JP2003246771A - New phenol compound, new resol resin, their cured product, electrophotographic photoreceptor containing the cured product, and process cartridge and electrophotographic apparatus having the electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new phenol compound, a new resol resin, an electrophotographic photoreceptor obtained by using their cured product and having high durability against the occurrence of a wear and a scratch, having a small increase of residual potential and a small potential fluctuation, being able to hold a high picture quality for a long time, and causing no image flow when using for a long time under an environment of a high temperature and a high humidity, and a process cartridge and an electrophotographic apparatus having the electrophotographic photoreceptor. <P>SOLUTION: The phenol compound has a substituted hydroxyphenyl group and an electric charge transferring structure wherein the substituted hydroxyphenyl group has a hydroxymethyl group, and the resol resin is obtained by reacting a phenol compound having a hydroxyphenyl group and an electric charge transferring structure with formaldehyde in the presence of a basic catalyst wherein the resol resin has an electric charge transferring structure. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel phenol compound, a novel resol resin, a cured product thereof, an electrophotographic photoreceptor containing them, a process cartridge having the electrophotographic photoreceptor and an electrophotographic apparatus.

[0002]

2. Description of the Related Art A compound having a hydroxyphenyl group,
Among so-called phenol compounds, a phenol compound having a hydroxymethyl group in its hydroxyphenyl group (hydroxymethyl group-containing phenol compound) is known to be used for various purposes. For example,
D. H. SOLOMON's book "THE CHEMISTRY OF ORG
Besides the application to paint as described in "ANIC FILM FORMERS", lithographic printing plate, photoresist, adhesive,
It is used in many fields such as molding materials, laminating materials and binders. For these applications, compounds such as phenol-formalin-resole resin, bishydroxymethyl-p-cresol and tetrakishydroxymethylbisphenol A are often used.

However, such known hydroxymethyl group-containing phenol compounds and phenol-formalin-resole resins do not have a charge transporting structure in the molecule. Further, since the number of hydroxymethyl groups contained in the molecule is small, sufficient hardening performance could not be obtained when both were used in paints or photosensitive printing plates.
In order to satisfy the film hardening performance, it was necessary to add a large amount of hydroxymethyl group-containing phenol compound and resol resin.

A compound having a charge-transporting structure and a hydroxyphenyl group-containing hydroxyphenyl group in the same molecule and forming a three-dimensionally crosslinked structure by heating alone to give a strong cured product has not yet been released. It doesn't exist.

In recent years, research and development of organic electrophotographic photoconductors using organic photoconductive materials have been actively carried out because of advantages such as high safety, excellent productivity, and low cost.
Many inventions have been made and put to practical use.

However, an electrophotographic photoreceptor containing a photoconductive polymer typified by poly-N-vinylcarbazole and a charge transfer complex formed of 2,4,7-trinitrofluorene as main components is It was not always satisfactory in terms of sensitivity, durability and residual potential.

In addition, a function-separated type electrophotographic photosensitive member in which a charge generating function and a charge transporting function are shared by different substances has the sensitivity and durability which have been considered to be defects of the conventional organic electrophotographic photosensitive member. It brought a significant improvement.

Further, the function-separated type electrophotographic photosensitive member has the advantage that the material selection range of each of the charge generating substance and the charge transporting substance is wide, and an electrophotographic photosensitive member having desired characteristics can be produced relatively easily. Have

As the charge generating substance, various azo pigments,
Polycyclic quinone pigment, phthalocyanine pigment, cyanine dye,
Squaric acid dyes and pyrylium salt dyes are known. In addition, pyrazoline compounds, hydrazone compounds, triphenylamine compounds and the like are known as charge transport substances.

Incidentally, with the recent trend toward higher image quality and higher speed and durability, organic electrophotographic photoreceptors are also required to have further improved mechanical durability.

Further, in recent years, electrophotographic apparatuses such as printers, copiers and facsimiles using electrophotographic photosensitive members have come to be used in a wide variety of fields, and a stable image can always be obtained even in various environments. There is a more stringent requirement to provide such a material, which is more likely to be exposed to chemical, electrical and mechanical impacts on the surface characteristics of the electrophotographic photosensitive member, and the requirements for the surface layer are increasing.

Since the electrophotographic photosensitive member is directly applied with the above-mentioned electric and mechanical external forces, durability against them is required. Specifically, it is required to have durability against abrasion and scratches on the surface due to rubbing, and deterioration of the surface layer due to attachment of active substances such as ozone and nitrogen oxides generated during charging.

Further, the electrophotographic photosensitive member is charged, exposed,
It is repeatedly applied to processes such as development, transfer, cleaning and charge removal. The electrostatic latent image formed by charging and exposure becomes a toner image by a fine particle developer called “toner”. Further, this toner image is transferred to a transfer material such as paper by a transfer means, but not all the toner is transferred, and a part thereof remains as a residual toner on the electrophotographic photosensitive member.

When the amount of the residual toner is large, the image on the transfer material is in a so-called bleed-out state in which further transfer failure occurs, and not only the image uniformity is lacked but also the fusion of the toner to the electrophotographic photosensitive member and the The problem of filming occurs. For these problems, it is required to improve the releasability of the surface layer of the electrophotographic photosensitive member.

In order to satisfy the above-mentioned requirements for the electrophotographic photosensitive member, various attempts have been made to improve the surface layer, and in particular, attempts to provide a protective layer have been actively made. Among them,
Many protective layers containing a resin as a main component have been proposed.

For example, Japanese Patent Application Laid-Open No. 57-30846 discloses a protective layer capable of controlling volume resistance by adding a metal oxide as a conductive powder to a resin. Further, Japanese Patent Laid-Open No. 5-181299 discloses that
It is disclosed that a curable phenol resin is used as a resin for a protective layer. Further, as an example in which a phenol resin is used as a binder resin for the surface layer, see JP-A-5-1812.
It is disclosed in Japanese Patent Publication No. 99 and the like.

However, even with these surface layers, those having sufficiently satisfactory characteristics as a protective layer such as durability against various impacts on the surface, occurrence of abrasion and scratches, and releasability have been obtained. The current situation is that there are none.

Further, by achieving an electrophotographic photosensitive member having a high durability and a small scraping amount, the resistance of the surface of the electrophotographic photosensitive member due to adhesion of charging products, paper powder, etc. is lowered, and in particular,
It becomes remarkable under high temperature and high humidity environment. These create a new problem that blurring of streaky images in the rotation direction of the electrophotographic photosensitive member, so-called image deletion occurs.

A highly durable electrophotographic photoreceptor having excellent stability against environmental changes has not yet had sufficient performance.

[0020]

The object of the present invention is to provide novel phenolic compounds and novel resole resins, especially
A novel phenolic compound that can impart excellent characteristics (surface characteristics) to electrophotographic photoreceptors, such as improved durability against abrasion and scratches, reduction of residual potential rise and potential fluctuation, and retention of high-quality image for a long period of time. And to provide a novel resol resin and a cured product thereof.

An object of the present invention is to provide an electrophotographic photoreceptor containing the above novel phenol compound or novel resole resin in the surface layer, that is, high durability against abrasion and scratches, and increase in residual potential and potential. An electrophotographic photoconductor that has a small fluctuation and can maintain high-quality images for a long time, and does not cause image deletion even when used for a long time under high temperature and high humidity, even in an electrophotographic photoconductor that has been made highly durable. ,
Another object of the present invention is to provide a process cartridge having the electrophotographic photosensitive member and an electrophotographic apparatus.

[0022]

The present invention is a phenol compound having a substituted hydroxyphenyl group and a charge transporting structure, wherein at least one of the substituted hydroxyphenyl groups has at least one hydroxymethyl group as a substituent. It is a phenol compound characterized by having.

Further, the present invention is a resole resin obtained by reacting a phenol compound having a hydroxyphenyl group and a charge transporting structure with formaldehyde under a basic catalyst, which has a charge transporting structure. Is a resol resin.

Further, the present invention provides a cured product of a phenol compound obtained by curing a phenol compound having a hydroxymethyl group, wherein the phenol compound is a phenol compound having a substituted hydroxyphenyl group and a charge transporting structure. A cured product of a phenolic compound, wherein at least one of the substituted hydroxyphenyl groups has at least one hydroxymethyl group as a substituent.

The present invention also provides a cured product obtained by curing a resol resin, which comprises reacting a phenol compound having a hydroxyphenyl group and a charge transporting structure with formaldehyde under a basic catalyst. The obtained resole resin is a resole resin having a charge transporting structure, which is a cured product of the resole resin.

The present invention further provides an electrophotographic photoreceptor having a photosensitive layer on a support, wherein the surface layer of the electrophotographic photoreceptor is a cured product of a phenol compound having a substituted hydroxyphenyl group and a charge transporting structure. An electrophotographic photoreceptor containing at least one of the substituted hydroxyphenyl groups and having at least one hydroxymethyl group as a substituent.

Further, the present invention provides an electrophotographic photoreceptor having a photosensitive layer on a support, wherein the surface layer of the electrophotographic photoreceptor is prepared by subjecting a phenol compound having a hydroxyphenyl group and a charge transporting structure to a basic catalyst. And a cured product of a resol resin obtained by reacting with formaldehyde, and the resol resin has a charge transporting structure.

Further, according to the present invention, the electrophotographic photosensitive member and at least one device selected from the group consisting of charging means, developing means, transfer means and cleaning means are integrally supported and attached to and detached from the main body of the electrophotographic apparatus. In a flexible process cartridge, the electrophotographic photosensitive member is an electrophotographic photosensitive member having a photosensitive layer on a support, and the surface layer of the electrophotographic photosensitive member has a substituted hydroxyphenyl group and a charge transporting structure. Containing a cured product of a phenolic compound having at least one of the substituted hydroxyphenyl groups,
A process cartridge having at least one hydroxymethyl group as a substituent.

Further, the present invention integrally supports an electrophotographic photosensitive member and at least one device selected from the group consisting of charging means, developing means, transfer means and cleaning means, and is attachable to and detachable from the main body of the electrophotographic apparatus. In a flexible process cartridge, the electrophotographic photosensitive member is an electrophotographic photosensitive member having a photosensitive layer on a support, and the surface layer of the electrophotographic photosensitive member has a hydroxyphenyl group and a charge transporting structure. A process cartridge comprising a cured product of a resole resin obtained by reacting a phenol compound with formaldehyde under a basic catalyst, wherein the resole resin has a charge transporting structure.

The present invention also provides an electrophotographic apparatus having an electrophotographic photoreceptor, a charging means, an exposing means, a developing means and a transferring means, wherein the electrophotographic photoreceptor has a photosensitive layer on a support. And a surface layer of the electrophotographic photosensitive member contains a cured product of a substituted hydroxyphenyl group and a phenol compound having a charge transporting structure, and at least one of the substituted hydroxyphenyl groups is at least 1 as a substituent. The electrophotographic apparatus is characterized by having two hydroxymethyl groups.

The present invention also provides an electrophotographic apparatus having an electrophotographic photoreceptor, a charging means, an exposing means, a developing means and a transferring means, wherein the electrophotographic photoreceptor has a photosensitive layer on a support. And a surface layer of the electrophotographic photosensitive member contains a cured product of a resol resin obtained by reacting a phenol compound having a hydroxyphenyl group and a charge transporting structure with formaldehyde under a basic catalyst, In the electrophotographic device, the resol resin has a charge transporting structure.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below.

The phenol compound having a hydroxyphenyl group and a charge transporting structure is a structure having a charge transporting function such as a triarylamine structure, a stilbene structure, a hydrazone structure, a pyrazoline structure and a triphenylmethane structure (charge transporting structure). And a hydroxyphenyl group in the same molecule. Among the charge transporting structures, a triarylamine structure is preferable.

The novel phenol compound of the present invention is a phenol compound having a hydroxyphenyl group and a charge transporting structure, wherein at least one of the hydroxyphenyl groups has a hydroxyphenyl group having a hydroxymethyl group as a substituent. It is a certain phenol compound (hydroxymethyl group-containing phenol compound).

In the present invention, a hydroxyphenyl group having a substituent is referred to as a substituted hydroxyphenyl group, and among the substituted hydroxyphenyl groups, a group having a hydroxymethyl group as a substituent is a hydroxymethyl group-containing hydroxyphenyl group. Express.

Among the hydroxyphenyl groups (including substituted hydroxyphenyl groups), the so-called p-hydroxyphenyl group in which the bonding position between the phenyl group and the other partial skeleton is the p-position as viewed from the hydroxy group. Is preferred.

Among the hydroxymethyl group-containing hydroxyphenyl groups, a hydroxymethyl group-containing one in which at least one bonding position of the hydroxymethyl group is at the o-position with respect to the hydroxy group in the hydroxymethyl group-containing hydroxyphenyl group. Hydroxyphenyl groups are preferred.

Furthermore, among the novel phenol compounds of the present invention, a hydroxymethyl group-containing phenol compound having a structure represented by one formula selected from the group consisting of the following formulas (1) to (5) is more preferable. preferable.

[0039]

[Outside 51]

(In the formula (1), R ¹¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched.
¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted phenyl group. Ar ¹¹ and Ar ¹² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted 1 group. A valent aromatic heterocyclic group is shown. Ar ¹³ represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group or a substituted or unsubstituted divalent aromatic heterocyclic group. m and n are 0 or 1 each independently. X ^{11 to} X ¹⁴ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{11 to} X ¹⁴ is a hydroxymethyl group. )

[Outside 52]

(In the formula (2), R ²¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched.
r ²¹ and Ar ²² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or
A substituted or unsubstituted monovalent aromatic heterocyclic group is shown. The two benzene rings may jointly form a ring via R ²¹ . p is 0 or 1. X ²¹ and X ²² each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ²¹ and X ²² is a hydroxymethyl group. )

[Outside 53]

(In the formula (3), R ³¹ and R ³² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ³¹ is a substituted or unsubstituted group. An alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic heterocyclic group is shown, which is bonded via R ^31. two benzene rings are two benzene rings linked via a good .R ^{3 2} also form a ring jointly through R ³¹ may form a ring jointly via R ^32.
q and r are 0 or 1 each independently. X ³¹
To X ³⁴ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{31 to} X ³⁴ is a hydroxymethyl group. )

[Outside 54]

[0043] (In the formula ^{(4), R} 41 ~R ⁴³ are each independently of the two bonded through a ^{.R 41} showing a branched divalent may hydrocarbon group having 1 to 8 carbon atoms The benzene rings may form a ring jointly via R ^41. R
Two benzene rings bound via ⁴² may jointly form a ring via R ⁴² . Two benzene rings linked via R ⁴³ may form a ring jointly via R ^43. s, t, and u are 0 or 1 each independently. X ^{41 to} X ⁴⁶ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{41 to} X ⁴⁶ is a hydroxymethyl group. )

[Outside 55]

(In the formula (5), R ⁵² represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Z ⁵¹ ,
Z ^{52 s} are each independently a hydrogen atom, a halogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic heterocyclic group is shown. A benzene ring having a benzene ring and ^{Z 52} having a Z ^{51 may} form a ring jointly via ^{Z 51} or ^{Z 52.} v is 0 or 1. w is 1 to 4
Is an integer. X ^{51, X 52} are each independently represent a hydrogen atom or a hydroxymethyl ^{group, X} 51, X
^At least one of ⁵² is a hydroxymethyl group. ) Further, the novel resol resin of the present invention, as described above,
A resol resin obtained by reacting a phenol compound having a hydroxyphenyl group and a charge transporting structure with formaldehyde under a basic catalyst, which is a resol resin having a charge transporting structure.

As the charge transporting structure, similar to the above-mentioned hydroxymethyl group-containing phenol compound of the present invention, a triarylamine structure, a stilbene structure, a hydrazone structure,
Examples thereof include a structure having a charge transporting function (charge transporting structure) such as a pyrazoline structure and a triphenylmethane structure, and among them, a triarylamine structure is preferable.

The hydroxyphenyl group contained in the phenol compound used as the raw material for the resole resin is preferably p-hydroxyphenyl group.

Further, among the phenol compounds having a hydroxyphenyl group and a charge transporting structure, which are raw materials of the resol resin having a charge transporting structure of the present invention, selected from the group consisting of the following formulas (6) to (10). More preferred is a phenolic resin having a structure represented by the formula:

[0048]

[Outside 56]

(In the formula (6), R ⁶¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched.
⁶² represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted phenyl group. Ar ⁶¹ and Ar ⁶² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted 1 group. A valent aromatic heterocyclic group is shown. Ar ⁶³ represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group or a substituted or unsubstituted divalent aromatic heterocyclic group. m ′ and n ′ are each independently 0 or 1. )

[Outside 57]

(In the formula (7), R ⁷¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched.
r ⁷¹ and Ar ⁷² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or
A substituted or unsubstituted monovalent aromatic heterocyclic group is shown. The two benzene rings may together form a ring via R ⁷¹ . p ′ is 0 or 1. )

[Outside 58]

(In the formula (8), R ⁸¹ and R ⁸² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁸¹ is a substituted or unsubstituted group. An alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic heterocyclic group is shown, which is bonded via R ^81. two benzene rings are two benzene rings linked via a good .R ^{8 2} also form a ring jointly through R ⁸¹ may form a ring jointly via R ^82.
q'and r'are 0 or 1 each independently. )

[Outside 59]

[0052] (In the formula ^{(9), R} 91 ~R ⁹³ are each independently a C1-8 branched two linked via ^{.R 91} showing also be divalent hydrocarbon group of The benzene rings may form a ring jointly via R ^91. R
Two benzene rings bound via ⁹² may jointly form a ring via R ⁹² . Two benzene rings linked via R ⁹³ may form a ring jointly via R ^93. s ', t', and u'are 0 or 1 each independently. )

[Outside 60]

(In the formula (10), R ¹⁰² represents 1 to 1 carbon atoms.
8 represents an optionally branched divalent hydrocarbon group. Z
¹⁰¹ and Z ¹⁰² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted group. Or, it represents an unsubstituted monovalent aromatic heterocyclic group. Benzene ring having Z ¹⁰¹ and Z
^The benzene ring having ¹⁰² is Z ¹⁰¹ or Z ¹⁰²
You may form a ring jointly through. v'is 0 or 1
Is. w ′ is an integer of 1 to 4. ) Next, structures of the substituents and the like in the above formulas (1) to (10) will be described.

Examples of the branched divalent hydrocarbon group having 1 to 8 carbon atoms include methylene group, ethylene group, propylene group and butylene group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group and a naphthylmethyl group. Examples of the monovalent aromatic hydrocarbon ring group include a phenyl group, a naphthyl group, an anthryl group and a pyrenyl group. Examples of the monovalent aromatic heterocyclic group include a pyridyl group, a thienyl group, a furyl group and a quinolyl group. Examples of the divalent aromatic hydrocarbon ring group include a phenylene group, a naphthylene group, an anthrylene group and a pyrenylene group. As the divalent aromatic heterocyclic group,
Examples thereof include a pyridylene group and a thienylene group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Also, the above Z ⁵¹
A benzene ring having Z and a benzene ring having Z ⁵² are
⁵¹ or Z ⁵² may jointly form a ring,
Specific examples of the ring include cyclic structures such as a fluorene skeleton and a dihydrophenanthrene skeleton.

The substituent which each of the above groups may have is as follows:
Alkyl group such as methyl group, ethyl group, propyl group and butyl group, aralkyl group such as benzyl group, phenethyl group and naphthylmethyl group, phenyl group, naphthyl group, anthryl group, pyrenyl group, fluorenyl group, carbazolyl group, dibenzofuryl group Group and monovalent aromatic hydrocarbon ring group such as dibenzothiophenyl group, methoxy group,
Examples thereof include alkoxy groups such as ethoxy group and propoxy group, aryloxy groups such as phenoxy group and naphthoxy group, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, nitro group, cyano group and the like.

The hydroxymethyl group-containing phenol compound of the present invention is prepared by reacting a phenol compound having a hydroxyphenyl group and a charge transporting structure with formaldehyde in the presence of a basic catalyst to give one or more hydroxyphenyl groups to the phenol compound. It is obtained by introducing a hydroxymethyl group.

The molar ratio of the phenol compound having a hydroxyphenyl group and the charge transporting structure to formaldehyde is preferably 1: 2 to 1:30, and more preferably 1: 6 to 1:18 from the viewpoint of yield. .

The reaction temperature is preferably 0 to 80 ° C, more preferably 10 to 60 ° C. If it is less than 0 ° C, the reaction is slow, and if it exceeds 80 ° C, gelation may occur. Although the reaction time varies depending on the reaction temperature, for example, in the case of 40 ° C., it is preferably 4 hours to 10 days, further 12 hours to
Five days is preferred.

The reaction between the phenol compound and formaldehyde usually occurs predominantly at the o-position and the p-position of the hydroxyphenyl group, but when the hydroxyphenyl group is a p-hydroxyphenyl group, the formaldehyde source is used. The addition of the hydroxymethyl group of is often at the o-position. However, m-
It may be added to the rank.

Further, the resole resin having a charge transporting structure of the present invention can be obtained by the same method as in the synthesis of the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention described above.

In the present invention, the resole resin means that the degree of introduction of hydroxymethyl groups and the intermolecular condensation product are appropriately set by controlling the hydroxymethylation reaction arbitrarily.
A mixture in which the mixing ratio and molecular weight distribution of hydroxymethyl groups are freely changed. Thus, intentionally or unintentionally, not only monomers but also oligomeric bodies are included and have a broader composition than phenolic compounds.

The resole resin may include not only a monomer structure but also oligomers such as dimers and trimers as exemplified later. Depending on the reaction conditions, the hydroxymethyl group generated during the hydroxymethylation reaction may undergo dehydration, condensation such as deformaldehyde, or addition reaction at the hydroxymethyl groups or at other sites on the hydroxyphenyl group during the reaction. By causing this, a bond between molecules is generated and oligomerization occurs.

The preferable molar ratio of the phenol compound having a hydroxyphenyl group and a charge transporting structure to formaldehyde is the same as in the case of the above-mentioned synthesis of the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention. Is.

The amount of the basic catalyst used is preferably 5 to 300 mol% with respect to the phenol compound having a hydroxyphenyl group and a charge transporting structure. These basic catalysts also have a function of dissolving a phenol compound having a hydroxyphenyl group and a charge transporting structure in an aqueous reaction solvent, and thus may be appropriately increased or decreased depending on the solvent used.

The reaction temperature is preferably 0 to 80 ° C, more preferably 10 to 60 ° C. If the temperature is lower than 0 ° C, the rate of the condensation reaction becomes slow, and if the temperature exceeds 80 ° C, gelation may occur. Although the reaction time varies depending on the reaction temperature, for example,
In the case of 50 ° C, 2 hours to 5 days is preferable. in this case,
If the reaction time is too long, gelation may occur.
Further, the resole resin having a charge transporting structure of the present invention may include a product obtained by oligomerizing the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention by condensation of a hydroxymethyl group or the like. .

As for formaldehyde used in synthesizing the hydroxymethyl group-containing phenol compound having a charge transporting structure or the resol resin having a charge transporting structure of the present invention, either formalin or paraformaldehyde may be used. .

The basic catalyst used in synthesizing the hydroxymethyl group-containing phenol compound having a charge transporting structure and the resol resin having a charge transporting structure of the present invention may be any of known organic bases and inorganic bases. You may use the thing.

Examples of the organic basic catalyst include amines such as ammonia (water), tetramethylammonium hydroxide, tetraethylammonium hydroxide, triethylamine, diethylamine, monoethylamine, trimethylamine, dimethylamine, monomethylamine, morpholine and N-methylmorpholine. A catalyst is preferable, and a tertiary alkylamine is particularly preferable.

The inorganic basic catalyst is preferably a catalyst containing an alkali metal or alkaline earth metal such as sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide.

The cured product of the phenol compound and the cured product of the resole compound of the present invention have the same meaning as a general cured product, that is, a monomer or an oligomer causes a reaction such as condensation or addition with a functional group, It is a state in which a polymer network is formed three-dimensionally, and it can be considered that the polymer is cured by becoming insoluble in a solvent that can be dissolved before curing.

When the hydroxymethyl group-containing phenol compound having a charge-transporting structure or the resol resin having a charge-transporting structure of the present invention is used in the surface layer of an electrophotographic photosensitive member, a curable composition obtained from the phenol compound is used. When the basic catalyst and the salt produced by neutralizing the basic catalyst remain, the resistance of the cured composition decreases, and the image quality of an electrophotographic image may deteriorate particularly under high temperature and high humidity.

Therefore, it is preferable to go through the step of removing the basic catalyst after obtaining the hydroxymethyl group-containing phenol compound having a charge transporting structure and the resol resin having a charge transporting structure of the present invention.

The basic catalyst is preferably neutralized with an acid after the reaction, and the acid used is an inorganic acid such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, benzenesulfonic acid, p-
Either an organic acid such as toluene sulfonic acid or acetic acid may be used. Furthermore, it is preferable to remove the salt generated by this neutralization step by repeating washing with water.

When the basic catalyst is an amine catalyst,
After completion of the reaction, it can be removed under reduced pressure. At that time, the tertiary amines can be most easily removed.

If the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention has crystallinity, the catalyst can be removed by providing general purification steps such as recrystallization and reprecipitation. .

Next, a specific example of the hydroxyphenyl group-containing phenol compound having a charge transporting structure and the phenol compound having a charge transporting structure used for obtaining the resole resin having a charge transporting structure of the present invention will be described. An example is shown below. However, the present invention is not limited to these specific examples.

[0077]

[Outside 61]

[0078]

[Outside 62]

[0079]

[Outside 63]

[0080]

[Outside 64]

[0081]

[Outside 65]

[0082]

[Outside 66]

[0083]

[Outside 67]

[0084]

[Outside 68]

[0085]

[Outside 69]

Specific examples of the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention are shown below. However, the present invention is not limited to these specific examples.

[0087]

[Outside 70]

[0088]

[Outside 71]

The above specific example is an example in which all of the o-positions of the hydroxy group are substituted with hydroxymethyl groups, but in the present invention, at least one of the hydroxyphenyl groups is a substituted hydroxy group having a hydroxymethyl group as a substituent. Any phenyl group will do. A mixture of hydroxymethyl groups having different substitution numbers is also included in the phenol compound of the present invention.

Next, as the putative structure of the oligomer contained in the resol resin having the charge transporting structure of the present invention,
An example of one synthesized using the above (P-22) as a raw material is shown. However, the present invention is not limited to these examples.

[0091]

[Outside 72]

[0092]

[Outside 73]

There are many combinations of the structure of the oligomer body, such as the bonding position, the form of the bond, and the number of connected monomers, and the above-mentioned putative structure is only an example. The resole resin of the present invention is a mixture of such an oligomer and a monomer having a hydroxymethyl group.

In the phenol compound and resol resin of the present invention, the hydroxymethyl groups easily undergo dehydration condensation and deformaldehyde reaction by heating to form a new bond.

Also, a methylene bond is formed by causing a dehydration condensation reaction with the hydrogen atom at the o-position as seen from the hydroxy group of the (mainly) hydroxyphenyl group which has not been substituted with the hydroxymethyl group.

These reactions are modeled as reaction formulas as follows.

[0097]

[Outside 74]

These reactions are reactions that specifically occur when the hydroxyphenyl group is substituted with a hydroxymethyl group, and such curing reaction does not proceed with other substituents.

The curing reaction begins to proceed at a relatively low temperature of around 130 to 160 ° C. The phenol compound of the present invention and the resole resin are diluted with a solvent to form a coating material, and after the coating material is applied on the target surface, the solvent is removed, and the coating material is heated to a temperature at which the curing reaction proceeds with drying, and the coating material is heated with drying It is preferable to carry out curing.

As the putative structure of the cured product of the present invention, an example of a structure obtained by curing a phenol compound or a resole resin synthesized from the above (P-22) as a raw material is shown.
However, the present invention is not limited to this example.

[0101]

[Outside 75]

(In the formula (S-22), M represents a methyl group.) The hydroxymethyl group on the hydroxyphenyl group possessed by the phenol compound has high reactivity such as dehydration, deformaldehyde and addition by heat. It is shown that the intermolecular bond can be easily generated by the presence of the above-mentioned compound to form a three-dimensional cured structure. Curing is accomplished mainly by the reaction of intermolecular hydroxymethyl groups to generate benzyl ether bonds and methylene bonds.

The above formula (S-22) is an estimated structure to the last, and as a matter of course, it may vary depending on the structure such as side reaction and the manufacturing conditions.

The cured product obtained from the phenol compound and the resole resin of the present invention are both of the above formula (S
-22) has a similar structure.

The phenol compound and the resol resin of the present invention can be applied to devices requiring a thin film having a charge transporting function, in addition to the electrophotographic photoreceptor described in detail below. For example, it can be used as a member or a film that requires a charge transport function of a device such as an image sensor, an electroluminescence element, an optical memory, a solar cell, and an electrophotographic plate.

Next, the electrophotographic photosensitive member of the present invention will be described. The following description of the electrophotographic photoreceptor is based on an example using (the cured product of) the phenol compound of the present invention, but the same applies to the case of using (the cured product of) the resol resin of the present invention. is there.

The photosensitive layer of the electrophotographic photosensitive member of the present invention is a single layer type having a charge generating substance and a charge transporting substance in the same layer, a charge generating layer containing the charge generating substance and a charge containing the charge transporting substance. Any of these known configurations, such as a normal layer type in which a transport layer is laminated in this order, an inverse layer type in which a charge transport layer containing a charge transport substance and a charge generating layer containing a charge generating substance are laminated in this order, May be From the viewpoint of electrophotographic characteristics, a forward layer type photosensitive layer is preferable.

However, when the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention is used in the surface layer of an electrophotographic photoreceptor, a high durability effect can be obtained. Used as a material for a protective layer provided on a photosensitive layer having a layer structure such as a mold, a forward layer type, and a reverse layer type, or bound to a charge transport substance for a single layer type photosensitive layer or a forward layer type photosensitive layer. It is preferably used as a material having both functions of a resin, and more preferably used as a protective layer.

In FIG. 1 (a), an electrophotographic photosensitive member comprising a support 4 on which a charge generating layer 3 and a charge transporting layer 2 are provided in this order, and a protective layer 1 is further provided as a surface layer of the electrophotographic photosensitive member. Shows an example of.

As shown in FIGS. 1B and 1C, an intermediate layer 5 and a conductive layer 6 for the purpose of preventing interference fringes are provided between the support 4 and the charge generation layer 3. May be.

When the photosensitive layer is a single-layer type photosensitive layer, it can be provided by forming one layer having a charge generating substance and a charge transporting substance at the same time.

The support of the electrophotographic photosensitive member of the present invention may be any one having conductivity, and those having conductivity itself, such as aluminum, aluminum alloy or stainless steel, can be used. , Aluminum, aluminum alloy or indium oxide
The above-mentioned support or plastic having a layer formed by vacuum deposition of a tin oxide alloy or the like, and conductive particles (for example, carbon black, tin oxide, titanium oxide and silver particles) together with a suitable binder resin on plastic or paper. It is possible to use a support impregnated in the above, a plastic having a conductive binder resin, or the like.

An intermediate layer (adhesive layer) having a barrier function and an adhesive function can be provided between the support and the photosensitive layer. The intermediate layer is for improving the adhesiveness of the photosensitive layer, improving the coatability,
It is formed to protect the support, cover defects in the support, improve charge injection from the support, protect the photosensitive layer against electrical breakdown, and the like. The intermediate layer is casein, polyvinyl alcohol, ethyl cellulose, ethylene-acrylic acid copolymer, polyamide, modified polyamide, polyurethane,
It can be formed of gelatin or aluminum oxide. The thickness of the intermediate layer is preferably 5 μm or less,
3 μm is more preferable.

The charge generating substance used in the electrophotographic photoreceptor of the present invention includes (1) azo pigments such as monoazo, disazo and trisazo (2) phthalocyanine pigments such as metal phthalocyanine and non-metal phthalocyanine (3) indigo and thioindigo Such as indigo pigments (4) perylene pigments such as perylene anhydride and perylene imide (5) polycyclic quinone pigments such as anthraquinone and pyrenequinone (6) squarylium dye (7) pyrylium salts and thiapyrylium salts (8) triphenyl Methane dye (9) Inorganic substances such as selenium, selenium-tellurium and amorphous silicon (10) Quinacridone pigment (11) Azurenium salt pigment (12) Cyanine dye (13) Xanthene dye (14) Quinoneimine dye (15) Styryl dye (15) 16) Cadmium sulfide (17) zinc oxide and the like. Among these, azo pigments, phthalocyanine pigments, perylene pigments, polycyclic quinone pigments and azulenium salt pigments are preferable, and azo pigments and phthalocyanine pigments are more preferable.

Examples of the binder resin used in the charge generating layer include polycarbonate resin, polyester resin, polyarylate resin, butyral resin, polystyrene resin, polyvinyl acetal resin, diallyl phthalate resin, acrylic resin, methacrylic resin, vinyl acetate resin. , Phenol resin, silicone resin, polysulfone resin, styrene-butadiene copolymer resin, alkyd resin, epoxy resin, urea resin and vinyl chloride-vinyl acetate copolymer resin. These are
One kind or two or more kinds can be used as a mixed or copolymer polymer.

The solvent used for the coating liquid for the charge generating layer is selected from the solubility and dispersion stability of the binder resin and the charge generating substance to be used, but as the organic solvent, alcohols, sulfoxides, ketones, Ethers, esters, aliphatic halogenated hydrocarbons, aromatic compounds and the like can be used.

The charge generation layer contains 0.3% of the above charge generation material.
It is formed by sufficiently dispersing it with a binder resin and a solvent in an amount of up to 4 times by a method such as a homogenizer, ultrasonic wave, ball mill, sand mill, attritor or roll mill, coating and drying. The thickness of the charge generation layer is preferably 5 μm or less, and particularly preferably 0.01 to 1 μm.

Further, various sensitizers, antioxidants, ultraviolet absorbers, plasticizers and known charge generating substances can be added to the charge generating layer as required.

Examples of the charge transport material used in the electrophotographic photoreceptor of the present invention include triarylamine compounds, hydrazone compounds, styryl compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds and triarylmethane compounds. .

As the binder resin used for the charge transport layer, polyacrylic ester resin, polystyrene resin,
Preferred are polyester resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyphenylene oxide resin, epoxy resin, polyurethane resin, alkyd resin and unsaturated resin. Particularly preferable resins include polymethyl methacrylate resin, polystyrene resin, styrene-acrylonitrile copolymer resin, polycarbonate resin and diallyl phthalate resin.

The charge transport layer is generally formed by dissolving the above charge transport substance and the binder resin in a solvent and coating the solution. The mixing ratio of the charge transport material and the binder resin is preferably 2: 1 to 1: 2.

As the solvent used for the coating liquid for the charge transport layer, ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, ethers such as dimethoxymethane, tetrahydrofuran and dioxane, toluene and xylene, etc. Aromatic hydrocarbons, chlorinated hydrocarbons such as chlorobenzene, dichloromethane, chloroform and carbon tetrachloride are used.

When applying this solution, a coating method such as a dip coating method, a spray coating method or a spinner coating method can be used. Further, the drying is preferably 10 ° C to 200 ° C.
C., more preferably 20.degree. C. to 150.degree. C., preferably 5 minutes to 5 hours, more preferably 10 minutes to 2 hours under blast drying, static drying or vacuum drying. it can. The charge transport layer is electrically connected to the charge generation layer, receives charge carriers injected from the charge generation layer in the presence of an electric field, and
It has a function of transporting these charge carriers to the interface on the surface side. Since this charge transport layer has a limit of transporting charge carriers, it is not preferable to make the film thickness unnecessarily thick. The thickness of the charge transport layer is preferably 5 to 40 μm, and particularly preferably 7 to 30 μm.

When the hydroxymethyl group-containing phenol compound having a charge-transporting structure of the present invention is used in the charge-transporting layer, it can be used in place of the charge-transporting substance and the binder resin. Since the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention has both the function as a charge transporting substance and the function as a binder resin by itself, the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention is used. Even if only the compound is dissolved in a solvent to form a charge transport layer coating liquid and the charge transport layer is formed, the compound has a function as an electrophotographic photoreceptor. If necessary, the hydroxymethyl group-containing phenol compound having a charge-transporting structure of the present invention may be mixed with the charge-transporting substance or the binder resin.

When the hydroxymethyl group-containing phenol compound having a charge-transporting structure of the present invention is used in the charge-transporting layer, solvents such as methanol, ethanol, propanol and butanol alcohols, acetone and methyl ethyl ketone ketones, Esters such as methyl acetate, ethyl acetate and butyl acetate, ethers such as dimethoxymethane, tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as chlorobenzene, chloroform and carbon tetrachloride. Is mentioned.

When applying the coating liquid for charge transport layer, the same coating method as described above can be used. The drying is preferably performed at a temperature in the range of 10 ° C to 200 ° C, more preferably 20 ° C to 180 ° C, preferably 5 ° C.
It can be performed under blast drying, static drying or vacuum drying for a time in the range of minutes to 5 hours, more preferably 10 minutes to 2 hours.

The phenol compound of the present invention preferably undergoes a thermosetting reaction simultaneously with the removal of the solvent in the drying step after coating the charge transport layer.

The hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention is crosslinked and three-dimensionally cured mainly by causing a condensation reaction of the hydroxymethyl group under the drying condition after coating. As a result, the strength of the film is improved and high durability can be imparted.

When the charge transport layer is the surface layer of the electrophotographic photosensitive member, in addition to the hydroxymethyl group-containing phenol compound having the charge transporting structure of the present invention, the durability of the electrophotographic photosensitive member, slipperiness, toner In order to improve transferability and the like, fluorine atom-containing resin particles such as tetrafluoroethylene resin and vinylidene fluoride resin, lubricant particles such as silicone resin particles, silica particles and alumina particles may be dispersed and contained.

Further, an antioxidant, an ultraviolet absorber, a plasticizer and a known charge transporting substance can be added to the charge transporting layer as required.

When the charge transport layer is the surface layer of an electrophotographic photoreceptor, the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention is used in an amount of 1 to 100 with respect to the total mass of the charge transport layer. It is preferably mass%, and more preferably 50 to 95 mass%.

When the photosensitive layer is of a single layer type, the above charge generating substance and the above charge transporting substance are mixed at an arbitrary ratio, and the binder resin used in the above charge generating layer or the above charge transporting layer is used together, Is dissolved in a solvent and applied to form. The mixing ratio of the combination of the charge generating substance and the charge transporting substance and the binder resin is preferably 3: 1 to 1: 3.

As the solvent for the coating liquid for a single-layer type photosensitive layer, the same solvent as used for forming the above-mentioned charge generation layer or the above charge transport layer can be used.

When applying the single-layer type photosensitive layer coating liquid,
The same coating method as described above can be used. The drying is preferably performed at a temperature in the range of 10 ° C to 200 ° C, more preferably 20 ° C to 180 ° C, preferably 5 ° C.
It can be performed under blast drying, static drying or vacuum drying for a time in the range of minutes to 5 hours, more preferably 10 minutes to 2 hours.

The phenol compound of the present invention is preferably subjected to a thermosetting reaction simultaneously with the removal of the solvent in the drying step after coating the single-layer type photosensitive layer.

Even in the single-layer type photosensitive layer, there is a limit to the transport of charge carriers, so that the film thickness cannot be increased more than necessary. The thickness of the single-layer type photosensitive layer is preferably 5 to 40 μm, and particularly preferably 7 to 30 μm.

When the hydroxymethyl group-containing phenol compound having a charge-transporting structure of the present invention is used in the single-layer type photosensitive layer, instead of the charge-transporting substance or the binder resin, as in the case of using it in the charge-transporting layer. To use. The hydroxymethyl group-containing phenol compound having a charge-transporting structure of the present invention has both a charge-transporting function and a function as a binder resin, so that a single-layer type photosensitive layer can be formed without mixing another resin. can do.

However, similarly to the above, if necessary, the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention and the above charge transporting substance or the above binder resin may be mixed and used. Other conditions are the same as in the case of forming the charge transport layer.

Even in the case of a single-layer type photosensitive layer, in order to improve the durability, slipperiness and toner transferability of the electrophotographic photoreceptor, a fluorine atom-containing tetrafluoroethylene resin, vinylidene fluoride resin or the like is contained. Lubricant particles such as resin particles, silicone resin particles, silica particles and alumina particles may be dispersed and contained.

Further, an antioxidant, an ultraviolet absorber, a plasticizer and a known charge transporting substance may be added to the photosensitive layer if necessary.

When the single-layer type photosensitive layer is the surface layer of an electrophotographic photosensitive member, the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention is added to the total weight of the single-layer type photosensitive layer. 1 to 95% by mass, more preferably 10 to 90% by mass.

When the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention is used by being incorporated in the protective layer, the hydroxymethyl group containing phenol compound having a charge transporting structure of the present invention is contained on the photosensitive layer. The protective layer can be provided by applying the protective layer coating liquid, and curing and drying.

The protective layer containing the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention is
Since it is a three-dimensionally crosslinked cured film, sufficient durability can be achieved even with a relatively thin film thickness. Further, since the obtained curable protective layer has a charge transporting function, there is almost no increase in residual potential and potential fluctuation during durable use, which are observed when a conventional protective layer is provided, and stable image quality can be obtained over a long period of time. It is possible to provide an electrophotographic photosensitive member that does not cause image deletion even when used for a long time under high temperature and high humidity.

When the surface layer of the electrophotographic photoreceptor of the present invention is a protective layer, the protective layer coating solution obtained by dissolving or diluting the phenol compound of the present invention with a solvent is applied onto the photosensitive layer. After molding and coating, a polymerization reaction occurs to form a curable protective layer.

As the solvent for preparing the protective layer coating solution,
When the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention is sufficiently dissolved and lubricating particles or the like are used, its dispersibility is required to be good. Furthermore, it must be a solvent that does not adversely affect the photosensitive layer that comes into contact with the protective layer coating liquid.

Therefore, as the solvent, methanol,
Alcohols such as ethanol and 2-propanol, ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate, ethyl acetate and butyl acetate, ethers such as dimethoxymethane, tetrahydrofuran and dioxane, aromatic carbonization such as toluene and xylene. Hydrogen, halogen-based hydrocarbons such as chlorobenzene and dichloromethane are preferable, and these may be used as a mixture. Among these, as a solvent showing good solubility for the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention and having no adverse effect on the photosensitive layer which is the base during coating, methanol, ethanol And alcohols such as 2-propanol are more preferred.

In addition to the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention, the protective layer of the electrophotographic photosensitive member of the present invention may be a known phenol resin or charge transporting agent for improving the strength of the protective layer. You may mix and use the other resin used when forming a layer. As the phenolic resin, any known resin such as novolac resin and resol resin may be mixed. In order to improve the characteristics of the protective layer, known charge transporting substances may be mixed and used in addition to the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention.

In addition to the hydroxymethyl group-containing phenol compound having a charge-transporting structure of the present invention, a known charge-transporting substance may be used in the protective layer. The charge-transporting substance that can be used in this case can be the one used in forming the photosensitive layer.

As the method for applying the protective layer of the electrophotographic photosensitive member of the present invention, general coating methods such as dip coating method, spray coating method, spinner coating method, roller coating method, Mayer bar coating method and blade coating method are used. Any method can be used.

The thickness of the protective layer is preferably 0.1 μm to 10 μm, and more preferably 0.5 μm to 7 μm.

Fluorine atom-containing resin particles such as tetrafluoroethylene resin and vinylidene fluoride resin, and silicone resin are also used for the protective layer in order to improve the durability, slipperiness and toner transferability of the electrophotographic photoreceptor. Lubricant particles such as particles, silica particles and alumina particles may be dispersed and contained.

In the present invention, in order to prevent deterioration of the surface layer of the electrophotographic photosensitive member due to adhesion of active substances such as ozone and nitrogen oxides generated during charging, an antioxidant or the like is used. Additives may be added.

When the protective layer is the surface layer of the electrophotographic photosensitive member, the hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention is contained in an amount of 10 to 100% by mass based on the total mass of the protective layer. And more preferably 50 to 100% by mass.

FIG. 2 shows a schematic structure of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.

In FIG. 2, reference numeral 11 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around the shaft 12 in the direction of the arrow at a predetermined peripheral speed. In the rotating process, the electrophotographic photosensitive member 11 is uniformly charged to its peripheral surface by a (primary) charging unit 13 at a predetermined positive or negative potential, and then exposed to an exposing unit (not shown) such as slit exposure or laser beam scanning exposure. ), The exposure light 14 intensity-modulated corresponding to the time-series electric digital image signal of the target image information output from
Receive. Thus, with respect to the peripheral surface of the electrophotographic photosensitive member 11,
An electrostatic latent image corresponding to the target image information is sequentially formed.

The formed electrostatic latent image is then subjected to toner development by the developing means 15, and the electrophotographic photosensitive body 1 is provided between the electrophotographic photosensitive body 11 and the transfer means 16 from a paper feeding portion (not shown).
The transfer material 17 that is taken out and fed in synchronization with the rotation of 1.
Then, the toner images formed and carried on the surface of the electrophotographic photosensitive member 11 are sequentially transferred by the transfer unit 16.

The transfer material 17 that has received the transfer of the toner image is
An image formed article (print, print, etc.) is separated from the surface of the electrophotographic photosensitive member and introduced into the fixing unit 18 to undergo image fixing.
It is printed out as a copy) outside the device.

The surface of the electrophotographic photosensitive member 11 after the image transfer is
The cleaning unit 19 removes the residual toner after transfer to make it a clean surface, and the charge is removed by pre-exposure light 20 from a pre-exposure unit (not shown), and then repeatedly used for image formation.

If the charging means 13 is a contact charging means using a charging roller or the like, pre-exposure is not always necessary. Further, a cleanerless process may be used in an apparatus having a structure for recycling the transfer residual toner.

In the present invention, among the components such as the electrophotographic photoreceptor 11, the charging unit 13, the developing unit 15, the transfer unit 16 and the cleaning unit 19 described above, a plurality of components are housed in a container and integrated as a process cartridge. Alternatively, the process cartridge may be configured so as to be attached to and detached from the main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. For example, the charging unit 13,
At least one of the developing means 15 and the cleaning means 19 is integrally supported together with the electrophotographic photosensitive member 11 to form a cartridge, and a process cartridge 21 which is detachable from the apparatus body by using a guide means 22 such as a rail of the apparatus body. can do.

When the electrophotographic apparatus is a copying machine or a printer, the exposure light 14 is reflected light or transmitted light from the original, or the original is read by a sensor and converted into a signal,
Laser beam scanning performed according to this signal,
The light is emitted by driving the LED array or driving the liquid crystal shutter array.

The charging means 13 may be a corona charger, a brush charger, a magnetic brush charger, a blade charger, etc., in addition to the above-mentioned charging roller.

The developing means 15 may be a jumping developing device, a one-component contact developing device, a two-component contact developing device, or the like.

The transfer means 16 may be a roller transfer device, a corona transfer device, a blade transfer device, a belt transfer device or an intermediate transfer member.

The fixing means 18 may be a heat roller fixing device, a heat belt fixing device, a pressure roller fixing device, or the like.

The cleaning means 19 may be blade cleaning, roller cleaning, brush cleaning, suction type cleaning, or the like.

The electrophotographic photoreceptor of the present invention can be used not only in electrophotographic copying machines, but also in laser beam printers, CRT printers, LED printers, FAX machines,
It can be widely applied to electrophotographic application fields such as liquid crystal printers and laser plate making.

[0168]

EXAMPLES The present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to these examples. In addition, "part" in an Example shows a mass part.

<Synthesis Example> A hydroxymethyl group-containing phenol compound having a charge transporting structure of the present invention, and
An example of synthesizing a resol resin having a charge transporting structure will be shown.

(Synthesis Example 1) 50 parts of a phenol compound having a structure represented by the above formula (P-5) was dissolved in 250 parts of an aqueous potassium hydroxide solution (10%) / 200 parts of methanol. To this reaction solution, 150 parts of formalin (37%) was added dropwise over 1 hour while stirring at room temperature. 4 reaction liquids
The mixture was stirred at 5 ° C. for 72 hours.

After completion of the reaction, the product was crystallized by pouring it into an aqueous solution of sulfuric acid for neutralization.

Ethyl acetate was added to the obtained paste-like precipitate to dissolve it, and the mixture was washed 4 to 5 times with a separating funnel.

Finally, the organic layer was taken out, anhydrous magnesium sulfate was added for dehydration, and the organic layer was concentrated by an evaporator to obtain a crude crystal of the product.

The crude crystals were recrystallized using 40 parts of methanol / 300 parts of diisopropyl ether to obtain the desired product as a white powder. The yield was 70%.

Reversed phase HPLC (column: Shodex C1
8-5B (Showa Denko KK, solvent: methanol / water =
80/20) and GPC (gel permeation chromatography) (column: TOSOHTSK guard column HXL, TSKgelG2000HXL × 2, TS
Kgel G3000HXL x 1 connection (manufactured by Tosoh Corporation,
Purity was measured by solvent: THF). Tetrahydroxymethyl body (having four hydroxymethyl groups)
The content rate was 86%.

(Synthesis Example 2) 50 parts of the phenol compound having the structure represented by the above formula (P-5) was dissolved in 50 parts of ammonia water (28%), 150 parts of methanol and 20 parts of triethylamine. Formalin (37%) 1
After 50 parts of the solution was added dropwise with stirring over 30 minutes, the reaction solution was added to 6 parts.
The mixture was heated to 0 ° C. and reacted for 24 hours with stirring.

After completion of the reaction, the reaction solution was concentrated under reduced pressure.
When the viscosity of the mixture started to increase, 200 parts of methanol / 100 parts of water were added, and the solvent was further removed under reduced pressure. This operation was repeated twice to remove the residual amine catalyst.

After removing the solvent, methanol was added to the viscous resin component to obtain a product as a resole resin varnish having a solid content of 60% by mass. The varnish yield was 77 parts.

The content rates of the monomer and the dimer were measured by the same GPC as used in Synthesis Example 1. As a result, the monomer content was 70% and the dimer content was 24% (using the raw material phenol compound as a structural unit).

(Synthesis Example 3) The above formula (P
Instead of the phenol compound having the structure represented by the formula (5), 50 parts of the phenol compound having the structure represented by the formula (P-15) is added with potassium hydroxide (10%) 15
0 parts and 1000 parts of methanol were mixed. This reaction liquid was heated to 50 ° C. to dissolve the phenol compound, and 75 parts of formalin (37% liquid) was added dropwise over 1 hour.

After the dropping was completed, the reaction was carried out at 50 ° C. for another 50 hours, and the post-treatment was carried out in the same manner as in Synthesis Example 1. The obtained phenol compound was recrystallized in the same manner as in Synthesis Example 1.

That is, recrystallization was performed using 10 parts of methanol / 250 parts of diisopropyl ether to obtain the desired product as a white powder. The yield was 56%.

HPLC similar to that used in Synthesis Example 1
And the purity was measured by GPC. The dihydroxymethyl derivative content was 87%.

(Synthesis Example 4) The above formula (P
-50) In place of the phenol compound having the structure represented by the formula (5), 50 parts of the phenol compound having the structure represented by the formula (P-15) was added to 50 parts of ammonia water (28%).
Parts, 550 parts of methanol and 100 of triethylamine
Part was dissolved. After adding 75 parts of formalin (37%) dropwise with stirring over 30 minutes, the reaction solution was heated to 50 ° C. and reacted for 24 hours while stirring.

A novel resol resin of the present invention was synthesized in the same manner as in Synthesis Example 2 except that the phenol compound having the structure represented by the above formula (P-15) was used instead.

The obtained resol resin was subjected to a step of removing the catalyst under reduced pressure in the same manner as in Synthesis Example 2. Then, methanol was added to obtain a product as a resole resin varnish having a solid content of 60% by mass. The varnish yield was 75 parts.

The content of the monomer and dimer was measured by the same GPC as that used in Synthesis Example 1. As a result, the amount of the monomer was 66% and the amount of the dimer was 28% (using the raw material phenol compound as a structural unit).

(Synthesis Example 5) The above formula (P
Instead of the phenol compound having the structure represented by the formula (5), 50 parts of the phenol compound having the structure represented by the formula (P-22) is added with potassium hydroxide (10%) 25
0 parts and 200 parts of methanol were mixed. Add this reaction mixture to 4
The phenol compound was dissolved by heating to 0 ° C., and 150 parts of formalin (37% liquid) was added dropwise over 1 hour.

After the completion of the dropping, the reaction was carried out at 40 ° C. for a further 36 hours, and the post-treatment was carried out in the same manner as in Synthesis Example 1. The obtained phenol compound was recrystallized in the same manner as in Synthesis Example 1.
Recrystallization was performed using 40 parts of methanol / 320 parts of diisopropyl ether to obtain the desired product as a white powder. The yield was 68%.

HPLC similar to that used in Synthesis Example 1
And the purity was measured by GPC. The tetrahydroxymethyl compound content was 88%.

(Synthesis Example 6) The above formula (P
Instead of the phenol compound having the structure represented by -5), 50 parts of the phenol compound having the structure represented by the above formula (P-22) was added to 50 parts of ammonia water (28%).
Parts, 150 parts of methanol and 20 parts of triethylamine. After adding 150 parts of formalin (37%) dropwise with stirring over 30 minutes, the reaction solution was heated to 50 ° C. and reacted for 24 hours while stirring.

A novel resol resin of the present invention was synthesized in the same manner as in Synthesis Example 2 except for the above.

The obtained resol resin was subjected to a step of removing the catalyst under reduced pressure in the same manner as in Synthesis Example 2. Then, methanol was added to obtain a product as a resole resin varnish having a solid content of 60% by mass. The varnish yield was 76 parts.

The content rates of the monomer and the dimer were measured by the same GPC as used in Synthesis Example 1. As a result, the monomer was 52% and the dimer was 34% (using the raw material phenol compound as a structural unit).

(Synthesis Example 7) The above formula (P
Instead of the phenol compound having the structure represented by the formula (5), 50 parts of the phenol compound having the structure represented by the formula (P-26) is added to 50 parts of ammonia water (28%).
Parts, 250 parts of methanol and 20 parts of triethylamine. After 200 parts of formalin (37%) was added dropwise with stirring over 30 minutes, the reaction solution was heated to 50 ° C. and reacted for 16 hours while stirring.

A novel resol resin of the present invention was synthesized in the same manner as in Synthesis Example 2 except for the above.

The obtained resol resin was subjected to the step of removing the catalyst under reduced pressure in the same manner as in Synthesis Example 2. Then, methanol was added to obtain a product as a resole resin varnish having a solid content of 60% by mass. The varnish yield was 78 parts.

The content rates of the monomer and the dimer were measured by the same GPC as used in Synthesis Example 1. As a result, the monomer content was 46% and the dimer content was 38% (using the raw material phenol compound as a structural unit).

(Synthesis Example 8) The above formula (P
Instead of the phenol compound having the structure represented by the formula (5), 50 parts of the phenol compound having the structure represented by the formula (P-32) was added to 50 parts of ammonia water (28%).
Parts, 450 parts of methanol and 30 parts of triethylamine. After 250 parts of formalin (37%) was added dropwise with stirring for 30 minutes, the reaction solution was heated to 50 ° C. and reacted for 12 hours while stirring.

A resole resin having a charge transporting function was synthesized in the same manner as in Synthesis Example 2 except for the above.

The obtained resol resin was subjected to a step of removing the catalyst under reduced pressure in the same manner as in Synthesis Example 2. Then, methanol was added to obtain a product as a resole resin varnish having a solid content of 60% by mass. The varnish yield was 77 parts.

The content rates of the monomer and the dimer were measured by the same GPC as used in Synthesis Example 1. As a result, the monomer content was 50% and the dimer content was 35% (using the starting phenol compound as a structural unit).

Example 1 Length 357.5 mm, Diameter 3
With a 0 mm aluminum cylinder (JIS A3003 aluminum alloy) as a support, a polyamide resin (trade name: Amilan CM8000, Toray Industries, Inc.)
5% by mass methanol solution (manufactured by K.K.) was applied by a dipping method to form an intermediate layer having a film thickness of 0.5 μm.

Next, it has a structure represented by the following formula as a charge generating substance and has strong peaks at 9.0 ° and 27.1 ° of Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction. 4 parts of an oxytitanium phthalocyanine pigment which is a crystalline form having

[Outer 76]

2 parts of polyvinyl butyral resin (trade name: S-REC BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 110 parts of cyclohexanone were dispersed in a sand mill for 4.5 hours using glass beads having a diameter of 1 mm. Then, it was diluted with 130 parts of ethyl acetate to obtain a coating liquid for the charge generation layer.
This charge generation layer coating liquid was applied onto the above intermediate layer by a dipping method to form a charge generation layer having a thickness of 0.18 μm.

Then, 7.5 parts of a charge transport material having a structure represented by the following formula:

[Outside 77]

10 parts of bisphenol Z type polycarbonate (trade name: Iupilon Z-200, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 60 parts of monochlorobenzene / 20 parts of dimethoxymethane. This solution is applied onto the charge generation layer by dip coating, dried at 110 ° C. for 1 hour with hot air,
A charge transport layer having a film thickness of 17 μm was formed.

Next, as a protective layer, 30 parts of a hydroxymethyl group-containing phenol compound having a charge transporting structure obtained in Synthesis Example 1 and 70 parts of ethanol were mixed, and 2
The mixture was stirred and dissolved for a period of time to obtain a coating liquid for protective layer. Using this coating liquid for protective layer, a film was formed on the above charge transport layer by a dip coating method and then dried with hot air at 145 ° C. for 1 hour to form a protective layer having a thickness of 3 μm.

The coatability of the protective layer coating solution was good, and the protective layer formed was a uniform and uniform film.

For evaluation of the curability of the formed protective layer,
Methyl ethyl ketone was soaked in a paper wiper to be attached to the surface of the film, and the film was observed by rubbing to see how the film melted. As a result, the protective layer cannot be wiped off,
It was found to be completely cured.

The electrophotographic photosensitive member thus produced was placed in an electrophotographic apparatus and evaluated by the method described below.

The electrophotographic characteristics were evaluated by a laser electrostatic transfer type copying machine (trade name: GP-405, Canon Inc.).
It was attached to a modified machine manufactured by M.D.

As the sensitivity, the charging was set so that the dark potential was −700 V, and the amount of light necessary for lowering the potential of −700 V to −200 V was measured by irradiating this with a laser beam having a wavelength of 780 nm. (ΜJ / cm ² )
And Furthermore, the potential when irradiated with a light amount of 20 μJ / cm ² was measured as the residual potential Vr (V).

Further, using the same copying machine, the evaluation of the image output durability of 30,000 sheets was performed, and the image quality was evaluated at the initial stage and after the durability and the amount of abrasion was measured.

In the image quality evaluation, each item of gradation reproducibility before and after displaying a durable image, occurrence of image scratches, occurrence of fog on a white background image, and density change was evaluated.

The abrasion amount was measured from the reduction amount of the total film thickness using an eddy current film thickness measuring instrument manufactured by Fischer GmbH, Germany.

Further, as an evaluation of the potential fluctuation after the durable use, the sensitivity Δ500 and the residual potential Vr were measured after the 30,000 sheets of images were printed and endured.

Durability under high temperature and high humidity As an evaluation of image deletion that occurs during use, the electrophotographic photoreceptor prepared above is mounted on the above copying machine under the environment of 30 ° C./80%, and the same durability is obtained. The test was conducted.

It was observed at which point in the course of the durability test up to 30,000 sheets the image deletion occurred.

The evaluation results are shown in Table 1.

Example 2 The same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, in place of the protective layer of Example 1 as a protective layer, 50 parts (solid content: 60% by mass) of a varnish of the resol resin having the charge transporting structure obtained in Synthesis Example 2 and 50 parts of ethanol were used. Were mixed and stirred for 2 hours to be dissolved to obtain a coating liquid for protective layer. This protective layer coating liquid was formed on the above charge transport layer by a dip coating method in the same manner as in Example 1 and then dried with hot air at 145 ° C. for 1 hour to form a protective layer having a thickness of 3 μm. did. The coating property of the coating liquid for the protective layer is good,
The formed protective layer was a uniform and uniform film.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 3 The same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, instead of the protective layer of Example 1 as a protective layer, 24 parts of the hydroxymethyl group-containing phenol compound having a charge transporting structure obtained in Synthesis Example 3 and a resol type phenol resin (trade name: PL -4852, Gunei Chemical Industry Co., Ltd. 10 parts (solid content: 60 mass%) and ethanol 66 parts were mixed and stirred for 2 hours to be dissolved to obtain a protective layer coating liquid. This protective layer coating liquid was formed on the above charge transport layer by a dip coating method in the same manner as in Example 1 and then dried with hot air at 145 ° C. for 1 hour to give a film thickness of 3 μm.
To form a protective layer. The coating property of the protective layer coating solution was good, and the formed protective layer was a uniform and uniform film.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 4) The same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, in place of the protective layer of Example 1 as the protective layer, 40 parts (solid content: 60% by mass) of the varnish of the resol resin having the charge transporting structure obtained in Synthesis Example 4, and the resol type phenol. Resin (trade name: PL-4852, manufactured by Gunei Chemical Industry Co., Ltd.) 10 parts (solid content: 60% by mass) and ethanol 50 parts are mixed and stirred for 2 hours to be dissolved, and a protective layer coating solution. And This protective layer coating solution was applied onto the above charge transport layer by a dip coating method in the same manner as in Example 1.
After forming the film, it was dried with hot air at 145 ° C. for 1 hour to form a protective layer having a film thickness of 3 μm. The coating property of the protective layer coating solution was good, and the formed protective layer was a uniform and uniform film.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 5 The same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, instead of the protective layer of Example 1 as a protective layer, 30 parts of the hydroxymethyl group-containing phenol compound having a charge transporting structure obtained in Synthesis Example 5 and 70 parts of ethanol were mixed, and the mixture was mixed for 2 hours. The mixture was stirred and dissolved to obtain a coating liquid for protective layer. This protective layer coating liquid was formed on the above charge transport layer by a dip coating method in the same manner as in Example 1 and then dried with hot air at 145 ° C. for 1 hour to form a protective layer having a thickness of 3 μm. did. The coating property of the protective layer coating solution was good, and the formed protective layer was a uniform and uniform film.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 6) On the same aluminum cylinder as in Example 1, the same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated.

Next, in place of the protective layer of Example 1 as the protective layer, 50 parts (solid content: 60% by mass) of varnish of the resole resin having the charge transporting structure obtained in Synthesis Example 6 and 50 parts of ethanol were used. And stir for 2 hours to dissolve,
The coating liquid for the protective layer was used. This coating liquid for protective layer was used in Example 1
In the same manner as above, a film was formed on the charge transport layer by a dip coating method, and then dried with hot air at 145 ° C. for 1 hour to give a film thickness of 3 μm.
m protective layer was formed. The coating property of the protective layer coating solution was good, and the formed protective layer was a uniform and uniform film.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 7 The same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, as the protective layer, instead of the protective layer of Example 1, 50 parts (solid content: 60% by mass) of a varnish of the resol resin having the charge transporting structure obtained in Synthesis Example 7 and 50 parts of ethanol. And stir for 2 hours to dissolve,
The coating liquid for the protective layer was used. This coating liquid for protective layer was used in Example 1
In the same manner as above, a film was formed on the charge transport layer by a dip coating method, and then dried with hot air at 145 ° C. for 1 hour to give a film thickness of 3 μm.
m protective layer was formed. The coating property of the protective layer coating solution was good, and the formed protective layer was a uniform and uniform film.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 8 The same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, instead of the protective layer of Example 1 as a protective layer, 50 parts (solid content: 60% by mass) of the varnish of the resol resin having the charge transporting structure obtained in Synthesis Example 8 and ethanol 50 were used. The parts were mixed and stirred for 2 hours to be dissolved to obtain a coating liquid for protective layer. This protective layer coating solution was applied onto the above charge transport layer by a dip coating method in the same manner as in Example 1.
After forming the film, it was dried with hot air at 145 ° C. for 1 hour to form a protective layer having a film thickness of 3 μm. The coating property of the protective layer coating solution was good, and the formed protective layer was a uniform and uniform film.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 9 The same intermediate layer and charge generation layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, instead of the charge transport layer of Example 1 as the charge transport layer, the hydroxymethyl group-containing phenol compound 12.5 having the charge transporting structure obtained in Synthesis Example 3 was obtained.
Part and bisphenol Z type polycarbonate resin (trade name: Iupilon Z-200, manufactured by Mitsubishi Gas Chemical Co., Inc.)
5 parts to 1,4-dioxane 40 parts / dimethoxymethane 3
Dissolved in 2 parts. This solution is applied onto the above charge generation layer by dip coating and dried with hot air at 145 ° C. for 1 hour to give a film thickness of 20 μm.
Was formed on the charge transport layer.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 1 The same intermediate layer and charge generation layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, the charge transport layer coating liquid of Example 1 was applied as a charge transport layer onto the above charge generating layer by dip coating, and 110
It was dried in hot air at 1 ° C. for 1 hour to form a charge transport layer having a thickness of 30 μm.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 2 The same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, as a protective layer, the average particle size is 0.02 μm.
m antimony-doped tin oxide particles (trade name: T-1,
Fluorine atom-containing compound (trade name: LS-1) having a structure represented by the following formula: 100 parts by Mitsubishi Materials Co., Ltd.
090, Shin-Etsu Silicone Co., Ltd. 7 parts

[Outside 78]

50 parts of treated tin oxide particles and 150 parts of ethanol which had been surface-treated with 7% of the surface treatment were dispersed in a sand mill for 60 hours, and then polytetrafluoroethylene particles (average particle size: 0. 20 parts of 18 μm) were added and the mixture was dispersed for 8 hours. Then, 30 parts of an acrylic resin monomer having a structure represented by the following formula,

[Outside 79]

As a photopolymerization initiator, 2 parts of 2-methylthioxanthone was added and dissolved to prepare a coating liquid for protective layer.

This protective layer coating solution is applied onto the above charge transport layer by dip coating to form a film.
Photocuring was performed for 60 seconds at a light intensity of 0 mW / cm ² , and then dried with hot air at 120 ° C. for 2 hours to form a protective layer having a film thickness of 3 μm.

An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except for the above. The evaluation results are shown in Table 1.

Comparative Example 3 The same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, as a protective layer, a resol type phenol resin (trade name: PL-4852, Gunei Chemical Industry Co., Ltd.)
Made by mixing 50 parts (solid content: 60% by mass) / ethanol 50 parts as a coating solution for the protective layer by dip coating on the charge transport layer, followed by hot air drying at 145 ° C. for 1 hour to obtain a film thickness. Formed a protective layer having a thickness of 3 μm.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1. Since this electrophotographic photosensitive member has low sensitivity and high residual potential, the image density cannot be obtained and the electrophotographic photosensitive member is not at a level capable of a durability test by image formation.

Comparative Example 4 The same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, a phenol compound 30 having a structure represented by the following formula as a protective layer and having no charge transport function is provided.
Department

[Outside 80]

A solution prepared by mixing 70 parts of ethanol was used as a coating solution for protective layer and was applied onto the above charge transport layer by dip coating.
It was dried with hot air at 5 ° C. for 1 hour to form a protective layer having a film thickness of 3 μm.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Since the electrophotographic photosensitive member had a very high residual potential, the image density could not be obtained, and the durability test by image output was not at a level.

(Comparative Example 5) On the same aluminum cylinder as in Example 1, the same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated.

Next, a solution prepared by mixing 30 parts of a phenol compound having the structure represented by the above formula (P-22) / 70 parts of methanol was used as a coating solution, and was applied on the above charge transport layer by dip coating at 145 ° C. It was dried with hot air for 1 hour to form a protective layer having a film thickness of 3 μm.

For evaluation of the curability of the formed layer, a paper wiper was impregnated with methyl ethyl ketone, adhered onto the surface of the film, and rubbed to observe the melting state of the film. As a result, it was found that the film on the charge transport layer could be easily wiped off and was not cured.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Since the surface layer of this electrophotographic photosensitive member was not cured, the surface layer was scraped off immediately after the start of durability,
During durability, the charge transport layer became the outermost layer and was worn.
The durability of 30,000 sheets was not achieved as in Example 1, and the charge transport layer became thin and fell below the usage limit, resulting in poor image output.

(Comparative Example 6) On the same aluminum cylinder as in Example 1, the same intermediate layer, charge generation layer and charge transport layer as in Example 1 were applied.

Next, similar to the protective layer, 30 parts of a phenol compound having a structure represented by the following formula:

[Outside 81]

A solution prepared by mixing 60 parts of methanol and 10 parts of methyl ethyl ketone as a coating solution was applied onto the above charge transport layer by dip coating and dried with hot air at 145 ° C. for 1 hour to give a film thickness of 3
A μm layer was formed.

To evaluate the curability of the formed layer, a paper wiper was impregnated with methyl ethyl ketone, adhered on the surface of the film, and rubbed to observe the melting condition of the film. As a result, it was found that the film on the charge transport layer could be easily wiped off and was not cured.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Since the surface layer of this electrophotographic photosensitive member was not cured, the surface layer was scraped off immediately after the start of durability,
During durability, the charge transport layer became the outermost layer and was worn.
The durability of 30,000 sheets was not achieved as in Example 1, and the charge transport layer became thin and fell below the usage limit, resulting in poor image output.

Comparative Example 7 The same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, similar to the protective layer, 4 parts of a phenol compound having a structure represented by the following formula:

[Outside 82]

A solution prepared by mixing 96 parts of cyclohexanone as a coating solution is spray-coated on the above charge transport layer to give 1
It was dried with hot air at 45 ° C. for 1 hour to form a layer having a film thickness of 3 μm.

To evaluate the curability of the formed layer, a paper wiper was impregnated with methyl ethyl ketone, adhered on the surface of the film, and rubbed to observe the melting condition of the film. As a result, it was found that the film on the charge transport layer could be easily wiped off and was not cured.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Since the surface layer of this electrophotographic photosensitive member was not cured, the surface layer was scraped off immediately after the start of durability,
During durability, the charge transport layer became the outermost layer and was worn.
The durability of 30,000 sheets was not achieved as in Example 1, and the charge transport layer became thin and fell below the usage limit, resulting in poor image output.

(Comparative Example 8) The same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, similar to the protective layer, 30 parts of a phenol compound having a structure represented by the following formula

[Outside 83]

A solution prepared by mixing 70 parts of methanol was used as a coating solution, and was applied on the above charge transport layer by dip coating.
It was dried with hot air for an hour to form a layer having a film thickness of 3 μm.

To evaluate the curability of the formed layer, a paper wiper was impregnated with methyl ethyl ketone, adhered on the surface of the film, and rubbed to observe the melting condition of the film. As a result, it was found that the film on the charge transport layer could be easily wiped off and was not cured.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Since the surface layer of this electrophotographic photosensitive member was not cured, the surface layer was scraped off immediately after the start of durability,
During durability, the charge transport layer became the outermost layer and was worn.
The durability of 30,000 sheets was not achieved as in Example 1, and the charge transport layer became thin and fell below the usage limit, resulting in poor image output.

(Comparative Example 9) The same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, similar to the protective layer, 30 parts of a hydroxymethyl group-containing compound having a structure represented by the following formula:

[Outside 84]

A solution prepared by mixing 70 parts of methanol was used as a coating solution, and was applied on the above charge transport layer by dip coating.
It was dried with hot air for an hour to form a layer having a film thickness of 3 μm.

For evaluation of the curability of the formed layer, a paper wiper was impregnated with methyl ethyl ketone, adhered onto the surface of the film, and rubbed to observe the melting state of the film. As a result, it was found that the film on the charge transport layer could be easily wiped off and was not cured.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Since the surface layer of this electrophotographic photosensitive member was not cured, the surface layer was scraped off immediately after the start of durability,
During durability, the charge transport layer became the outermost layer and was worn.
The durability of 30,000 sheets was not achieved as in Example 1, and the charge transport layer became thin and fell below the usage limit, resulting in poor image output.

(Comparative Example 10) The same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, similar to the protective layer, 30 parts of a hydroxymethyl group-containing compound having a structure represented by the following formula:

[Outside 85]

A solution prepared by mixing 70 parts of methanol was used as a coating solution, and was applied on the above charge transport layer by dip coating.
It was dried with hot air for an hour to form a layer having a film thickness of 3 μm.

To evaluate the curability of the formed layer, a paper wiper was impregnated with methyl ethyl ketone, adhered on the surface of the film, and rubbed to observe the melting state of the film. As a result, it was found that the film on the charge transport layer could be easily wiped off and was not cured.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Since the surface layer of this electrophotographic photosensitive member was not cured, the surface layer was scraped off immediately after the start of durability,
During durability, the charge transport layer became the outermost layer and was worn.
The durability of 30,000 sheets was not achieved as in Example 1, and the charge transport layer became thin and fell below the usage limit, resulting in poor image output.

Comparative Example 11 The same intermediate layer, charge generation layer and charge transport layer as in Example 1 were coated on the same aluminum cylinder as in Example 1.

Next, 3 parts of a phenol compound having the structure represented by the above formula (P-5) and 4 parts of a burette-modified polyisocyanate solution (solid content 67 mass%) having the structure represented by the following formula are added.

[Outside 86]

A solution prepared by dissolving 120 parts of cyclohexanone in the mixture was spray-coated on the charge transport layer as a coating solution, dried at room temperature for 10 minutes, and then dried at 150 ° C. for 1 hour with hot air to give a film thickness of 3 μm. Layers were formed.

For evaluation of the curability of the formed layer, a paper wiper was impregnated with methyl ethyl ketone, adhered on the surface of the film, and rubbed to observe the melting state of the film. As a result, it was found that the film on the charge transport layer was not easily wiped off, and although the film did not reach the surface layer of the electrophotographic photoreceptor of the example, the film was cured to some extent.

This electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[0302]

[Table 1]

[0303]

INDUSTRIAL APPLICABILITY According to the present invention, a novel phenol compound and a novel resol resin, in particular, improved durability against abrasion and scratch generation, reduced residual potential rise and potential fluctuation,
It is possible to provide a novel phenol compound and a novel resole resin, which can impart excellent characteristics (surface characteristics) such as retention of high-quality image quality for a long time to an electrophotographic photoreceptor, and a cured product thereof.

Further, an electrophotographic photoreceptor containing the novel phenol compound or novel resole resin in the surface layer, that is, high durability against abrasion and scratches,
An electrophotographic photosensitive member that has a small residual potential rise and potential fluctuation, can maintain high-quality image for a long period of time, and does not cause image deletion even after long-term use in a high temperature and high humidity environment, and the electrophotographic photosensitive member It is possible to provide a process cartridge and an electrophotographic apparatus having the above.

[Brief description of drawings]

FIG. 1 is a diagram showing a layer structure of an electrophotographic photosensitive member of the present invention.

FIG. 2 is a diagram showing a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

1 protective layer 2 Charge transport layer 3 Charge generation layer 4 support 5 Middle class 6 Conductive layer 11 Electrophotographic photoreceptor 12 axes 13 charging means 14 Exposure means 15 Developing means 16 Transfer means 17 Transfer material 18 Fixing means 19 Cleaning means 20 Pre-exposure means 21 Process cartridge 22 rails

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor ▲ Yoshi ▼ Kimihiro Mura             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Tatsuya Ikezue             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Daisuke Tanaka             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F term (reference) 2H068 AA03 AA13 BA12 BB35 BB49                       FA27                 4H006 AA01 AA03 AB76 AB78 BJ30                       BJ50 BN20 BN30 BP30 BU46                 4J033 CA02 CA14 CA18 CA24 CA25                       CC04 CC07 HA13 HA23 HA28                       HB10

Claims (66)

[Claims] 1. A phenol compound having a substituted hydroxyphenyl group and a charge transporting structure, wherein at least one of the substituted hydroxyphenyl groups has at least one hydroxymethyl group as a substituent. . 2. The phenol compound according to claim 1, wherein at least one of the substituted hydroxyphenyl groups is a substituted p-hydroxyphenyl group. 3. At least one of the hydroxymethyl groups
The phenol compound according to claim 1 or 2, wherein one bonding position is at the o-position with respect to the hydroxy group of the substituted hydroxyphenyl group having the hydroxymethyl group as a substituent. 4. The phenol compound according to claim 1, wherein the charge transporting structure is a triarylamine structure. 5. A structure having a structure represented by one formula selected from the group consisting of the following formulas (1) to (5):
The phenol compound according to any one of 1. [Outer 1] (In the formula (1), R ¹¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. R ¹² represents a hydrogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted phenyl group is shown. Ar ¹¹ and Ar ¹² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group,
Alternatively, it represents a substituted or unsubstituted monovalent aromatic heterocyclic group. Ar ¹³ represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group or a substituted or unsubstituted divalent aromatic heterocyclic group. m and n are each independently 0 or 1
Is. X ^{11 to} X ¹⁴ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{11 to} X ¹⁴ is a hydroxymethyl group. ) [Outer 2] (In the formula (2), R ²¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ²¹ and Ar
²² is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic group. Indicates a heterocyclic group. The two benzene rings may jointly form a ring via R ²¹ . p is 0
Or 1. X ²¹ and X ²² are each independently
A hydrogen atom or a hydroxymethyl group is shown, X ²¹ ,
At least one of X ²² is a hydroxymethyl group. ) [Outside 3] (In the formula (3), R ³¹ and R ³² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ³¹ is a substituted or unsubstituted alkyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted 1
A valent aromatic heterocyclic group is shown. 2 bound through R ³¹
The two benzene rings may jointly form a ring via R ³¹ . Two benzene rings linked via R ^{3 2} is, R
^A ring may be jointly formed through ³² . q and r are 0 or 1 each independently. X ^{31 to} X ³⁴ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{31 to} X ³⁴ is a hydroxymethyl group. ) [Outer 4] (In the formula (4), R ^{41 to} R ⁴³ each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms and which may be branched. Two benzene rings bonded via R ⁴¹ are , R
^A ring may be jointly formed through ⁴¹ . Two benzene rings linked via R ⁴² may form a ring jointly via R ^42. Two benzene rings linked via R ⁴³ may form a ring jointly via R ^43. s,
t and u are 0 or 1 each independently. X ⁴¹
To X ⁴⁶ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{41 to} X ⁴⁶ is a hydroxymethyl group. ) [Outer 5] (In the formula (5), R ⁵² represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Z ⁵¹ and Z ⁵² each independently represent a hydrogen atom, a halogen atom, a substituent or a substituent. An unsubstituted alkyl group, a substituted or unsubstituted aralkyl group,
A substituted or unsubstituted monovalent aromatic hydrocarbon ring group or a substituted or unsubstituted monovalent aromatic heterocyclic group is shown.
A benzene ring having a benzene ring and ^{Z 52} having a Z ^{51 may} form a ring jointly via ^{Z 51} or ^{Z 52.} v is 0 or 1. w is an integer of 1 to 4. X ⁵¹ and X ⁵² each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ⁵¹ and X ⁵² is a hydroxymethyl group. ) 6. A resole resin obtained by reacting a phenol compound having a hydroxyphenyl group and a charge transporting structure with formaldehyde under a basic catalyst, wherein the resole resin has a charge transporting structure. . 7. The resole resin according to claim 6, wherein at least one of the hydroxyphenyl groups is a p-hydroxyphenyl group. 8. The resol resin according to claim 6, wherein the charge transporting structure is a triarylamine structure. 9. The phenol compound having a hydroxyphenyl group and a charge transporting structure is represented by the following formula (6):
The resole resin according to any one of claims 6 to 8, which has a structure represented by one formula selected from the group consisting of (10). [Outside 6] (In the formula (6), R ⁶¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. R ⁶² represents a hydrogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted phenyl group is shown. Ar ⁶¹ and Ar ⁶² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group,
Alternatively, it represents a substituted or unsubstituted monovalent aromatic heterocyclic group. Ar ⁶³ represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group or a substituted or unsubstituted divalent aromatic heterocyclic group. m ′ and n ′ are each independently 0 or 1. ) [Outer 7] (In the formula (7), R ⁷¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁷¹ , Ar
⁷² is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic group. Indicates a heterocyclic group. The two benzene rings may together form a ring via R ⁷¹ . p'is
It is 0 or 1. ) [Outside 8] (In the formula (8), R ⁸¹ and R ⁸² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁸¹ represents a substituted or unsubstituted alkyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted 1
A valent aromatic heterocyclic group is shown. 2 bound via R ⁸¹
The two benzene rings may jointly form a ring via R ⁸¹ . Two benzene rings linked via R ^{8 2} is, R
^A ring may be jointly formed via ⁸² . q'and r'are
Each is independently 0 or 1. ) [Outside 9] (In the formula (9), R ^{91 to} R ⁹³ each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Two benzene rings bonded via R ⁹¹ are , R
^A ring may be jointly formed through ⁹¹ . Two benzene rings linked via R ⁹² may form a ring jointly via R ^92. Two benzene rings linked via R ⁹³ may form a ring jointly via R ^93.
s ', t', and u'are 0 or 1 each independently. ) [Outside 10] (In the formula (10), R ¹⁰² represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Z ¹⁰¹ , Z
¹⁰² are each independently a hydrogen atom, a halogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic heterocyclic group is shown. A benzene ring having a benzene ring and ^{Z 102} having a Z ^{101 may} form a ring jointly via ^{Z 101} or ^{Z 102.} v ′ is 0 or 1.
w ′ is an integer of 1 to 4. ) 10. The resol resin according to claim 6, wherein the basic catalyst is an amine catalyst. 11. The resol resin according to claim 10, wherein the amine catalyst is a tertiary alkylamine. 12. The resol resin according to claim 6, wherein the basic catalyst is a catalyst containing an alkali metal or a catalyst containing an alkaline earth metal. 13. A cured product of a phenol compound obtained by curing a phenol compound having a hydroxymethyl group, wherein the phenol compound is a phenol compound having a substituted hydroxyphenyl group and a charge transporting structure, At least one of the phenyl groups
One has at least one hydroxymethyl group as a substituent, and a cured product of a phenol compound. 14. The cured product of the phenol compound according to claim 13, wherein at least one of the substituted hydroxyphenyl groups is a substituted p-hydroxyphenyl group. 15. The phenol according to claim 13, wherein at least one bonding position of the hydroxymethyl group is o-position to the hydroxy group of the substituted hydroxyphenyl group having the hydroxymethyl group as a substituent. A cured product of a compound. 16. The cured product of the phenol compound according to claim 13, wherein the charge transporting structure is a triarylamine structure. 17. The curing of the phenol compound according to claim 13, wherein the phenol compound has a structure represented by one formula selected from the group consisting of the following formulas (1) to (5). object. [Outside 11] (In the formula (1), R ¹¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. R ¹² represents a hydrogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted phenyl group is shown. Ar ¹¹ and Ar ¹² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group,
Alternatively, it represents a substituted or unsubstituted monovalent aromatic heterocyclic group. Ar ¹³ represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group or a substituted or unsubstituted divalent aromatic heterocyclic group. m and n are each independently 0 or 1
Is. X ^{11 to} X ¹⁴ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{11 to} X ¹⁴ is a hydroxymethyl group. ) [Outside 12] (In the formula (2), R ²¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ²¹ and Ar
²² is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic group. Indicates a heterocyclic group. The two benzene rings may jointly form a ring via R ²¹ . p is 0
Or 1. X ²¹ and X ²² are each independently
A hydrogen atom or a hydroxymethyl group is shown, X ²¹ ,
At least one of X ²² is a hydroxymethyl group. ) [Outside 13] (In the formula (3), R ³¹ and R ³² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ³¹ is a substituted or unsubstituted alkyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted 1
A valent aromatic heterocyclic group is shown. 2 bound through R ³¹
The two benzene rings may jointly form a ring via R ³¹ . Two benzene rings linked via R ^{3 2} is, R
^A ring may be jointly formed through ³² . q and r are 0 or 1 each independently. X ^{31 to} X ³⁴ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{31 to} X ³⁴ is a hydroxymethyl group. ) [Outer 14] (In the formula (4), R ^{41 to} R ⁴³ each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms and which may be branched. Two benzene rings bonded via R ⁴¹ are , R
^A ring may be jointly formed through ⁴¹ . Two benzene rings linked via R ⁴² may form a ring jointly via R ^42. Two benzene rings linked via R ⁴³ may form a ring jointly via R ^43. s,
t and u are 0 or 1 each independently. X ⁴¹
To X ⁴⁶ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{41 to} X ⁴⁶ is a hydroxymethyl group. ) [Outer 15] (In the formula (5), R ⁵² represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Z ⁵¹ and Z ⁵² each independently represent a hydrogen atom, a halogen atom, a substituent or a substituent. An unsubstituted alkyl group, a substituted or unsubstituted aralkyl group,
A substituted or unsubstituted monovalent aromatic hydrocarbon ring group or a substituted or unsubstituted monovalent aromatic heterocyclic group is shown.
A benzene ring having a benzene ring and ^{Z 52} having a Z ^{51 may} form a ring jointly via ^{Z 51} or ^{Z 52.} v is 0 or 1. w is an integer of 1 to 4. X ⁵¹ and X ⁵² each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ⁵¹ and X ⁵² is a hydroxymethyl group. ) 18. A cured product obtained by curing a resol resin, wherein the resol resin is obtained by reacting a phenol compound having a hydroxyphenyl group and a charge transporting structure with formaldehyde under a basic catalyst. A cured product of a resol resin, which is a resol resin having a charge transporting structure. 19. The method according to claim 18, wherein at least one of the hydroxyphenyl groups is a p-hydroxyphenyl group.
A cured product of the resol resin described in 1. 20. The cured product of the resole resin according to claim 18, wherein the charge transporting structure of the resole resin is a triarylamine structure. 21. The phenol compound having a hydroxyphenyl group and a charge transporting structure is represented by the following formula (6):
21. The cured product of the resole resin according to claim 18, which has a structure represented by one formula selected from the group consisting of: [Outside 16] (In the formula (6), R ⁶¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. R ⁶² represents a hydrogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted phenyl group is shown. Ar ⁶¹ and Ar ⁶² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group,
Alternatively, it represents a substituted or unsubstituted monovalent aromatic heterocyclic group. Ar ⁶³ represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group or a substituted or unsubstituted divalent aromatic heterocyclic group. m ′ and n ′ are each independently 0 or 1. ) [Outer 17] (In the formula (7), R ⁷¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁷¹ , Ar
⁷² is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic group. Indicates a heterocyclic group. The two benzene rings may together form a ring via R ⁷¹ . p'is
It is 0 or 1. ) [Outer 18] (In the formula (8), R ⁸¹ and R ⁸² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁸¹ represents a substituted or unsubstituted alkyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted 1
A valent aromatic heterocyclic group is shown. 2 bound via R ⁸¹
The two benzene rings may jointly form a ring via R ⁸¹ . Two benzene rings linked via R ^{8 2} is, R
^A ring may be jointly formed via ⁸² . q'and r'are
Each is independently 0 or 1. ) [Outer 19] (In the formula (9), R ^{91 to} R ⁹³ each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Two benzene rings bonded via R ⁹¹ are , R
^A ring may be jointly formed through ⁹¹ . Two benzene rings linked via R ⁹² may form a ring jointly via R ^92. Two benzene rings linked via R ⁹³ may form a ring jointly via R ^93.
s ', t', and u'are 0 or 1 each independently. ) [Outside 20] (In the formula (10), R ¹⁰² represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Z ¹⁰¹ , Z
¹⁰² are each independently a hydrogen atom, a halogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic heterocyclic group is shown. A benzene ring having a benzene ring and ^{Z 102} having a Z ^{101 may} form a ring jointly via ^{Z 101} or ^{Z 102.} v ′ is 0 or 1.
w ′ is an integer of 1 to 4. ) 22. The cured product of the resole resin according to claim 18, wherein the basic catalyst is an amine catalyst. 23. The cured product of the resole resin according to claim 22, wherein the amine catalyst is a tertiary alkylamine. 24. The cured product of the resole resin according to claim 18, wherein the basic catalyst is a catalyst containing an alkali metal or a catalyst containing an alkaline earth metal. 25. An electrophotographic photosensitive member having a photosensitive layer on a support, wherein the surface layer of the electrophotographic photosensitive member contains a cured product of a substituted hydroxyphenyl group and a phenol compound having a charge transporting structure, An electrophotographic photoreceptor, wherein at least one of the substituted hydroxyphenyl groups has at least one hydroxymethyl group as a substituent. 26. The electrophotographic photosensitive member according to claim 25, wherein at least one of the substituted hydroxyphenyl groups is a substituted p-hydroxyphenyl group. 27. The electron according to claim 25 or 26, wherein at least one bonding position of the hydroxymethyl group is o-position to the hydroxy group of the substituted hydroxyphenyl group having the hydroxymethyl group as a substituent. Photoreceptor. 28. The electrophotographic photosensitive member according to claim 25, wherein the charge transporting structure is a triarylamine structure. 29. The electrophotographic photosensitive member according to claim 25, wherein the phenol compound has a structure represented by one formula selected from the group consisting of the following formulas (1) to (5). . [Outside 21] (In the formula (1), R ¹¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. R ¹² represents a hydrogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted phenyl group is shown. Ar ¹¹ and Ar ¹² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group,
Alternatively, it represents a substituted or unsubstituted monovalent aromatic heterocyclic group. Ar ¹³ represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group or a substituted or unsubstituted divalent aromatic heterocyclic group. m and n are each independently 0 or 1
Is. X ^{11 to} X ¹⁴ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{11 to} X ¹⁴ is a hydroxymethyl group. ) [Outer 22] (In the formula (2), R ²¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ²¹ and Ar
²² is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic group. Indicates a heterocyclic group. The two benzene rings may jointly form a ring via R ²¹ . p is 0
Or 1. X ²¹ and X ²² are each independently
A hydrogen atom or a hydroxymethyl group is shown, X ²¹ ,
At least one of X ²² is a hydroxymethyl group. ) [Outside 23] (In the formula (3), R ³¹ and R ³² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ³¹ is a substituted or unsubstituted alkyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted 1
A valent aromatic heterocyclic group is shown. 2 bound through R ³¹
The two benzene rings may jointly form a ring via R ³¹ . Two benzene rings linked via R ^{3 2} is, R
^A ring may be jointly formed through ³² . q and r are 0 or 1 each independently. X ^{31 to} X ³⁴ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{31 to} X ³⁴ is a hydroxymethyl group. ) [Outer 24] (In the formula (4), R ^{41 to} R ⁴³ each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms and which may be branched. Two benzene rings bonded via R ⁴¹ are , R
^A ring may be jointly formed through ⁴¹ . Two benzene rings linked via R ⁴² may form a ring jointly via R ^42. Two benzene rings linked via R ⁴³ may form a ring jointly via R ^43. s,
t and u are 0 or 1 each independently. X ⁴¹
To X ⁴⁶ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{41 to} X ⁴⁶ is a hydroxymethyl group. ) [Outer 25] (In the formula (5), R ⁵² represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Z ⁵¹ and Z ⁵² each independently represent a hydrogen atom, a halogen atom, a substituent or a substituent. An unsubstituted alkyl group, a substituted or unsubstituted aralkyl group,
A substituted or unsubstituted monovalent aromatic hydrocarbon ring group or a substituted or unsubstituted monovalent aromatic heterocyclic group is shown.
A benzene ring having a benzene ring and ^{Z 52} having a Z ^{51 may} form a ring jointly via ^{Z 51} or ^{Z 52.} v is 0 or 1. w is an integer of 1 to 4. X ⁵¹ and X ⁵² each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ⁵¹ and X ⁵² is a hydroxymethyl group. ) 30. A protective layer is provided on the photosensitive layer, and the surface layer of the electrophotographic photosensitive member is the protective layer.
9. The electrophotographic photosensitive member according to any one of 9. 31. In an electrophotographic photoreceptor having a photosensitive layer on a support, the surface layer of the electrophotographic photoreceptor reacts a phenol compound having a hydroxyphenyl group and a charge transporting structure with formaldehyde under a basic catalyst. An electrophotographic photoreceptor containing a cured product of a resol resin obtained by the above, wherein the resol resin has a charge transporting structure. 32. At least one of the hydroxyphenyl groups is a p-hydroxyphenyl group.
The electrophotographic photosensitive member according to 1. 33. The electrophotographic photosensitive member according to claim 31, wherein the charge transporting structure is a triarylamine structure. 34. The phenol compound having a hydroxyphenyl group and a charge transporting structure is represented by the following formula (6):
The electrophotographic photoreceptor according to any one of claims 31 to 33, having a structure represented by one formula selected from the group consisting of: [Outside 26] (In the formula (6), R ⁶¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. R ⁶² represents a hydrogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted phenyl group is shown. Ar ⁶¹ and Ar ⁶² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group,
Alternatively, it represents a substituted or unsubstituted monovalent aromatic heterocyclic group. Ar ⁶³ represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group or a substituted or unsubstituted divalent aromatic heterocyclic group. m ′ and n ′ are each independently 0 or 1. ) [Outer 27] (In the formula (7), R ⁷¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁷¹ , Ar
⁷² is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic group. Indicates a heterocyclic group. The two benzene rings may together form a ring via R ⁷¹ . p'is
It is 0 or 1. ) [Outside 28] (In the formula (8), R ⁸¹ and R ⁸² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁸¹ represents a substituted or unsubstituted alkyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted 1
A valent aromatic heterocyclic group is shown. 2 bound via R ⁸¹
The two benzene rings may jointly form a ring via R ⁸¹ . Two benzene rings linked via R ^{8 2} is, R
^A ring may be jointly formed via ⁸² . q'and r'are
Each is independently 0 or 1. ) [Outside 29] (In the formula (9), R ^{91 to} R ⁹³ each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Two benzene rings bonded via R ⁹¹ are , R
^A ring may be jointly formed through ⁹¹ . Two benzene rings linked via R ⁹² may form a ring jointly via R ^92. Two benzene rings linked via R ⁹³ may form a ring jointly via R ^93.
s ', t', and u'are 0 or 1 each independently. ) [Outside 30] (In the formula (10), R ¹⁰² represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Z ¹⁰¹ , Z
¹⁰² are each independently a hydrogen atom, a halogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic heterocyclic group is shown. A benzene ring having a benzene ring and ^{Z 102} having a Z ^{101 may} form a ring jointly via ^{Z 101} or ^{Z 102.} v ′ is 0 or 1.
w ′ is an integer of 1 to 4. ) 35. The electrophotographic photosensitive member according to claim 31, wherein the basic catalyst is an amine catalyst. 36. The electrophotographic photosensitive member according to claim 35, wherein the amine catalyst is a tertiary alkylamine. 37. The electrophotographic photosensitive member according to claim 31, wherein the basic catalyst is a catalyst containing an alkali metal or a catalyst containing an alkaline earth metal. 38. The protective layer is provided on the photosensitive layer, and the surface layer of the electrophotographic photosensitive member is the protective layer.
7. The electrophotographic photosensitive member according to any one of 7. 39. A process in which an electrophotographic photosensitive member and at least one device selected from the group consisting of a charging device, a developing device, a transfer device, and a cleaning device are integrally supported, and which is detachable from the main body of the electrophotographic device. In the cartridge, the electrophotographic photoreceptor is an electrophotographic photoreceptor having a photosensitive layer on a support, and the surface layer of the electrophotographic photoreceptor comprises a substituted hydroxyphenyl group and a phenol compound having a charge transporting structure. A process cartridge containing a cured product, wherein at least one of the substituted hydroxyphenyl groups has at least one hydroxymethyl group as a substituent. 40. The process cartridge according to claim 39, wherein at least one of the substituted hydroxyphenyl groups is a substituted p-hydroxyphenyl group. 41. The process according to claim 39, wherein at least one bonding position of the hydroxymethyl group is o-position to the hydroxy group of the substituted hydroxyphenyl group having the hydroxymethyl group as a substituent. cartridge. 42. The process cartridge according to claim 39, wherein the charge transporting structure is a triarylamine structure. 43. The process cartridge according to claim 39, wherein the phenol compound has a structure represented by one formula selected from the group consisting of the following formulas (1) to (5). [Outside 31] (In the formula (1), R ¹¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. R ¹² represents a hydrogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted phenyl group is shown. Ar ¹¹ and Ar ¹² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group,
Alternatively, it represents a substituted or unsubstituted monovalent aromatic heterocyclic group. Ar ¹³ represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group or a substituted or unsubstituted divalent aromatic heterocyclic group. m and n are each independently 0 or 1
Is. X ^{11 to} X ¹⁴ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{11 to} X ¹⁴ is a hydroxymethyl group. ) [Outside 32] (In the formula (2), R ²¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ²¹ and Ar
²² is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic group. Indicates a heterocyclic group. The two benzene rings may jointly form a ring via R ²¹ . p is 0
Or 1. X ²¹ and X ²² are each independently
A hydrogen atom or a hydroxymethyl group is shown, X ²¹ ,
At least one of X ²² is a hydroxymethyl group. ) [Outside 33] (In the formula (3), R ³¹ and R ³² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ³¹ is a substituted or unsubstituted alkyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted 1
A valent aromatic heterocyclic group is shown. 2 bound through R ³¹
The two benzene rings may jointly form a ring via R ³¹ . Two benzene rings linked via R ^{3 2} is, R
^A ring may be jointly formed through ³² . q and r are 0 or 1 each independently. X ^{31 to} X ³⁴ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{31 to} X ³⁴ is a hydroxymethyl group. ) [Outer 34] (In the formula (4), R ^{41 to} R ⁴³ each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms and which may be branched. Two benzene rings bonded via R ⁴¹ are , R
^A ring may be jointly formed through ⁴¹ . Two benzene rings linked via R ⁴² may form a ring jointly via R ^42. Two benzene rings linked via R ⁴³ may form a ring jointly via R ^43. s,
t and u are 0 or 1 each independently. X ⁴¹
To X ⁴⁶ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{41 to} X ⁴⁶ is a hydroxymethyl group. ) [Outside 35] (In the formula (5), R ⁵² represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Z ⁵¹ and Z ⁵² each independently represent a hydrogen atom, a halogen atom, a substituent or a substituent. An unsubstituted alkyl group, a substituted or unsubstituted aralkyl group,
A substituted or unsubstituted monovalent aromatic hydrocarbon ring group or a substituted or unsubstituted monovalent aromatic heterocyclic group is shown.
A benzene ring having a benzene ring and ^{Z 52} having a Z ^{51 may} form a ring jointly via ^{Z 51} or ^{Z 52.} v is 0 or 1. w is an integer of 1 to 4. X ⁵¹ and X ⁵² each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ⁵¹ and X ⁵² is a hydroxymethyl group. ) 44. The process cartridge according to claim 39, wherein the electrophotographic photosensitive member has a protective layer on the photosensitive layer, and the surface layer of the electrophotographic photosensitive member is the protective layer. 45. A process in which an electrophotographic photosensitive member and at least one device selected from the group consisting of a charging device, a developing device, a transfer device, and a cleaning device are integrally supported, and which is detachable from the main body of the electrophotographic device. In the cartridge, the electrophotographic photosensitive member is an electrophotographic photosensitive member having a photosensitive layer on a support, and the surface layer of the electrophotographic photosensitive member comprises a hydroxyphenyl group and a phenol compound having a charge transporting structure as a base. A process cartridge containing a cured product of a resole resin obtained by reacting with formaldehyde under a neutral catalyst, wherein the resole resin has a charge transporting structure. 46. At least one of the hydroxyphenyl groups is a p-hydroxyphenyl group.
The process cartridge described in 1. 47. The process cartridge according to claim 45, wherein the charge transporting structure is a triarylamine structure. 48. The phenol compound having a hydroxyphenyl group and a charge transporting structure is represented by the following formula (6):
48. The process cartridge according to claim 45, having a structure represented by one formula selected from the group consisting of: [Outside 36] (In the formula (6), R ⁶¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. R ⁶² represents a hydrogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted phenyl group is shown. Ar ⁶¹ and Ar ⁶² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group,
Alternatively, it represents a substituted or unsubstituted monovalent aromatic heterocyclic group. Ar ⁶³ represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group or a substituted or unsubstituted divalent aromatic heterocyclic group. m ′ and n ′ are each independently 0 or 1. ) [Outside 37] (In the formula (7), R ⁷¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁷¹ , Ar
⁷² is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic group. Indicates a heterocyclic group. The two benzene rings may together form a ring via R ⁷¹ . p'is
It is 0 or 1. ) [Outside 38] (In the formula (8), R ⁸¹ and R ⁸² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁸¹ represents a substituted or unsubstituted alkyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted 1
A valent aromatic heterocyclic group is shown. 2 bound via R ⁸¹
The two benzene rings may jointly form a ring via R ⁸¹ . Two benzene rings linked via R ^{8 2} is, R
^A ring may be jointly formed via ⁸² . q'and r'are
Each is independently 0 or 1. ) [Outside 39] (In the formula (9), R ^{91 to} R ⁹³ each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Two benzene rings bonded via R ⁹¹ are , R
^A ring may be jointly formed through ⁹¹ . Two benzene rings linked via R ⁹² may form a ring jointly via R ^92. Two benzene rings linked via R ⁹³ may form a ring jointly via R ^93.
s ', t', and u'are 0 or 1 each independently. ) [Outside 40] (In the formula (10), R ¹⁰² represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Z ¹⁰¹ , Z
¹⁰² are each independently a hydrogen atom, a halogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic heterocyclic group is shown. A benzene ring having a benzene ring and ^{Z 102} having a Z ^{101 may} form a ring jointly via ^{Z 101} or ^{Z 102.} v ′ is 0 or 1.
w ′ is an integer of 1 to 4. ) 49. The process cartridge according to claim 45, wherein the basic catalyst is an amine catalyst. 50. The process cartridge according to claim 49, wherein the amine catalyst is a tertiary alkylamine. 51. The process cartridge according to claim 45, wherein the basic catalyst is a catalyst containing an alkali metal or a catalyst containing an alkaline earth metal. 52. The process cartridge according to claim 45, wherein the electrophotographic photosensitive member has a protective layer on the photosensitive layer, and a surface layer of the electrophotographic photosensitive member is the protective layer. 53. An electrophotographic apparatus having an electrophotographic photoreceptor, a charging means, an exposing means, a developing means and a transferring means, wherein the electrophotographic photoreceptor is an electrophotographic photoreceptor having a photosensitive layer on a support. The surface layer of the electrophotographic photoreceptor contains a cured product of a substituted hydroxyphenyl group and a phenol compound having a charge transporting structure, and at least one of the substituted hydroxyphenyl groups is at least one hydroxymethyl group as a substituent. An electrophotographic apparatus comprising: 54. The electrophotographic apparatus according to claim 53, wherein at least one of the substituted hydroxyphenyl groups is a substituted p-hydroxyphenyl group. 55. The electron according to claim 53, wherein at least one bonding position of the hydroxymethyl group is o-position to the hydroxy group of the substituted hydroxyphenyl group having the hydroxymethyl group as a substituent. Photographic equipment. 56. The electrophotographic apparatus according to claim 53, wherein the charge transporting structure is a triarylamine structure. 57. The electrophotographic apparatus according to claim 53, wherein the phenol compound has a structure represented by one formula selected from the group consisting of the following formulas (1) to (5). [Outside 41] (In the formula (1), R ¹¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. R ¹² represents a hydrogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted phenyl group is shown. Ar ¹¹ and Ar ¹² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group,
Alternatively, it represents a substituted or unsubstituted monovalent aromatic heterocyclic group. Ar ¹³ represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group or a substituted or unsubstituted divalent aromatic heterocyclic group. m and n are each independently 0 or 1
Is. X ^{11 to} X ¹⁴ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{11 to} X ¹⁴ is a hydroxymethyl group. ) [Outside 42] (In the formula (2), R ²¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ²¹ and Ar
²² is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic group. Indicates a heterocyclic group. The two benzene rings may jointly form a ring via R ²¹ . p is 0
Or 1. X ²¹ and X ²² are each independently
A hydrogen atom or a hydroxymethyl group is shown, X ²¹ ,
At least one of X ²² is a hydroxymethyl group. ) [Outer 43] (In the formula (3), R ³¹ and R ³² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ³¹ is a substituted or unsubstituted alkyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted 1
A valent aromatic heterocyclic group is shown. 2 bound through R ³¹
The two benzene rings may jointly form a ring via R ³¹ . Two benzene rings linked via R ^{3 2} is, R
^A ring may be jointly formed through ³² . q and r are 0 or 1 each independently. X ^{31 to} X ³⁴ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{31 to} X ³⁴ is a hydroxymethyl group. ) [Outer 44] (In the formula (4), R ^{41 to} R ⁴³ each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms and which may be branched. Two benzene rings bonded via R ⁴¹ are , R
^A ring may be jointly formed through ⁴¹ . Two benzene rings linked via R ⁴² may form a ring jointly via R ^42. Two benzene rings linked via R ⁴³ may form a ring jointly via R ^43. s,
t and u are 0 or 1 each independently. X ⁴¹
To X ⁴⁶ each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ^{41 to} X ⁴⁶ is a hydroxymethyl group. ) [Outer 45] (In the formula (5), R ⁵² represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Z ⁵¹ and Z ⁵² are each independently a hydrogen atom, a halogen atom, a substituent or a substituent. An unsubstituted alkyl group, a substituted or unsubstituted aralkyl group,
A substituted or unsubstituted monovalent aromatic hydrocarbon ring group or a substituted or unsubstituted monovalent aromatic heterocyclic group is shown.
A benzene ring having a benzene ring and ^{Z 52} having a Z ^{51 may} form a ring jointly via ^{Z 51} or ^{Z 52.} v is 0 or 1. w is an integer of 1 to 4. X ⁵¹ and X ⁵² each independently represent a hydrogen atom or a hydroxymethyl group, and at least one of X ⁵¹ and X ⁵² is a hydroxymethyl group. ) 58. The electrophotographic apparatus according to claim 53, wherein the electrophotographic photosensitive member has a protective layer on the photosensitive layer, and the surface layer of the electrophotographic photosensitive member is the protective layer. . 59. An electrophotographic apparatus having an electrophotographic photoreceptor, a charging means, an exposing means, a developing means and a transferring means, wherein the electrophotographic photoreceptor is an electrophotographic photoreceptor having a photosensitive layer on a support. The surface layer of the electrophotographic photoreceptor contains a cured product of a resol resin obtained by reacting a phenol compound having a hydroxyphenyl group and a charge transporting structure with formaldehyde under a basic catalyst, and the resol resin is And an electrophotographic apparatus having a charge transporting structure. 60. At least one of the hydroxyphenyl groups is a p-hydroxyphenyl group.
The electrophotographic apparatus according to 1. 61. The electrophotographic apparatus according to claim 59, wherein the charge transporting structure is a triarylamine structure. 62. The phenol compound having a hydroxyphenyl group and a charge transporting structure is represented by the following formula (6):
62. The electrophotographic apparatus according to claim 59, which has a structure represented by one formula selected from the group consisting of: [Outside 46] (In the formula (6), R ⁶¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. R ⁶² represents a hydrogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted phenyl group is shown. Ar ⁶¹ and Ar ⁶² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group,
Alternatively, it represents a substituted or unsubstituted monovalent aromatic heterocyclic group. Ar ⁶³ represents a substituted or unsubstituted divalent aromatic hydrocarbon ring group or a substituted or unsubstituted divalent aromatic heterocyclic group. m ′ and n ′ are each independently 0 or 1. ) [Outer 47] (In the formula (7), R ⁷¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁷¹ , Ar
⁷² is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic group. Indicates a heterocyclic group. The two benzene rings may together form a ring via R ⁷¹ . p'is
It is 0 or 1. ) [Outer 48] (In the formula (8), R ⁸¹ and R ⁸² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ⁸¹ represents a substituted or unsubstituted alkyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted 1
A valent aromatic heterocyclic group is shown. 2 bound via R ⁸¹
The two benzene rings may jointly form a ring via R ⁸¹ . Two benzene rings linked via R ^{8 2} is, R
^A ring may be jointly formed via ⁸² . q'and r'are
Each is independently 0 or 1. ) [Outer 49] (In the formula (9), R ^{91 to} R ⁹³ each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Two benzene rings bonded via R ⁹¹ are , R
^A ring may be jointly formed through ⁹¹ . Two benzene rings linked via R ⁹² may form a ring jointly via R ^92. Two benzene rings linked via R ⁹³ may form a ring jointly via R ^93.
s ', t', and u'are 0 or 1 each independently. ) [Outer 50] (In the formula (10), R ¹⁰² represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Z ¹⁰¹ , Z
¹⁰² are each independently a hydrogen atom, a halogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent aromatic hydrocarbon ring group, or a substituted or unsubstituted monovalent aromatic heterocyclic group is shown. A benzene ring having a benzene ring and ^{Z 102} having a Z ^{101 may} form a ring jointly via ^{Z 101} or ^{Z 102.} v ′ is 0 or 1.
w ′ is an integer of 1 to 4. ) 63. The electrophotographic apparatus according to claim 59, wherein the basic catalyst is an amine catalyst. 64. The electrophotographic apparatus according to claim 63, wherein the amine catalyst is a tertiary alkylamine. 65. The electrophotographic apparatus according to claim 59, wherein the basic catalyst is a catalyst containing an alkali metal or a catalyst containing an alkaline earth metal. 66. The electrophotographic apparatus according to claim 59, wherein the electrophotographic photosensitive member has a protective layer on the photosensitive layer, and the surface layer of the electrophotographic photosensitive member is the protective layer. .