 8 carbon atoms. The fluorene structure is formed by condensing a 5-membered ring and a 6-membered ring, and has high planarity. On the other hand, only the carbon atom located at the 9-position of the fluorene structure is a carbon atom forming an sp3 hybridized orbital, and R ¹ and R ² point in a different direction from the plane formed by the three condensed rings. Presence of an alkyl group having an appropriate carbon number range as R ¹ and R ² is presumed to alleviate the hole trapping effect due to the use of the secondary amine.

In the general formula (1), the number of carbon atoms in the alkyl group represented by R ¹ and R ² bonded to the 9-position of the fluorene structure is 1 or more and 8 or less, more preferably 1 or more and 6 or less, and further It is preferably 1 or more and 5 or less.

Examples of alkyl groups represented by R ¹ and R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 1-methyl Examples include hexyl group, 4-tert-butylcyclohexyl group, n-heptyl group, 2-methylheptyl group, n-octyl group and the like.

The amine compound represented by the general formula (1) has alkyl groups having 4 or less carbon atoms as substituents represented by R ³ and R ⁴ in order to improve solubility and compatibility with surrounding materials. You may have a group. Since R ³ and R ⁴ are directly bonded to the benzene ring of fluorene, if the carbon chain of the alkyl group that may be present as a substituent represented by R ³ and R ⁴ is too long, inhibition due to steric hindrance, etc. may occur. influence becomes greater. Therefore, the number of carbon atoms of the alkyl group that may be included as a substituent represented by R ³ and R ⁴ is 4 or less. Examples of alkyl groups which may be possessed as substituents represented by R ³ and R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- A butyl group and the like can be mentioned.

The amine compound represented by the general formula (1) has an alkylene group having 2 or more and 6 or less carbon atoms represented by R ⁵ between the benzene ring and the polymerizable functional group.

The alkylene group represented by R ⁵ includes n-propylene group, iso-propylene group, n-butylene group, iso-butylene group, sec-butylene group, tert-butylene group, n-pentylene group, 1-methyl-n -butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl- n-propylene group, n-hexylylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, etc. is mentioned.

In the present invention, the compound of formula (1) is used in combination with a triarylamine-based hole-transporting compound having a functional or higher acryloyloxy group or methacryloyloxy group as a composition for forming a polymer. is necessary. The compound of the above formula (1) also has an acryloyloxy group or a methacryloyloxy group, and the commonality of the functional groups of the compounds constituting the polymer ensures good affinity, and the effects of the present invention are good. It is speculated that the

In the surface layer of the electrophotographic photoreceptor according to the present invention, the content of the structure derived from the triarylamine-based hole-transporting compound having two or more functional acryloyloxy groups or methacryloyloxy groups is From the viewpoint of, it is preferably 50% by mass or more.

（式（４）中、Ａはアルキル基を有してもよいａ価の正孔輸送性基を示し、ａは２から４の整数を示し、Ｐ^１は下記一般式（５）で表される１価の官能基を示す。また、複数のＰ^１は互いに同一であっても異なっていてもよい。

（式（５）中、Ｒ^５１は水素原子、またはメチル基を示し、Ｒ^５２はアルキレン基を示す。）） The triarylamine-based hole-transporting compound having a bifunctional or higher acryloyloxy group or methacryloyloxy group is preferably a compound represented by the following general formula (4).

(In formula (4), A represents an a-valent hole-transporting group which may have an alkyl group, a represents an integer of 2 to 4, and P ¹ is represented by the following general formula (5). P ¹ may be the same or different from each other.

(In formula (5), R ⁵¹ represents a hydrogen atom or a methyl group, and R ⁵² represents an alkylene group.))

A hole-transporting group means a functional group containing an amine structure having three aryl groups (triarylamine structure). Aryl groups include aromatic hydrocarbon groups such as phenyl, biphenyl, fluorenyl, and naphthyl groups.

（式（２）中、Ｒ^１１およびＲ^１２は、それぞれ独立に、炭素数１以上８以下のアルキル基を示す。Ｒ^１３およびＲ^１４は、それぞれ独立に、水素原子、または、炭素数４以下のアルキル基を示す。Ｒ^１５およびＲ^１７は、それぞれ独立に、炭素数２以上６以下のアルキレン基を示す。Ｒ^１６およびＲ^１８は、それぞれ独立に、水素原子、または、メチル基を示す。） More preferably, the triarylamine-based hole-transporting compound having a bifunctional or more functional acryloyloxy group or methacryloyloxy group has a structure represented by the following general formula (2).

(In formula (2), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 8 carbon atoms. R ¹³ and R ¹⁴ each independently represent a hydrogen atom or 4 or less carbon atoms. R ¹⁵ and R ¹⁷ each independently represent an alkylene group having 2 to 6 carbon atoms, and R ¹⁶ and R ¹⁸ each independently represent a hydrogen atom or a methyl group. )

The hole-transporting compound represented by formula (2) will be described. The hole-transporting compound represented by the general formula (2) has an alkyl group having 1 to 8 carbon atoms represented by R ¹¹ and R ¹² bonded to the 9-position of the so-called fluorene structure. The fluorene structure is formed by condensing a 5-membered ring and a 6-membered ring, and has high planarity. On the other hand, only the carbon atom located at the 9-position of the fluorene structure is a carbon atom forming an sp3 hybridized orbital, and the alkyl groups represented by R ¹¹ and R ¹² are oriented in a direction different from the plane formed by the three condensed rings. To position. Due to the positional relationship, even if the number of carbon atoms in the alkyl groups represented by R ¹¹ and R ¹² is large, it is thought that the structure is such that the hole transport property is not easily impaired.

In the general formula (2), the alkyl groups represented by R ¹¹ and R ¹² bonded to the 9-position of the fluorene structure may reduce potential stability if the carbon chain is too long. Therefore, the alkyl group represented by R ¹¹ and R ¹² has 8 or less carbon atoms, more preferably 6 or less carbon atoms, and still more preferably 2 or more and 5 or less carbon atoms. If the carbon chain of the alkyl group represented by R ¹¹ and R ¹² becomes too long, the steric hindrance to the aromatic amino group, etc. increases, and the disorder of the surface layer increases, thereby impairing hole transportability. can be considered.

Examples of alkyl groups represented by R ¹¹ and R ¹² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 1-methyl Examples include hexyl group, 4-tert-butylcyclohexyl group, n-heptyl group, 2-methylheptyl group, n-octyl group and the like.

In the hole-transporting compound of general formula (2), the substituent represented by R ¹³ and R ¹⁴ is an alkyl You may have a group. Since R ¹³ and R ¹⁴ are directly bonded to the benzene ring of fluorene, if the carbon chain of the alkyl group that may be present as a substituent represented by R ¹³ and R ¹⁴ is too long, inhibition due to steric hindrance, etc. may occur. influence becomes greater. Therefore, the number of carbon atoms of the alkyl group that may be present as a substituent represented by R ¹³ and R ¹⁴ is 4 or less. Examples of the alkyl group which may have as a substituent represented by R ¹³ and R ¹⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- A butyl group and the like can be mentioned.

The hole-transporting compound represented by the general formula (2) has an alkylene group having 2 or more and 6 or less carbon atoms represented by R ¹⁵ and R ¹⁷ between the benzene ring and the polymerizable functional group. The partial structures represented by ^R15 and ^R17 are important for the hole-transporting property of the hole-transporting compound represented by general formula (2).

Alkylene groups represented by R ¹⁵ and R ¹⁷ include ethylene group, n-propylene group, iso-propylene group, n-butylene group, iso-butylene group, sec-butylene group, tert-butylene group and n-pentylene group. , 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene group, n-hexylylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl -n-butylene group and the like.

In the general formulas (1) and (2), the substitution position of the amino group with respect to the fluorene structure is the 2-position or 4-position of the so-called fluorene from the viewpoint of the ease of compound synthesis and the electrical properties of the electrophotographic photoreceptor. - position is preferred. In particular, a structure in which an amino group is substituted at the 2-position is preferred.

In forming the surface layer of the electrophotographic photoreceptor according to the present invention, it is preferable to use a combination of the amine compound represented by the general formula (1) and the hole-transporting compound represented by the general formula (2). is.

The amine compound represented by the general formula (1) and the hole-transporting compound represented by the general formula (2) each have a similar alkyl group-substituted fluorene structure, and are compatible when used in combination. It is believed to be high and evenly distributed within the surface layer.

（式（３）中、Ｒ^２１およびＲ^２２は、それぞれ独立に、炭素数１以上４以下のアルキル基、または、置換または無置換のアリール基を示す。前記アリール基が有する置換基は、炭素数４以下のアルキル基である。Ｒ^２１およびＲ^２２は互いに結合して環を形成してもよい。Ｒ^２３は、炭素数１以上４以下のアルキル基を示す。Ｒ^２４およびＲ^２５は、それぞれ独立に、炭素数４以下のアルキレン基を示す。Ｒ^２６およびＲ^２７は、水素原子、または、メチル基を示す。） The composition used for forming the surface layer of the electrophotographic photoreceptor according to the present invention preferably further contains a compound represented by the following general formula (3).

(In formula (3), R ²¹ and R ²² each independently represent an alkyl group having 1 to 4 carbon atoms or a substituted or unsubstituted aryl group. an alkyl group having a number of 4 or less, R ²¹ and R ²² may be combined to form a ring, R ²³ represents an alkyl group having 1 to 4 carbon atoms, R ²⁴ and R ²⁵ are Each independently represents an alkylene group having 4 or less carbon atoms, and R ²⁶ and R ²⁷ represent a hydrogen atom or a methyl group.)

The compound represented by general formula (3) will be described. The compound represented by general formula (3) does not have hole-transport properties. The compound represented by general formula (3) is preferably used together with the hole-transporting compound represented by general formula (2). The compound represented by the general formula (3) has a moderately small molecular weight, improves the strength and the like of the surface layer, and has the effect of improving durability.

R ²¹ and R ²² in general formula (3) each independently represent an alkyl group having 1 to 4 carbon atoms or a substituted or unsubstituted aryl group. The substituent that the aryl group has is an alkyl group having 4 or less carbon atoms. Substituents possessed by the substituted aryl group which may be possessed by the groups represented by R ²¹ and R ²² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Examples include butyl group and tert-butyl group.

R ²¹ and R ²² are preferably alkyl groups having 1 to 4 carbon atoms. The molecular weight becomes compact, and it is easy to improve the strength of the surface layer. At least one of R ²¹ and R ²² is more preferably an alkyl group having 2 or more carbon atoms.

R ²¹ and R ²² may combine with each other to form a ring. In the case of forming a ring, examples of rings formed by R ²¹ and R ²² include cyclopentane ring, cyclohexane ring and cycloheptane ring.

R ²³ in general formula (3) is an alkyl group having 1 to 4 carbon atoms. R ²³ is preferably a methyl group or an ethyl group.

R ²⁴ and R ²⁵ in general formula (3) are alkylene groups having 4 or less carbon atoms, preferably methylene, ethylene or propylene.

If the content of the compound represented by the general formula (3) in the composition for forming the surface layer is too high, the hole transportability and potential stability of the formed surface layer are greatly reduced. Therefore, in the composition, the content ratio of the triarylamine-based hole-transporting compound having a bifunctional or more functional acryloyloxy group or methacryloyloxy group and the compound represented by the general formula (3) is the mass It is preferably 0.5 or more and 10 or less as a standard. Moreover, it is more preferably 0.7 or more and 4.0 or less, and still more preferably 1.0 or more and 3.0 or less.

The polymerizable functional group possessed by the polymerizable compound used in the present invention is preferably an acryloyloxy group or a methacryloyloxy group from the viewpoint of abrasion resistance of the surface layer and polymerization reaction rate. R ⁶ , R ¹⁶ , R ¹⁸ , R ²⁶ and R ²⁷ therefore represent a hydrogen atom or a methyl group.

Next, examples of compounds represented by general formula (1) are shown below. However, it is not limited to the following examples.

Examples of hole-transporting compounds represented by formula (2) are shown below. However, it is not limited to the following examples.

Examples of compounds represented by general formula (3) are shown below. However, it is not limited to the following examples.

Examples of compounds represented by general formula (4) other than the hole-transporting compound represented by general formula (2) are shown below. However, it is not limited to the following examples.

反応式（１）で示すように、ヨード体とアミン化合物を用いて、２級アミン体の合成を行った。反応容器にヨード体の３４．４部と、反応式（１）中のアミン体３０部、ｏ－ジクロロベンゼン６０部を混合し、炭酸カリウム１２部、銅粉８部を加えて、内温約２１０℃で約１６時間撹拌を行い反応した。反応後、濾過、トルエン洗浄、濃縮を行い粗生成物を得た。
粗生成物中に混在する、１級～３級のそれぞれのアミン体から２級アミン体のみをシリカゲルカラムクロマトグラフィーにより分離し、２級アミン中間体を得た。収量は２７．４部、収率は５５．０％であった。 Representative synthesis examples of the compounds used in the present invention are shown below.
<Synthesis Example 1>
A synthesis example of a secondary amine compound having a monofunctional polymerizable acrylic group represented by formula (1-8) will be shown.

As shown in reaction formula (1), a secondary amine compound was synthesized using an iodine compound and an amine compound. In a reaction vessel, 34.4 parts of the iodine body, 30 parts of the amine body in the reaction formula (1), and 60 parts of o-dichlorobenzene were mixed, 12 parts of potassium carbonate and 8 parts of copper powder were added, and the internal temperature was about approx. The mixture was stirred at 210° C. for about 16 hours to react. After the reaction, filtration, washing with toluene and concentration were carried out to obtain a crude product.
Secondary amine intermediates were obtained by separating only secondary amines from primary to tertiary amines mixed in the crude product by silica gel column chromatography. The yield was 27.4 parts and the yield was 55.0%.

得られた２級アミン中間体の２５部に対し、反応式（２）に示すように加水分解を行って酢酸エステル体からＯＨ体にした。２級アミン中間体の２５部に、テトラヒドロフラン６４部、メタノール６４部、２４％水酸化ナトリウム水溶液４５部を混合し、内温６０℃に加熱、撹拌して、１時間反応して加水分解を行った。反応後、反応混合物から酢酸エチルで抽出後、有機層を水洗、食塩水洗浄、脱水、濃縮を行った。シリカゲルクロマトグラフィーにより精製して２級アミンのヒドロキシ中間体を得た。収量は２０．４部、収率は９０．２％であった。

25 parts of the resulting secondary amine intermediate was hydrolyzed as shown in Reaction Formula (2) to convert the acetic ester form to the OH form. 64 parts of tetrahydrofuran, 64 parts of methanol, and 45 parts of a 24% aqueous sodium hydroxide solution are mixed with 25 parts of the secondary amine intermediate, heated to an internal temperature of 60° C., stirred, and reacted for 1 hour for hydrolysis. Ta. After the reaction, the reaction mixture was extracted with ethyl acetate, and the organic layer was washed with water, brine, dehydrated and concentrated. Purification by silica gel chromatography gave the hydroxy intermediate of the secondary amine. The yield was 20.4 parts and the yield was 90.2%.

上記反応により得られたヒドロキシ中間体の２０部、トルエン２００部、４－メトキシフェノール０．４部を混合し、アクリル酸４．７部を反応容器に投入した。ｐ－トルエンスルホン酸一水和物０．６５部を添加して１１２℃還流条件で６時間加熱し、反応式（３）で示すようにアクリル化反応を行った。
反応後、冷却し１０％水酸化ナトリウム水溶液を用いて中和し、酢酸エチルで抽出を行った。水洗浄、脱水、濃縮を行い粗生成物を得た。続いて、粗生成物をシリカゲルカラムクロマトグラフィーにより精製して式（１－８）で表される２級アミン化合物を得た。収量は１５．４部、収率は６７．８％であった。

20 parts of the hydroxy intermediate obtained by the above reaction, 200 parts of toluene and 0.4 parts of 4-methoxyphenol were mixed, and 4.7 parts of acrylic acid was added to the reactor. After adding 0.65 parts of p-toluenesulfonic acid monohydrate, the mixture was heated at 112° C. under reflux conditions for 6 hours to carry out an acrylation reaction as shown in reaction formula (3).
After the reaction, the mixture was cooled, neutralized with a 10% aqueous sodium hydroxide solution, and extracted with ethyl acetate. A crude product was obtained by washing with water, dehydration and concentration. Subsequently, the crude product was purified by silica gel column chromatography to obtain a secondary amine compound represented by formula (1-8). The yield was 15.4 parts and the yield was 67.8%.

Furthermore, the varnish containing the secondary amine compound represented by the formula (1-8) was obtained by adjusting the kind of solvent and the amount of solvent for the obtained secondary amine compound.
Similarly, other secondary amine compounds represented by general formula (1) can be synthesized.

反応式（４）で示すように、ヨード体とアミン化合物を用いて、トリアリールアミン体の合成を行った。反応容器に、ヨード体の９４．５部と、反応式（４）中のアミン体３４．５部、ｏ－ジクロロベンゼン８０部を混合し、炭酸カリウム２６．９部、銅粉１６．６部を加えて、内温約２１０℃で約２４時間撹拌を行い反応した。反応後、濾過、トルエン洗浄、濃縮を行い粗生成物を得た。 <Synthesis Example 2>
A synthesis example of a hole-transporting compound having a bifunctional polymerizable acrylic group represented by formula (2-7) will be shown.

As shown in reaction formula (4), a triarylamine compound was synthesized using an iodo compound and an amine compound. In a reaction vessel, 94.5 parts of the iodine body, 34.5 parts of the amine body in the reaction formula (4), and 80 parts of o-dichlorobenzene are mixed, and 26.9 parts of potassium carbonate and 16.6 parts of copper powder are mixed. was added, and the mixture was stirred at an internal temperature of about 210° C. for about 24 hours to react. After the reaction, filtration, washing with toluene and concentration were carried out to obtain a crude product.

引き続き、上記で得られた粗生成物を全量用いて、反応式（５）で示すように、得られた中間体の加水分解を行い酢酸エステルから水酸基にした。上記で得られた粗生成物に、テトラヒドロフラン１００部、メタノール１００部、２４％水酸化ナトリウム水溶液７０部を混合し、内温６０℃に加熱、撹拌して１時間反応して加水分解を行った。反応後、反応混合物から酢酸エチルで抽出後、有機層を水洗、食塩水洗浄、脱水、濃縮を行った。シリカゲルクロマトグラフィーにより精製してジヒドロキシ中間体を得た。収量は３６．９部、収率（２段階の反応後）は５３．２％であった。

Subsequently, using the whole amount of the crude product obtained above, the obtained intermediate was hydrolyzed as shown in Reaction Formula (5) to convert the acetate ester to a hydroxyl group. 100 parts of tetrahydrofuran, 100 parts of methanol, and 70 parts of a 24% aqueous sodium hydroxide solution were mixed with the crude product obtained above, heated to an internal temperature of 60° C., stirred, and reacted for 1 hour for hydrolysis. . After the reaction, the reaction mixture was extracted with ethyl acetate, and the organic layer was washed with water, brine, dehydrated and concentrated. Purification by silica gel chromatography gave the dihydroxy intermediate. The yield was 36.9 parts and the yield (after two-step reaction) was 53.2%.

上記反応により得られたジヒドロキシ中間体の３６．５部、トルエン３６５部、４－メトキシフェノール０．７部を混合し、アクリル酸１１．８部を反応容器に投入した。ｐ－トルエンスルホン酸一水和物１．３部を添加して１１２℃還流条件で６時間加熱し、反応式（６）で示すように、アクリル化反応を行った。

36.5 parts of the dihydroxy intermediate obtained by the above reaction, 365 parts of toluene and 0.7 parts of 4-methoxyphenol were mixed, and 11.8 parts of acrylic acid was added to the reactor. 1.3 parts of p-toluenesulfonic acid monohydrate was added and the mixture was heated at 112° C. under reflux conditions for 6 hours to carry out an acrylate reaction as shown in Reaction Formula (6).

After the reaction, the mixture was cooled, neutralized with a 10% aqueous sodium hydroxide solution, and extracted with ethyl acetate. A crude product was obtained by washing with water, dehydration and concentration. Subsequently, the crude product was purified by silica gel column chromatography to obtain a hole-transporting compound represented by formula (2-7). The yield was 39.5 parts and the yield was 63.0%.

Furthermore, a varnish containing a hole-transporting compound represented by the formula (2-7) was obtained by adjusting the type and amount of the solvent for the obtained hole-transporting compound. Similarly, other hole-transporting compounds represented by general formula (2) can be synthesized.

まず、２－メチルバレルアルデヒド５０部、３７％ホルムアルデヒド４０．５部、ベンジルトリメチルアンモニウムヒドロキシド（４０％水溶液）８．５部をオートクレーブ中に混合した。その後、窒素を用いてオートクレーブ中の圧力を０．５ＭＰａに上げ、９０℃で１時間撹拌し、反応式（７）で示すように反応を行った。反応終了後、反応液を室温まで冷却し、分液した。さらに水で洗浄して濃縮し、無色液体約５０部を得た。 <Synthesis Example 3>
Synthesis examples of the bifunctional polymerizable acrylic compound represented by formula (3-3) are shown below.

First, 50 parts of 2-methylvaleraldehyde, 40.5 parts of 37% formaldehyde and 8.5 parts of benzyltrimethylammonium hydroxide (40% aqueous solution) were mixed in an autoclave. Thereafter, the pressure in the autoclave was increased to 0.5 MPa using nitrogen, and the mixture was stirred at 90° C. for 1 hour to carry out a reaction as shown in reaction formula (7). After completion of the reaction, the reaction solution was cooled to room temperature and separated. Further, it was washed with water and concentrated to obtain about 50 parts of a colorless liquid.

得られた無色液体５０部を、トリメチロールプロパン５２部およびｐ－トルエンスルホン酸１部と混合し、室温で一晩撹拌し、反応式（８）で示すように反応を行った。反応終了後、反応物をカラムクロマトグラフィー（固定相としてシリカゲル、移動相として酢酸エチルをそれぞれ使用）で精製し、無色油状物を約３０部得た。

50 parts of the resulting colorless liquid was mixed with 52 parts of trimethylolpropane and 1 part of p-toluenesulfonic acid, and the mixture was stirred overnight at room temperature to carry out a reaction as shown in reaction formula (8). After completion of the reaction, the reaction product was purified by column chromatography (using silica gel as a stationary phase and ethyl acetate as a mobile phase) to obtain about 30 parts of a colorless oil.

溶媒としてクロロホルム、触媒としてトリエチルアミン、脱水縮合剤としてジシクロヘキシルカルボジイミドをそれぞれ用い、反応式（９）で示すように、得られた無色油状物とアクリル酸との脱水縮合を行った。

Using chloroform as a solvent, triethylamine as a catalyst, and dicyclohexylcarbodiimide as a dehydration condensation agent, dehydration condensation of the resulting colorless oil and acrylic acid was carried out as shown in reaction formula (9).

The filtrate of the reaction product was concentrated and purified by column chromatography (using silica gel as the stationary phase and n-hexane/ethyl acetate=4/1 as the mobile phase, respectively) to obtain a colorless liquid. Furthermore, 4-methoxyphenol was added as a polymerization inhibitor in an amount adjusted to a concentration of 100 ppm. A compound represented by the formula (3-3) was thus obtained.
Similarly, other polymerizable compounds represented by general formula (3) can be synthesized.

Further, the surface layer of the electrophotographic photoreceptor may contain a known hole-transporting compound having a polymerizable functional group, as long as the effect of the present invention is not impaired. An aromatic amine compound may be used as a known hole-transporting compound having a polymerizable functional group.

The surface layer of the electrophotographic photoreceptor may additionally contain a polymer of a mixed composition containing another compound having a polymerizable functional group and no hole-transporting property. By using a compound having other polymerizable functional groups in combination, the mechanical strength of the obtained polymer can be further improved.

The polymerizable functional group possessed by the compound having a polymerizable functional group and no hole transport property is preferably a radically polymerizable functional group such as a styryl group, a vinyl group, an acryloyloxy group, a methacryloyloxy group, or the like. is preferred. Acryloyloxy or methacryloyloxy is more preferred.

The surface layer may contain various fine particles from the viewpoint of abrasion resistance. The fine particles may be inorganic fine particles or organic fine particles. As the inorganic fine particles, particles containing alumina, silica, zinc oxide, tin oxide, titanium oxide, etc. are used.

Various organic resin fine particles can be used as the organic fine particles. Examples of resins constituting the organic resin fine particles include polyolefin resins, polytetrafluoroethylene resins, polystyrene resins, polyacrylic acid ester resins, polymethacrylic acid ester resins, polyamide resins, polyester resins, polyurethane resins, and the like.

The film thickness of the surface layer is preferably 0.1 μm or more and 15 μm or less when the surface layer is a protective layer described later. Moreover, when the surface layer is a hole transport layer described later, the thickness is preferably 5 μm or more and 40 μm or less. Furthermore, when the surface layer is a single layer type photosensitive layer described later, the thickness is preferably 5 μm or more and 40 μm or less.

Next, the overall structure of the electrophotographic photoreceptor according to the present invention will be described.
<Electrophotographic photoreceptor>
A preferred structure of the electrophotographic photoreceptor in the present invention is a structure in which a charge generation layer and a hole transport layer are laminated in this order on a support. If necessary, a conductive layer or an undercoat layer may be provided between the charge generation layer and the support, and a protective layer may be provided on the hole transport layer. In the present invention, the charge generation layer and the hole transport layer are collectively referred to as a photosensitive layer. The photosensitive layer may be composed of a single-layer type photosensitive layer containing a charge-generating substance and a hole-transporting compound.
The surface layer in the present invention refers to a protective layer when the protective layer is provided on the electrophotographic photoreceptor, and refers to a hole transport layer or a single layer type photosensitive layer when the protective layer is not provided.

<Support>
The support used in the present invention is preferably a conductive support made of a material having conductivity. Examples of materials for the support include metals and alloys such as iron, copper, gold, silver, aluminum, zinc, titanium, lead, nickel, tin, antimony, indium, chromium, aluminum alloys, and stainless steel. A metal support or a resin support having a film formed by vacuum deposition of aluminum, an aluminum alloy, an indium oxide-tin oxide alloy, or the like can also be used. A support obtained by impregnating plastic or paper with conductive particles such as carbon black, tin oxide particles, titanium oxide particles, or silver particles, or a support containing a conductive resin can also be used. The shape of the support includes a cylindrical shape, a belt shape, a sheet shape, a plate shape, etc., and the cylindrical shape is the most common.

The surface of the support is subjected to treatments such as cutting, roughening, and alumite treatment from the viewpoints of suppressing interference fringes caused by scattering of laser light, improving surface defects of the support, and improving the conductivity of the support. may

A conductive layer may be provided between the support and the undercoat layer or charge generation layer described below for the purpose of suppressing interference fringes due to scattering of laser or the like, controlling resistance, or covering scratches on the support.

The conductive layer can be formed by applying a conductive layer coating liquid obtained by dispersing carbon black, a conductive pigment, a resistance control pigment, etc. together with a binder resin, and drying the obtained coating film. can. A compound that is cured and polymerized by heating, ultraviolet irradiation, radiation irradiation, or the like may be added to the conductive layer coating liquid. A conductive layer formed by dispersing a conductive pigment or a resistance adjusting pigment tends to have a roughened surface.

The film thickness of the conductive layer is preferably 0.1 μm or more and 50 μm or less, more preferably 0.5 μm or more and 40 μm or less, and even more preferably 1 μm or more and 30 μm or less.

Binder resins used in the conductive layer include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid esters, methacrylic acid esters, vinylidene fluoride, and trifluoroethylene, polyvinyl alcohol resins, Polyvinyl acetal resins, polycarbonate resins, polyester resins, polysulfone resins, polyphenylene oxide resins, polyurethane resins, cellulose resins, phenolic resins, melamine resins, silicone resins, epoxy resins and isocyanate resins.

Examples of conductive pigments and resistance-adjusting pigments include metal (alloy) particles such as aluminum, zinc, copper, chromium, nickel, silver, and stainless steel, and plastic particles vapor-deposited with these particles. Particles of metal oxides such as zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, and antimony- or tantalum-doped tin oxide may also be used. These may be used alone or in combination of two or more.

An undercoat layer is provided between the support or the conductive layer and the charge generation layer for the purpose of improving adhesion of the charge generation layer, improving hole injection from the support, and protecting the charge generation layer against electrical breakdown. (Intermediate layer) may be provided.

The undercoat layer can be formed by applying an undercoat layer coating liquid obtained by dissolving a binder resin in a solvent and drying the resulting coating film.

Binder resins used in the undercoat layer include polyvinyl alcohol resin, poly-N-vinylimidazole, polyethylene oxide resin, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide resin, and N-methoxymethylated 6-nylon resin. , copolymerized nylon resins, phenolic resins, polyurethane resins, epoxy resins, acrylic resins, melamine resins and polyester resins.

The undercoat layer may further contain metal oxide particles. Metal oxide particles include particles containing titanium oxide, zinc oxide, tin oxide, zirconium oxide, and aluminum oxide. The metal oxide particles may also be metal oxide particles whose surfaces are treated with a surface treatment agent such as a silane coupling agent.

The film thickness of the undercoat layer is preferably 0.05 μm or more and 30 μm or less, more preferably 1 μm or more and 25 μm or less. The undercoat layer may further contain organic resin fine particles and a leveling agent.

Next, the charge generating layer will be explained. The charge-generating layer is formed by applying a charge-generating layer coating liquid obtained by dispersing a charge-generating substance together with a binder resin and a solvent to form a coating film, and drying the obtained coating film. can do. Also, the charge generation layer may be a deposited film of a charge generation substance.

Charge-generating substances used in the charge-generating layer include azo pigments, phthalocyanine pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, squarylium dyes, pyrylium salts, thiapyrylium salts, triphenylmethane dyes, quinacridone pigments, azulenium salt pigments, Examples include cyanine dyes, anthanthrone pigments, pyranthrone pigments, xanthene dyes, quinoneimine dyes, and styryl dyes. Only one kind of these charge generation substances may be used, or two or more kinds thereof may be used. Among these charge-generating substances, phthalocyanine pigments and azo pigments are preferred from the viewpoint of sensitivity, and phthalocyanine pigments are more preferred.

Among the phthalocyanine pigments, oxytitanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine exhibit excellent charge generation efficiency. Furthermore, among hydroxygallium phthalocyanines, from the viewpoint of sensitivity, crystalline hydroxy gallium phthalocyanine having peaks at Bragg angles 2θ of 7.4° ± 0.3° and 28.2° ± 0.3° in CuKα characteristic X-ray diffraction. Gallium phthalocyanine crystals are more preferred.

Examples of the binder resin used in the charge generation layer include polymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid esters, methacrylic acid esters, vinylidene fluoride and trifluoroethylene, polyvinyl alcohol resins, Polyvinyl acetal resins, polycarbonate resins, polyester resins, polysulfone resins, polyphenylene oxide resins, polyurethane resins, cellulose resins, phenol resins, melamine resins, silicon resins, epoxy resins, and the like can be mentioned.
The mass ratio of the charge generating substance and the binder resin is preferably in the range of 1:0.3 to 1:4.

The thickness of the charge generation layer is preferably 0.05 μm or more and 1 μm or less, more preferably 0.1 μm or more and 0.5 μm or less.

Next, the hole transport layer will be explained. When the hole-transporting layer is the surface layer, as described above, a triarylamine-based hole-transporting compound having a bifunctional or higher acryloyloxy group or a methacryloyloxy group and a compound represented by the general formula (1) It contains a polymer of a composition containing and.

On the other hand, when a protective layer is provided on the hole-transporting layer, the hole-transporting layer is formed by forming a coating film of a hole-transporting layer coating solution in which a hole-transporting compound and a binder resin are mixed in a solvent. It can be formed by drying the coating film. The hole-transporting compound and the binder resin used in the hole-transporting layer are described below.

Examples of hole-transporting compounds include carbazole compounds, hydrazone compounds, N,N-dialkylaniline compounds, diphenylamine compounds, triphenylamine compounds, triphenylmethane compounds, pyrazoline compounds, styryl compounds, and stilbene compounds.

Examples of binder resins include acrylic acid esters, methacrylic acid esters, polyvinyl alcohol resins, polyvinyl acetal resins, polycarbonate resins, and polyester resins. Also, curable resins such as curable phenol resins, curable urethane resins, curable melamine resins, curable epoxy resins, curable acrylic resins, and curable methacrylic resins can be used.

Solvents used in the hole transport layer coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aliphatic halogenated hydrocarbon solvents, aromatic hydrocarbon solvents, and the like. is mentioned.

The film thickness of the hole transport layer is preferably 1 μm or more and 100 μm or less, more preferably 3 μm or more and 50 μm or less, further preferably 5 μm or more and 40 μm or less.

In the present invention, a protective layer may be provided on the photosensitive layer. Durability can be improved by providing a protective layer. Moreover, when the electrophotographic photoreceptor has a protective layer, the protective layer is the surface layer in the present invention. That is, the protective layer is a polymer of a composition containing at least a triarylamine-based hole-transporting compound having a bifunctional or higher acryloyloxy group or a methacryloyloxy group, and a compound represented by the general formula (1). contains
The protective layer may also contain conductive particles and/or charge transport materials and a resin.

Conductive particles include particles of metal oxides such as titanium oxide, zinc oxide, tin oxide, and indium oxide.

Charge-transporting substances include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having groups derived from these substances. Among these, triarylamine compounds and benzidine compounds are preferred.

Examples of resins include polyester resins, acrylic resins, phenoxy resins, polycarbonate resins, polystyrene resins, phenol resins, melamine resins, and epoxy resins. Among them, polycarbonate resins, polyester resins, and acrylic resins are preferred.

The protective layer may contain additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a leveling agent, a lubricating agent, and an abrasion resistance improver. Specifically, hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane-modified resins, silicone oils, fluororesin particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, boron nitride particles. etc.

A method of forming the protective layer will be described later as a method of forming a surface layer in a method of manufacturing an electrophotographic photoreceptor.

Various additives can be added to each layer of the electrophotographic photoreceptor. Specifically, organic pigments, organic dyes, coating film surface conditioners, electron transport agents, oils, waxes, antioxidants, light absorbers, polymerization initiators, radical deactivators, organic resin fine particles, inorganic particles, etc. mentioned.

The surface of each layer of the electrophotographic photoreceptor may be surface-treated using a polishing sheet, a shape transfer mold member, glass beads, zirconia beads, or the like. Also, the constituent material of the coating liquid may be used to form unevenness on the surface. When applying the coating solution for each layer, for example, dip coating method, spray coating method, circular amount control type (ring) coating method, spin coating method, roller coating method, Meyer bar coating method, blade coating method, etc. Any known coating method can be used.

Next, a process cartridge equipped with the electrophotographic photosensitive member according to the present invention and an image forming process will be described.

FIG. 1 shows an example of the configuration of a process cartridge having an electrophotographic photosensitive member according to the present invention. In FIG. 1, a cylindrical electrophotographic photosensitive member 1 is rotationally driven at a predetermined peripheral speed in the direction of the arrow. The peripheral surface of the rotationally driven electrophotographic photosensitive member 1 is uniformly charged to a predetermined positive or negative potential by charging means 2 . Next, the peripheral surface of the charged electrophotographic photosensitive member 1 receives exposure light (image exposure light) 3 output from exposure means (not shown) such as slit exposure or laser beam scanning exposure. In this way, electrostatic latent images corresponding to desired images are sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1 . The voltage applied to the charging means (charging roller, etc.) 2 may be either a voltage obtained by superimposing an AC component on a DC component or a voltage containing only a DC component.

The electrostatic latent image formed on the circumferential surface of the electrophotographic photosensitive member 1 is developed with toner contained in the developer of the developing means 4 to form a toner image. Next, the toner images formed and carried on the peripheral surface of the electrophotographic photosensitive member 1 are sequentially transferred onto a transfer material (paper, intermediate transfer member, etc.) 6 by a transfer bias from transfer means (transfer roller, etc.) 5 . go. The transfer material 6 is fed in synchronism with the rotation of the electrophotographic photosensitive member 1 .

After the toner image has been transferred, the surface of the electrophotographic photosensitive member 1 is subjected to a charge elimination treatment by pre-exposure light 7 from pre-exposure means (not shown), and then cleaned by cleaning means 8 to remove residual toner after transfer. , the electrophotographic photoreceptor 1 is repeatedly used for image formation. The pre-exposure means may be used before or after the cleaning process, and the pre-exposure means is not necessarily required.

The electrophotographic photoreceptor 1 may be installed in an electrophotographic apparatus such as a copying machine or a laser beam printer. Further, a process cartridge 9 constructed by housing a plurality of constituent elements such as the electrophotographic photosensitive member 1, the charging means 2, the developing means 4 and the cleaning means 8 in a container and integrally supporting the main body of the electrophotographic apparatus. may be detachably attached to. In FIG. 1, an electrophotographic photosensitive member 1, a charging means 2, a developing means 4 and a cleaning means 8 are integrally supported to form a process cartridge 9 detachably attached to the main body of the electrophotographic apparatus.

Next, an electrophotographic apparatus equipped with the electrophotographic photoreceptor according to the present invention will be described.
FIG. 2 shows an example of the configuration of an electrophotographic apparatus provided with the electrophotographic photoreceptor according to the present invention. A yellow process cartridge 17 , a magenta process cartridge 18 , a cyan process cartridge 19 , and a black process cartridge 20 are arranged side by side along the intermediate transfer member 10 . As shown in FIG. 2, the diameter, constituent materials, developer, charging method, and other means of the electrophotographic photosensitive member do not necessarily have to be the same for each color. For example, in the electrophotographic apparatus of FIG. 2, the diameter of the electrophotographic photosensitive member is larger for black than for color (yellow, magenta, and cyan). In contrast to the charging method for color colors in which a voltage in which an AC component is superimposed on a DC component is applied, black color adopts a method using corona discharge.

When the image forming operation starts, toner images of respective colors are sequentially superimposed on the intermediate transfer member 10 according to the image forming process described above. In parallel, the transfer paper 11 is sent out from the paper feed tray 13 by the paper feed path 12 and fed to the secondary transfer means 14 in synchronization with the rotation of the intermediate transfer member 10 . The toner image on the intermediate transfer member 10 is transferred to the transfer paper 11 by the transfer bias from the secondary transfer means 14 . The toner image transferred onto the transfer paper 11 is conveyed along the paper feed path 12 , fixed on the transfer paper by the fixing means 15 , and discharged from the paper discharge section 16 .

（式（１）中、Ｒ^１およびＲ^２は、それぞれ独立に、炭素数１以上８以下のアルキル基を示す。Ｒ^３およびＲ^４は、それぞれ独立に、水素原子、または、炭素数４以下のアルキル基を示す。Ｒ^５は、炭素数２以上６以下のアルキレン基を示す。Ｒ^６は、水素原子、または、メチル基を示す。） A method for producing an electrophotographic photoreceptor according to the present invention is a method for producing an electrophotographic photoreceptor having a support and a photosensitive layer on the support, wherein the production method comprises at least bifunctional acryloyloxy groups or a step (i) of forming a coating film of a surface layer coating liquid containing a triarylamine-based hole-transporting compound having a methacryloyloxy group and a compound represented by the following general formula (1); A step (ii) of polymerizing the coating film to form a surface layer of the electrophotographic photoreceptor is included.

(In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or 4 or less carbon atoms. represents an alkyl group of R ⁵ represents an alkylene group having 2 to 6 carbon atoms, and R ⁶ represents a hydrogen atom or a methyl group.)

The content ratio of the compound represented by the general formula (1) in the surface layer coating liquid is 0.1 mass with respect to the triarylamine-based hole-transporting compound in the surface layer coating liquid. % or more and 1.0 mass % or less .

Solvents used in the surface layer coating liquid include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aliphatic halogenated hydrocarbon solvents, aliphatic hydrocarbon solvents, aromatic A hydrocarbon solvent or the like can be used.

As a method of polymerizing the coating film of the surface layer coating liquid (polymerizing the polymerizable compound used in the present invention), a method of polymerizing using heat, light (ultraviolet rays, etc.), or radiation (electron beams, etc.). is mentioned. Among these, radiation is preferable, and electron beams are more preferable among radiation.

Polymerization using an electron beam is preferable because a very dense (high density) three-dimensional network structure can be obtained and abrasion resistance is improved. In addition, since the polymerization reaction takes a short time and is efficient, the productivity is also increased. In the case of electron beam irradiation, accelerators include, for example, a scanning type, an electrocurtain 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 150 kV or less from the viewpoint of suppressing deterioration of material properties due to the electron beam without impairing the polymerization efficiency. The electron beam absorption dose on the surface of the coating film of the surface layer coating liquid is preferably 5 kGy or more and 50 kGy or less, more preferably 10 kGy or more and 30 kGy or less.

Further, when the polymerizable compound used in the present invention is polymerized using an electron beam, the electron beam is irradiated in an inert gas atmosphere and then heated in the inert gas atmosphere for the purpose of suppressing the polymerization inhibition effect of oxygen. is preferred. Inert gases include nitrogen, argon, helium, and the like.

The present invention will be described in more detail below with reference to specific examples. In addition, "part" in an Example means "mass part." In addition, the electrophotographic photoreceptor is hereinafter simply referred to as "photoreceptor".
In the following description, Examples 2, 4, 8 and 12 are reference examples.

<Production of Electrophotographic Photoreceptor>
[Example 1]
A cylindrical aluminum cylinder having an outer diameter of 30.0 mm, a length of 357.5 mm and a thickness of 0.7 mm was used as a support (conductive support).

Next, 10 parts of zinc oxide particles (specific surface area: 19 m ² /g, powder resistivity: 4.7×10 ⁶ Ω·cm) are stirred and mixed with 50 parts of toluene. were added and stirred for 6 hours. Thereafter, toluene was distilled off under reduced pressure, and the residue was dried by heating at 130° C. for 6 hours to obtain surface-treated zinc oxide particles. As a silane coupling agent, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) was used.
Next, prepare 15 parts of polyvinyl butyral resin (weight average molecular weight: 40000, trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.) and 15 parts of blocked isocyanate (trade name: Duranate TPA-B80E, manufactured by Asahi Kasei Chemicals). did. These were dissolved in a mixed solution of 73.5 parts of methyl ethyl ketone and 73.5 parts of 1-butanol. 80.8 parts of the surface-treated zinc oxide particles and 0.8 parts of 2,3,4-trihydroxybenzophenone (manufactured by Wako Pure Chemical Industries, Ltd.) were added to the solution, and glass beads having a diameter of 0.8 mm were added thereto. was dispersed in an atmosphere of 23±3° C. for 3 hours using a sand mill apparatus using After dispersion, the following materials were prepared.
・ Silicone oil (trade name: SH28PA, manufactured by Dow Corning Toray Co., Ltd.) 0.01 part ・ Crosslinked polymethyl methacrylate (PMMA) particles (trade name: TECHPOLYMER SSX-102, manufactured by Sekisui Plastics Co., Ltd., average primary particle size 2 .5 μm) 5.6 parts These were added and stirred to prepare an undercoat layer coating solution.
This undercoat layer coating liquid was applied onto the support by dip coating to form a coating film, and the resulting coating film was dried at 160° C. for 40 minutes to form an undercoat layer having a thickness of 18 μm.

Next, two copies of a crystalline hydroxygallium phthalocyanine crystal (charge-generating substance) having peaks at 7.4° and 28.2° of Bragg angles 2θ±0.2 in CuKα characteristic X-ray diffraction were prepared. Further, 0.02 part of a calixarene compound represented by the following structural formula (A), 1 part of polyvinyl butyral (trade name: S-Lec BX-1, manufactured by Sekisui Chemical Co., Ltd.), and 60 parts of cyclohexanone were prepared. These were placed in a sand mill using glass beads with a diameter of 1 mm and dispersed for 4 hours. Thereafter, 70 parts of ethyl acetate was added to prepare a charge generation layer coating solution. This charge-generating layer coating solution was dip-coated on the undercoat layer, and the resulting coating film was dried at 90° C. for 15 minutes to form a charge-generating layer having a thickness of 0.17 μm.

Next, the following materials were prepared.
・6 parts of the compound represented by the following structural formula (B) ・3 parts of the compound represented by the following structural formula (C) ・1 part of the compound represented by the following structural formula (D) ・Bisphenol Z type polycarbonate resin (product Name: Iupilon Z400, manufactured by Mitsubishi Engineering-Plastics) 10 parts of these are dissolved in a mixed solvent of 35 parts of o-xylene, 35 parts of dimethoxymethane, and 30 parts of methyl benzoate to prepare a hole transport layer coating solution. prepared. This hole transport layer coating liquid was dip-coated on the charge generation layer, and the resulting coating film was dried at 110° C. for 50 minutes to form a hole transport layer having a thickness of 18 μm.

これを１－プロパノール４５部およびゼオローラＨ（日本ゼオン社製）４５部の混合溶媒に溶解した。その後、フッ化エチレン樹脂粉体（商品名：ルブロンＬ－２、ダイキン工業社製）３０部を添加し、高圧分散機（商品名：マイクロフルイダイザーＭ－１１０ＥＨ、米Ｍｉｃｒｏｆｌｕｉｄｉｃｓ社製）で分散することで、フッ化エチレン樹脂分散液を得た。
次に、式（１－８）で示されるアミン化合物０．００４部、式（２－７）で示される正孔輸送性化合物４部、式（３－３）で表される化合物１．６部を用意した。これらと、フッ化エチレン樹脂分散液８部と、１－プロパノール３部と、ゼオローラＨ３部と、を混合、撹拌して均一に分散させて保護層用塗布液を調製した。
この保護層用塗布液を前記正孔輸送層上に浸漬塗布し、得られた塗膜を１０分間５０℃で乾燥させ、下記の条件で電子線照射と加熱による重合硬化処理を行った。
酸素濃度５０ｐｐｍ以下の雰囲気にて、アルミニウムシリンダーを３００ｒｐｍの速度で回転させながら、電子線照射装置を用いて、照射距離３０ｍｍ、加速電圧７０ｋＶ、ビーム電流８ｍＡ、照射時間３．０秒の条件で電子線照射した。電子線照射後、酸素濃度５０ｐｐｍ以下の条件のまま、速やかに誘導加熱装置を用いて保護層塗膜表面を２４秒かけて１３５℃に到達させた。
次に、上記アルミニウムシリンダーを大気雰囲気に取り出し、さらに１２分間１００℃で加熱することによって、膜厚５μｍの保護層を形成した。 A fluorine atom-containing acrylic resin having a repeating structural unit represented by the following formula (F1) and a repeating structural unit represented by the following formula (F2) (weight average molecular weight: 83,000, copolymerization ratio (F1) / (F2 )=1/1 (molar ratio)) 1.5 parts were prepared.

This was dissolved in a mixed solvent of 45 parts of 1-propanol and 45 parts of Zeorora H (manufactured by Nippon Zeon Co., Ltd.). After that, 30 parts of fluoroethylene resin powder (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) is added and dispersed with a high-pressure disperser (trade name: Microfluidizer M-110EH, manufactured by Microfluidics, USA). Thus, an ethylene fluoride resin dispersion was obtained.
Next, 0.004 parts of the amine compound represented by the formula (1-8), 4 parts of the hole-transporting compound represented by the formula (2-7), and 1.6 parts of the compound represented by the formula (3-3) prepared the part. These, 8 parts of fluoroethylene resin dispersion, 3 parts of 1-propanol, and 3 parts of zeorola H were mixed and stirred to uniformly disperse to prepare a protective layer coating liquid.
This protective layer coating solution was dip-coated on the hole transport layer, the resulting coating film was dried at 50° C. for 10 minutes, and polymerized and cured by electron beam irradiation and heating under the following conditions.
In an atmosphere with an oxygen concentration of 50 ppm or less, while rotating the aluminum cylinder at a speed of 300 rpm, using an electron beam irradiation device, an irradiation distance of 30 mm, an acceleration voltage of 70 kV, a beam current of 8 mA, and an irradiation time of 3.0 seconds. ray irradiated. After the electron beam irradiation, the surface of the protective layer coating film was rapidly heated to 135° C. over 24 seconds using an induction heating device while maintaining the oxygen concentration of 50 ppm or less.
Next, the aluminum cylinder was taken out into the atmosphere and heated at 100° C. for 12 minutes to form a protective layer having a thickness of 5 μm.

Next, a mold member (mold) was installed in a press-contact shape transfer processing apparatus, and surface processing was performed on the electrophotographic photoreceptor before formation of recesses.
Specifically, a mold having a surface shape shown in FIG. 4 was installed in a pressure contact shape transfer processing apparatus having a configuration generally having a mold 22, a pressure member 23, and a support member 24 shown in FIG. Surface processing was performed on the electrophotographic photosensitive member 21 before forming the concave portions.

FIG. 4 is a diagram showing a mold used in Examples and Comparative Examples. FIG. 4(a) is a top view schematically showing the mold, and FIG. 4(b) is a schematic cross-sectional view of the convex portion of the mold in the direction corresponding to the axial direction of the electrophotographic photosensitive member 21 (S-- is a cross-sectional view in the S' cross section). FIG. 4(c) is a cross-sectional view of the protrusions of the mold in the direction corresponding to the circumferential direction of the electrophotographic photosensitive member 21 (cross-sectional view of the TT' cross section of FIG. 4(a)).

The maximum width of the convex portion of the mold shown in FIG. 4 (the maximum width in the direction corresponding to the axial direction of the electrophotographic photosensitive member 21 when the convex portion on the mold is viewed from above) X is 50 μm. . Also, the maximum length of the convex portion of the mold shown in FIG. 4 (the maximum length in the direction corresponding to the circumferential direction of the electrophotographic photosensitive member 21 when the convex portion on the mold is viewed from above) Y is 75 μm. Furthermore, the mold shown in FIG. 4 has projections with an area ratio of 56% and a height H of 4 μm. Note that the area ratio is the ratio of the area of the projections to the entire surface of the mold when viewed from above.

During processing, the temperatures of the electrophotographic photoreceptor 21 and the mold were controlled so that the surface temperature of the electrophotographic photoreceptor 21 was 120.degree. Then, while pressing the electrophotographic photosensitive member and the pressure member 23 against the mold with a pressure of 7.0 MPa, the electrophotographic photosensitive member 21 is rotated in the circumferential direction, and the entire surface layer (peripheral surface) of the electrophotographic photosensitive member 21 is pressed. A recess was formed in the Thus, an electrophotographic photoreceptor 21 was manufactured.

The surface of the obtained electrophotographic photoreceptor 21 is observed with a laser microscope (trade name: X-100, manufactured by Keyence Corporation) with a magnification of 50 times, and the concave portions provided on the surface of the electrophotographic photoreceptor 21 are observed. went. At the time of observation, adjustments were made so that the electrophotographic photosensitive member 21 was not tilted in the longitudinal direction, and that the apex of the arc of the electrophotographic photosensitive member 21 was in focus in the circumferential direction. A square area with a side of 500 μm was obtained by connecting images obtained by magnifying observation using an image connection application. Then, for the obtained results, image processing height data was selected using attached image analysis software, and filter processing was performed using filter type median.

As a result of the observation, the depth of the recess was 2 μm, the width of the opening in the axial direction was 50 μm, the length of the opening in the circumferential direction was 75 μm, and the area was 140000 μm ² . The area is the area of the recess when the surface of the electrophotographic photosensitive member 21 is viewed from above, and means the area of the opening of the recess.
A photoreceptor according to Example 1 was produced as described above.

[Example 2]
A photoconductor according to Example 2 was produced in the same manner as in Example 1, except that the amount of the compound represented by formula (1-8) was changed to 0.002 parts.

[Example 3]
A photoreceptor according to Example 3 was produced in the same manner as in Example 1, except that the amount of the compound represented by formula (1-8) was changed to 0.04 parts.

[Example 4]
In Example 1, the amount of the compound represented by the formula (1-8) was changed to 0.0004 parts, and the type and amount of the compound represented by the general formula (3) were changed to the formula (3-1). A photoreceptor according to Example 4 was produced in the same manner as in Example 1, except that the compound represented was changed to 1.6 parts.

[Example 5]
A photoconductor according to Example 5 was produced in the same manner as in Example 4, except that the amount of the compound represented by formula (1-8) was changed to 0.004 parts.

[Example 6]
A photoreceptor according to Example 6 was produced in the same manner as in Example 4, except that the amount of the compound represented by formula (1-8) was changed to 0.02 parts.

[Example 7]
A photoreceptor according to Example 7 was produced in the same manner as in Example 4, except that the amount of the compound represented by formula (1-8) used in Example 4 was changed to 0.04 parts.

[Example 8]
A photoreceptor according to Example 8 was produced in the same manner as in Example 4, except that the amount of the compound represented by formula (1-8) was changed to 0.08 parts.

[Example 9]
Example 4 was carried out in the same manner as in Example 4 except that the type and amount of the amine compound represented by the general formula (1) was changed to 0.02 parts of the compound represented by the formula (1-9). A photoreceptor according to No. 9 was produced.

[Example 10]
Example 4 in the same manner as in Example 4 except that the type and amount of the amine compound represented by the general formula (1) was changed to 0.02 parts of the compound represented by the formula (1-5) A photoreceptor according to No. 10 was produced.

[Example 11]
Example 4 in the same manner as in Example 4 except that the type and amount of the amine compound represented by the general formula (1) was changed to 0.02 parts of the compound represented by the formula (1-10) A photoreceptor according to No. 11 was produced.

[Example 12]
The amount of the compound represented by formula (1-8) used in Example 4 was 0.00056 parts. Further, 5.6 parts of the hole-transporting compound represented by the formula (4-10) was used instead of the hole-transporting compound represented by the general formula (2). The compound represented by formula (1-8) and the hole-transporting compound represented by formula (4-10), 8 parts of the fluoroethylene resin dispersion, 3 parts of 1-propanol, and Zeorora H3 The parts were mixed and stirred to disperse them uniformly to prepare a protective layer coating liquid. A photoreceptor according to Example 12 was produced in the same manner as in Example 4 except for the above.

[Example 13]
A photoreceptor according to Example 13 was produced in the same manner as in Example 12, except that the amount of the compound represented by formula (1-8) was changed to 0.0056 parts.

[Example 14]
A photoreceptor according to Example 14 was produced in the same manner as in Example 12 except that the amount of the compound represented by formula (1-8) used was changed to 0.056 parts.

[Comparative Example 1]
A photoreceptor according to Comparative Example 1 was produced in the same manner as in Example 12, except that the compound represented by formula (1-8) was not used in Example 12.

[Comparative Example 2]
In Comparative Example 2 in the same manner as in Example 12 except that 0.00056 parts of a comparative compound represented by the following structural formula (H) was used instead of the compound represented by Formula (1-8) in Example 12. A photoreceptor was produced.

[Comparative Example 3]
A photoreceptor according to Comparative Example 3 was produced in the same manner as in Comparative Example 1, except that the amount of the comparative compound used in Comparative Example 1 was changed to 0.0056 parts.

[Comparative Example 4]
A photoreceptor according to Comparative Example 4 was produced in the same manner as in Comparative Example 1, except that the amount of the comparative compound used in Comparative Example 1 was changed to 0.056 parts.
Table 1 shows the compounds used as the compound represented by the general formula (1) or the comparative compounds used in place of the compounds represented by the general formula (1) in the above Examples and Comparative Examples. Further, in the above Examples and Comparative Examples, the use of the compound represented by the general formula (1) or the comparative compound for a triarylamine-based hole-transporting compound having a bifunctional or higher acryloyloxy group or methacryloyloxy group. Table 1 shows the ratio (% by mass). In Table 1, a triarylamine-based hole-transporting compound having a bifunctional or more acryloyloxy group or methacryloyloxy group is simply referred to as a hole-transporting compound.

<Evaluation: residual potential>
The photoreceptors according to Examples 1 to 14 and Comparative Examples 1 to 4 produced above were evaluated for residual potential under the following conditions.
Using a photoreceptor testing device (trade name: CYNTHIA59, manufactured by Gentec), first, the charging device conditions were set so that the surface of the electrophotographic photoreceptor was −700 V in an environment of temperature 23° C./50% RH. It was set. This was irradiated with monochromatic light having a wavelength of 780 nm, and the amount of light necessary for lowering the potential of -700V to -200V was applied. Furthermore, the potential of the photoreceptor when it was irradiated with a light amount of 20 (μJ/cm ² ) was measured and defined as a residual potential (−V).
Table 1 shows the evaluation results.

<Evaluation: Evaluation of Image Density Unevenness in Repeated Use>
Image unevenness was evaluated using the photoreceptors according to Examples 1 to 14 and Comparative Examples 1 to 4 produced above. A copying machine (trade name: iR ADVANCE C5560F, manufactured by Canon Inc.) was used as an electrophotographic apparatus.
First, the copier and the electrophotographic photoreceptor were left in an environment with a temperature of 27° C. and a humidity of 70% RH for 24 hours or more, and then the electrophotographic photoreceptor was mounted in the cyan cartridge of the copier. The density of the printed image was 1.45±0.5 when measured with a spectral densitometer (trade name: X-rite 504, manufactured by Xrite), and the printing ratio was 5%. This printed image was continuously formed on 10,000 sheets of A4 size plain paper.

After that, the power supply to the copying machine was completely stopped, and the copying machine was rested for 15 hours. After the pause, power was supplied to the copying machine again, and a halftone image of a 1-dot Keima pattern was formed on A3 size plain paper in a single color of cyan. The amount of light was set so that the halftone density was 0.85. For this halftone image, a spectral densitometer (trade name: X-rite 504, manufactured by Xrite) was used to measure the image density at multiple points throughout, and the difference between the maximum density value and the minimum density value was used to determine the degree of image unevenness. determined the rank.
The evaluation rank was as follows.
Rank 5: No density difference is observed in halftones.
Rank 4: A slight density difference was observed in the halftone.
Rank 3: Less than 0.1 but slight density difference is observed in the halftone.
Rank 2: Density difference of 0.1 or more is observed in the halftone.
Rank 1: Density difference of 0.2 or more is observed in the halftone.

Table 1 shows the evaluation results.

By using the secondary amine compound represented by the general formula (1), it was possible to suppress the image unevenness that may occur at the contact portion of the charger when the electrophotographic apparatus is stopped. In particular, by using the secondary amine compound represented by the general formula (1) in a suitable ratio with respect to the triarylamine-based hole-transporting compound having a bifunctional or higher acryloyloxy group or methacryloyloxy group, Image unevenness could be effectively suppressed.

On the other hand, when a secondary amine compound other than the secondary amine compound represented by the general formula (1) was used, the effect of improving image unevenness was not observed, and the value of residual potential increased in some cases.

1, 21...Electrophotographic photosensitive member 2...Charging means 3...Exposure light 4...Development means 5...Transfer means 6...Transfer material 7...Pre-exposure light 8...Cleaning means 9...Process cartridge 10...Intermediate transfer member 11...Transfer paper 12...Paper feed path 13...Paper feed tray 14...Secondary transfer means 15...Fixing means 16...Paper discharge unit 17...Yellow process cartridge 18... Process cartridge for magenta 19... Process cartridge for cyan 20... Process cartridge for black 22... Mold 23... Pressure member 24... Support member

Claims (11)

An electrophotographic photoreceptor having a support and a photosensitive layer,
The surface layer of the electrophotographic photoreceptor comprises a triarylamine-based hole-transporting compound having at least a bifunctional or higher acryloyloxy group or a methacryloyloxy group , and a compound represented by the following general formula (1) . containing a polymer of a composition comprising
The content of the compound represented by the following general formula (1) in the composition is 0.1% by mass or more and 1.0% by mass relative to the triarylamine-based hole-transporting compound in the composition. is the following
An electrophotographic photoreceptor characterized by :

(In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or 4 or less carbon atoms. represents an alkyl group of R ⁵ represents an alkylene group having 2 to 6 carbon atoms, and R ⁶ represents a hydrogen atom or a methyl group.) The content ratio of the compound represented by the general formula (1) in the composition is 0.5% by mass or more and 1.0% with respect to the triarylamine-based hole-transporting compound in the composition. 2. The electrophotographic photoreceptor according to claim 1 , wherein the content is mass % or less . 3. The electrophotographic photoreceptor according to claim 1 , wherein the triarylamine-based hole-transporting compound has a structure represented by the following general formula (2).

(In formula (2), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 8 carbon atoms. R ¹³ and R ¹⁴ each independently represent a hydrogen atom or 4 or less carbon atoms. R ¹⁵ and R ¹⁷ each independently represent an alkylene group having 2 to 6 carbon atoms, and R ¹⁶ and R ¹⁸ each independently represent a hydrogen atom or a methyl group. ) The electrophotographic photoreceptor according to any one of claims 1 to 3 , wherein the composition further contains a compound represented by the following general formula (3).

(In formula (3), R ²¹ and R ²² each independently represent an alkyl group having 1 to 4 carbon atoms or a substituted or unsubstituted aryl group. an alkyl group having a number of 4 or less, R ²¹ and R ²² may be combined to form a ring, R ²³ represents an alkyl group having 1 to 4 carbon atoms, R ²⁴ and R ²⁵ are Each independently represents an alkylene group having 4 or less carbon atoms, and R ²⁶ and R ²⁷ represent a hydrogen atom or a methyl group.) 5. The electrophotographic photoreceptor according to claim 4 , wherein at least one of ^R21 and ^R22 in the general formula (3) is an alkyl group having 2 or more carbon atoms. An electrophotographic apparatus comprising the electrophotographic photoreceptor according to any one of claims 1 to 5 , charging means, exposure means, developing means and transfer means. 6. The electrophotographic photoreceptor according to any one of claims 1 to 5 and at least one means selected from the group consisting of charging means, developing means, transfer means and cleaning means are integrally supported; A process cartridge that can be attached to and detached from the main body of a photographic apparatus. A method for producing an electrophotographic photoreceptor having a support and a photosensitive layer on the support, comprising:
The manufacturing method is
A coating film of a surface layer coating liquid containing at least a triarylamine-based hole-transporting compound having a bifunctional or higher acryloyloxy group or methacryloyloxy group, and a compound represented by the following general formula (1): step (i) of forming a
Step (ii) of polymerizing the coating film to form a surface layer of the electrophotographic photoreceptor
has
The content ratio of the compound represented by the following general formula (1) in the surface layer coating liquid is 0.1 mass relative to the triarylamine-based hole-transporting compound in the surface layer coating liquid. % or more and 1.0% by mass or less ,
A method for producing an electrophotographic photoreceptor , characterized by :

(In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or 4 or less carbon atoms. represents an alkyl group of R ⁵ represents an alkylene group having 2 to 6 carbon atoms, and R ⁶ represents a hydrogen atom or a methyl group.) The content ratio of the compound represented by the general formula (1) in the surface layer coating liquid is 0.5 with respect to the triarylamine-based hole-transporting compound in the surface layer coating liquid. 9. The method for producing an electrophotographic photoreceptor according to claim 8 , wherein the amount is not less than 1.0% by mass and not more than 1.0% by mass . 10. The method for producing an electrophotographic photoreceptor according to claim 8, wherein the surface layer coating liquid further contains a compound represented by the following general formula (3).

(In formula (3), R ²¹ and R ²² each independently represent an alkyl group having 1 to 4 carbon atoms or a substituted or unsubstituted aryl group. an alkyl group having a number of 4 or less, R ²¹ and R ²² may be combined to form a ring, R ²³ represents an alkyl group having 1 to 4 carbon atoms, R ²⁴ and R ²⁵ are Each independently represents an alkylene group having 4 or less carbon atoms, and R ²⁶ and R ²⁷ represent a hydrogen atom or a methyl group.) R in the general formula (3) ²¹ and R ²² is an alkyl group having 2 or more carbon atoms.

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