JPH11344819A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an org. electrophotographic photoreceptor which attains high performance, a long service life and high reliability on a high level, in particular an org. electrophotographic photoreceptor superior in image quality reproducibility and wear resistance and superior also in durability and photosensitivity. SOLUTION: This electrophotographic photoreceptor has a photosensitive layer on the electrically conductive substrate and contains a high molecular electric charge transferring material and an additive represented by the formula (where A1 is >=4C linear alkyl) in at least one layer from the surface side remotest from the substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic copying machine,
The present invention relates to electrophotographic photoconductors used in electrophotographic processes such as facsimile machines, laser printers, and direct digital plate making machines. More specifically, it relates to electrophotographic photoconductors having high sensitivity, high image quality, and excellent durability. It is.

[0002]

2. Description of the Related Art An electrophotographic method using an electrophotographic photosensitive member applied to a copying machine, a facsimile, a laser printer, a direct digital plate making machine, and the like includes at least primary charging, image exposure, After the development process, this method comprises a process of transferring a toner image to an image carrier (transfer paper), fixing, and cleaning the surface of the electrophotographic photosensitive member.

The basic characteristics required of an electrophotographic photoreceptor in this electrophotographic method are that it can be charged to an appropriate potential in a dark place, that there is little dissipation of electric charge in a dark place, and that the charge is quickly released by light irradiation. That they can be dissipated.

Further, in addition to these characteristics, long-term reliability such as image quality characteristics, low pollution, and low cost are required. Conventionally, as a photoreceptor used in the electrophotographic method, a photoconductive layer mainly composed of selenium or a selenium alloy is provided on a conductive support, and an inorganic photoconductive material such as zinc oxide and cadmium sulfide is used. Those dispersed in a binder and those using an amorphous silicon-based material are generally known, but in recent years, the cost is low, the degree of freedom in photoconductor design is high, and there is no pollution. For this reason, organic photoconductors have been widely used.

[0005] Organic electrophotographic photoreceptors include a photoconductive resin represented by polyvinyl carbazole (PVK), P
VK-TNF (2,4,7-trinitrofluorenone)
A charge-transfer complex type represented by, a pigment dispersion type represented by a phthalocyanine-binder, a function-separated type photoconductor using a combination of a charge-generating substance and a charge-transporting substance, and the like are known. Photoreceptors are receiving attention.

The mechanism of the formation of an electrostatic latent image in a function-separated type photoreceptor is that, when the photoreceptor is charged and irradiated with light, the light passes through a transparent charge transport layer and is charged by the charge generating substance in the charge generation layer. The absorbed charge-generating substance, which has absorbed light, generates charge carriers, which are injected into the charge-transporting layer, move in the charge-transporting layer in accordance with the electric field generated by the charging, and charge the photoreceptor surface. The latent image is formed by neutralization. In a function-separated type photoreceptor, it is known and useful to use a charge transport material having absorption mainly in the ultraviolet region and a charge generation material having absorption mainly in the visible region.

However, many charge transporting materials for organic electrophotographic photoreceptors used in electrophotographic methods have been developed as low molecular weight compounds. However, since low molecular weight compounds alone do not have a film-forming property, they are usually used. Used by dispersing and mixing in an inert polymer. However, the charge transport layer composed of a low-molecular charge transport material and an inert polymer is generally soft, and when repeatedly used in an electrophotographic process, the film is abraded by a mechanical load on the photoreceptor surface by a developing system or a cleaning system. A disadvantage is the low abrasion resistance, which tends to occur.

Further, the charge transport layer of this structure has a limit in charge mobility, which has been an obstacle to speeding up or miniaturizing the electrophotographic process. This is due to the fact that the content of the low-molecular charge transporting substance is usually used at 50% by weight or less. That is, the charge mobility can be certainly increased by increasing the content of the low-molecular charge transport material, but at the same time, the film-forming property and the abrasion resistance deteriorate.

As a technique for improving the characteristics of the organic photoreceptor, an organic photoreceptor obtained by improving a binder resin (JP-A-5-216250) and a polymer type charge transporting material (JP-A-51-73888). No., JP-A-54-85
No. 27, JP-A-54-11737, JP-A-5-11
JP-A-6-150749, JP-A-57-78402, JP-A-63-285552, JP-A-1-17
No. 28, JP-A-1-19049, JP-A-3-19049
No. 50555, JP-A-4-225014, JP-A-5-331238, etc.) have been disclosed and attracted attention.

In addition, in addition to mechanical durability, the electrophotographic photoreceptor is deteriorated by ozone and NOx generated from various charging systems such as corona discharge, and the image quality is degraded due to a decrease in chargeability. Have problems.

As a technique for improving such characteristics in an organic photoreceptor, a method of incorporating various additives having an antioxidant effect into the outermost surface layer including a charge transporting layer (Japanese Patent Publication No. Sho.
0-33857, JP-B-51-34736, JP-A-56-130759, and JP-A-57-1.
No. 22444, JP-A-62-105151,
JP-A-3-278061) is disclosed.

From the results of the study by the present inventors, it is clear that a combination of a polymer charge transporting substance and a phenolic antioxidant (Japanese Patent Application Laid-Open No. 9-319123) achieves both abrasion resistance and image characteristics. It became. However, it has been found that when a low molecular weight antioxidant is contained in the polymer charge transport material, the wear resistance of the original polymer charge transport material is slightly reduced.

As described above, the conventional electrophotographic photoreceptors are insufficient to attain a high level of high performance, long life, and high reliability recently required of the electrophotographic engine. Is strongly desired.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electrophotographic photoreceptor which achieves high performance, long life and high reliability at a high level. An object of the present invention is to provide an organic electrophotographic photoreceptor excellent in abrasion resistance, durability and photosensitivity.

[0015]

Means for Solving the Problems The present inventors have intensively studied means for simultaneously realizing image characteristics and abrasion resistance required of an electrophotographic photosensitive member. It has been clarified that the above object can be achieved by using an electrophotographic photosensitive member containing at least one polymer charge transporting substance and an additive having a specific structure in at least one layer from the surface side farthest from the support.

This is because, when at least one layer contains a polymer charge transporting substance from the outermost surface of the organic photosensitive layer, even if it receives a mechanical hazard such as a developing system or a cleaning system in an electrophotographic process, the charge can be reduced. Since the mobile component is fixed by a chemical bond in the polymer matrix, it is very resistant to abrasion. Further, an additive having a specific structure (general formula (a)) has very high compatibility with a high-molecular charge transporting substance, and has a long chain structure, and thus has high stability in a film. For this reason, when the additive of the general formula (a) is contained in the polymer charge transport material, an antioxidant function is further imparted without impairing the abrasion resistance of the original polymer charge transport material. Thereby, the image characteristics can be maintained for a long period of time.

Further, the photosensitivity of the photoreceptor can be very good by using the polymer charge transporting material having the specific structure of the present invention, and it is important to design various electrophotographic image forming apparatuses. It was also found that great advantages could be obtained with.

Hereinafter, an electrophotographic photosensitive member used in the present invention will be described with reference to the drawings. FIG. 1 is a sectional view of an electrophotographic photosensitive member used in the present invention, in which a photosensitive layer (23) is formed on a conductive support (21).
FIG. 2 is a cross-sectional view showing another structure, in which a charge generation layer (31) and a charge transport layer (3) are formed on a conductive support (21).
The photosensitive layer (23) consisting of 3) is formed.
FIG. 3 is a sectional view showing still another configuration, in which an undercoat layer (2) is provided between a conductive support (21) and a photosensitive layer (23).
5) is formed.

Next, the additives used in the present invention will be described. As the additive used in the present invention, an additive represented by the following general formula (a) is effectively used. The alkylphenol additive represented by the general formula (a) is exemplified and specific examples are shown.

[0020]

Embedded image A ₁ is a linear alkyl group having 4 or more carbon atoms. The linear alkyl group having 4 or more carbon atoms of A ₁ preferably has 10 to 20 carbon atoms. As a specific example,
n-butyl group, n-pentyl group, n-hexyl group, n-
Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n
-Hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and the like. However, it is not limited to this specific example. A ₁ may be in any of the ortho, para and meta positions with respect to the —OH group.

Next, the polymer charge transporting material used in the present invention will be described. As the polymer charge transporting material used in the present invention, polymer charge transporting materials represented by the following formulas (1) to (10) are effectively used. (1) to (1)
Examples of the polymer charge transport material represented by formula (0) are shown below.

[0022]

Embedded image In the formula, R ₁ , R ₂ and R ₃ are each independently a substituted or unsubstituted alkyl group or a halogen atom, R ₄ is a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₅ and R ₆ are substituted or unsubstituted. A substituted aryl group, o, p, and q each independently represent an integer of 0 to 4, k and j each represent a composition, and 0.1 ≦
k ≦ 1, 0 ≦ j ≦ 0.9, n represents the number of repeating units and is an integer of 5 to 5000. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula.

[0023]

Embedded image In the formula, R ₁₀₁ and R ₁₀₂ each independently represent a substituted or unsubstituted alkyl group, aryl group or halogen atom.
l and m are integers from 0 to 4, Y is a single bond, and has 1 to 1 carbon atoms.
2 linear, branched or cyclic alkylene groups, -O
-, - S -, - SO -, - SO 2 -, - CO -, - CO
—O—Z—O—CO— (wherein, Z represents an aliphatic divalent group) or

[0024]

Embedded image (In the formula, a represents an integer of 1 to 20, b represents an integer of 1 to 2,000, and R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or aryl group.) Here, R ₁₀₁ and R ₁₀₂ and R ₁₀₃ and R ₁₀₄ may be the same or different.

Specific examples of the formula (1) R ₁ , R ₂ and R ₃ each independently represent a substituted or unsubstituted alkyl group or a halogen atom, and specific examples thereof include the following. , May be the same or different.

The alkyl group is preferably C ₁ -C ₁₂
In particular, it is a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are furthermore a fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄ alkoxy group, It may contain a phenyl group or a phenyl group substituted with a halogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-
Butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl group,
2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4
-Methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R ₄ represents a hydrogen atom or a substituted or unsubstituted alkyl group,
Specific examples of the alkyl group include R ₁ , R ₂ and R ₃ described above.
And the same. R ₅ and R ₆ represent a substituted or unsubstituted aryl group (aromatic hydrocarbon group and unsaturated heterocyclic group). Specific examples thereof include the following, and even if they are the same, they are different. You may.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] cycloheptenylidenephenyl group, and a non-fused polycyclic group such as a biphenylyl group and a terphenylyl group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.

The above aryl group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) an alkyl group. As the alkyl group, the above R ₁ ,
The same as R ₂ and R ₃ can be mentioned.

(3) An alkoxy group (-OR ₁₀₅ ). Examples of the alkoxy group (—OR ₁₀₅ ) include those in which R ₁₀₅ is an alkyl group defined in the above (2). Specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-
Propoxy group, t-butoxy group, n-butoxy group, s-
Butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like. (4) an aryloxy group. As the aryloxy group,
Aryl groups include those having a phenyl group and a naphthyl group. This is a C ₁ -C ₄ alkoxy group, C ₁
It may contain a C ₄ to C ₄ alkyl group or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be

(5) Substituted mercapto group or arylmercapto group. Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6) an alkyl-substituted amino group. Examples of the alkyl-substituted amino group include those in which the alkyl group is the alkyl group defined in the above (2). Specifically, a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group,
And an N, N-dibenzylamino group. (7) an acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

When the diol compound having a triarylamino group represented by the following general formula (A) is polymerized by a phosgene method, a transesterification method or the like,
It is introduced into the main chain by using a diol compound of the following general formula (B) in combination. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. The structural part represented by X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (A) with a bischloroformate derived from the following general formula (B). Is done. In this case, the polycarbonate produced is an alternating copolymer.

[0033]

Embedded image Specific examples of the diol compound of the general formula (B) include the following. 1,3-propanediol, 1,4
-Butanediol, 1,5-pentanediol, 1,6
-Hexanediol, 1,8-octanediol, 1,
10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol, poly Aliphatic diols such as tetramethylene ether glycol and 1,4-cyclohexanediol,
1,3-cyclohexanediol, cyclohexane-
And cyclic aliphatic diols such as 1,4-dimethanol.

The diol having an aromatic ring includes
4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2 -Bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-
Bis (4-hydroxyphenyl) cyclopentane, 2,
2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylsulfone,
4'-dihydroxydiphenylsulfoxide, 4,4 '
-Dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide,
4,4'-dihydroxydiphenyl oxide, 2,2-
Bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) xanthene, ethylene glycol-bis (4-hydroxybenzoate), diethylene glycol- Bis (4-hydroxybenzoate), triethylene glycol-bis (4
-Hydroxybenzoate), 1,3-bis (4-hydroxyphenyl) -tetramethyldisiloxane, phenol-modified silicone oil and the like.

[0035]

Embedded image In the formula, R ₇ and R ₈ represent a substituted or unsubstituted aryl group, A
r ₁ , Ar ₂ and Ar ₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the expression (1).

Specific examples of the formula (2) R ₇ and R ₈ represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different. . Aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a pyrenyl group, a 2-fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group as a condensed polycyclic group, A fluorenylidenephenyl group, a 5H-dibenzo [a, d] cycloheptenylidenephenyl group, a biphenylyl group, a terphenylyl group as a non-fused polycyclic group, or

[0037]

Embedded image (Where W is -O-, -S-, -SO-, -SO
Represents _2- , -CO- or the following divalent group. )

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image A divalent group represented by

Heterocyclic group. Heterocyclic groups include thienyl, benzothienyl, furyl, benzofuranyl,
A carbazolyl group; Ar ₁ , Ar ₂
And the arylene group represented by Ar ₃ include the divalent groups of the aryl groups represented by R ₇ and R ₈ , which may be the same or different. The above-mentioned aryl group and arylene group may have the following groups (1) to (7) as substituents. Further, these substituents are represented by R ₁₀₆ in the above general formula,
It has the same meaning as R ₁₀₇ and R ₁₀₈ .

(1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) an alkyl group. The alkyl group is preferably C
₁ -C ₁₂ especially more preferably C ₁ -C ₁₈ linear or branched alkyl group of C ₁ -C _4, these alkyl groups may further fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄ Alkoxy group, phenyl group, or halogen atom, C _1-
It may contain a phenyl group substituted with a C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group, and a 4-phenylbenzyl group.

(3) Alkoxy group (-OR ₁₀₉ ). The alkoxy group (-OR _109), represents an alkyl group as defined R ₁₀₉ is (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-
Butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyanoethoxy, benzyloxy, 4-methylbenzyloxy, trifluoromethoxy and the like. (4) an aryloxy group. As the aryloxy group,
Aryl groups include those having a phenyl group and a naphthyl group. This is a C ₁ -C ₄ alkoxy group, C ₁
It may contain a C ₄ to C ₄ alkyl group or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be

(5) Substituted mercapto group or arylmercapto group. Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6) an alkyl-substituted amino group represented by the following formula:

[0046]

Embedded image In the formula, R ₁₁₀ and R ₁₁₁ each independently represent an alkyl group or an aryl group defined in the above (2). As the aryl group include a phenyl group, a biphenyl group, a naphthyl group, which alkoxy group C ₁ ~C _4, C ₁ ~
It may contain a C ₄ alkyl group or a halogen atom as a substituent. Further, a ring may be formed together with a carbon atom on the aryl group. Specific examples of the alkyl-substituted amino group include a diethylamino group, an N-methyl-N-phenylamino group, an N, N-diphenylamino group, an N, N-di (p-tolyl) amino group, and a dibenzylamino group. , A piperidino group, a morpholino group, a urolidyl group and the like.

(7) An alkylenedioxy group or an alkylenedithio group such as a methylenedioxy group or a methylenedithio group.

When the diol compound having a triarylamino group represented by the following general formula (C) is polymerized by a phosgene method, a transesterification method, or the like,
It is introduced into the main chain by using a diol compound of the following general formula (B) in combination. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. Further, the structural part of X is introduced into the repeating unit also by a polymerization reaction between a diol compound having a triarylamino group of the following general formula (C) and a bischloroformate derived from the following general formula (B). . In this case, the polycarbonate produced is an alternating copolymer.

[0049]

Embedded image Examples of the diol compound of the general formula (B) include the same diol compounds as used in producing the charge transporting material of the formula (1).

[0050]

Embedded image In the formula, R ₉ and R ₁₀ are a substituted or unsubstituted aryl group,
Ar ₄ , Ar ₅ and Ar ₆ represent the same or different arylene groups. X, k, j and n are the same as in the case of the expression (1).

Specific examples of formula (3) R ₉ and R ₁₀ represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different. . Aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a pyrenyl group, a 2-fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group as a condensed polycyclic group, Examples include a fluorenylidenephenyl group, a 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and a non-condensed polycyclic group such as a biphenylyl group and a terphenylyl group. Heterocyclic group. As the heterocyclic group, a thienyl group,
Examples include a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.

The arylene groups represented by Ar ₄ , Ar ₅ and Ar ₆ include the divalent groups of the aryl groups represented by R ₉ and R ₁₀ , which may be the same or different. The above-mentioned aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) an alkyl group. As the alkyl group, preferably,
C ₁ -C _12, especially C ₁ -C ₈ , more preferably C ₁ -C
₄ is a linear or branched alkyl groups, these alkyl groups may be further substituted fluorine atom, a hydroxyl group, a cyano group, C ₁ ~
A C ₄ alkoxy group, a phenyl group, or a halogen atom,
It may contain a phenyl group substituted with a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group, and a 4-phenylbenzyl group.

(3) An alkoxy group (—OR ₁₁₂ ). Examples of the alkoxy group (—OR ₁₁₂ ) include those in which R ₁₁₂ is an alkyl group defined in the above (2). Specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a t-group -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) Aryloxy group. Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. This is a C ₁ -C ₄ alkoxy group, C ₁
It may contain a C ₄ to C ₄ alkyl group or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be

(5) Substituted mercapto group or arylmercapto group. Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.

(6) An alkyl-substituted amino group. As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specifically, a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group,
And an N, N-dibenzylamino group. (7) acyl group; specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

When the diol compound having a triarylamino group represented by the following general formula (D) is polymerized by a phosgene method, a transesterification method, or the like,
It is introduced into the main chain by using a diol compound of the following general formula (B) in combination. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. The structural part of X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group of the following general formula (D) and a bischloroformate derived from the following general formula (B). . In this case, the polycarbonate produced is an alternating copolymer.

[0058]

Embedded image Examples of the diol compound of the general formula (B) include the same diol compounds as used in producing the charge transport material of the formula (1).

[0059]

Embedded image In the formula, R ₁₁ and R ₁₂ are a substituted or unsubstituted aryl group,
Ar ₇ , Ar ₈ and Ar ₉ are the same or different arylene groups, s
Represents an integer of 1 to 5. X, k, j and n are (1)
Same as for expressions.

Specific examples of the formula (4) R ₁₁ and R _{12 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different. . Aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a pyrenyl group, a 2-fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group as a condensed polycyclic group, Examples include a fluorenylidenephenyl group, a 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and a non-condensed polycyclic group such as a biphenylyl group and a terphenylyl group. Heterocyclic group. As the heterocyclic group, a thienyl group,
Examples include a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.

The arylene groups represented by Ar ₇ , Ar ₈ and Ar ₉ include the divalent groups of the aryl groups represented by R ₁₁ and R ₁₂ , which may be the same or different. The above-mentioned aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) an alkyl group. As the alkyl group, preferably,
C ₁ -C _12, especially C ₁ -C ₈ , more preferably C ₁ -C
₄ is a linear or branched alkyl groups, these alkyl groups may be further substituted fluorine atom, a hydroxyl group, a cyano group, C ₁ ~
A C ₄ alkoxy group, a phenyl group, or a halogen atom,
It may contain a phenyl group substituted with a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group, and a 4-phenylbenzyl group.

(3) An alkoxy group (—OR ₁₁₃ ). Examples of the alkoxy group (—OR ₁₁₃ ) include those in which R ₁₁₃ is an alkyl group defined in the above (2). Specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a t-group -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like. (4) an aryloxy group. As the aryloxy group,
Examples of the aryl group include a phenyl group and a naphthyl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group,
4-methoxyphenoxy group, 4-chlorophenoxy group,
6-methyl-2-naphthyloxy group and the like.

(5) Substituted mercapto group or arylmercapto group. Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6) an alkyl-substituted amino group. Examples of the alkyl-substituted amino group include those in which the alkyl group is the alkyl group defined in the above (2). Specifically, a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group,
And an N, N-dibenzylamino group. (7) an acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

When the diol compound having a triarylamino group represented by the following general formula (E) is polymerized by a phosgene method, a transesterification method, or the like,
It is introduced into the main chain by using a diol compound of the following general formula (B) in combination. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. The structural part of X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group of the following general formula (E) and a bischloroformate derived from the following general formula (B). . In this case, the polycarbonate produced is an alternating copolymer.

[0065]

Embedded image Examples of the diol compound of the general formula (B) include the same diol compounds as used in producing the charge transport material of the formula (1).

[0066]

Embedded image In the formula, R ₁₃ and R ₁₄ are a substituted or unsubstituted aryl group,
Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are the same or different arylene groups,
X ₁ and X ₂ represent a substituted or unsubstituted ethylene group or a substituted or unsubstituted vinylene group. X, k, j and n are the same as in the case of the expression (1).

Specific examples of the formula (5) R ₁₃ and R ₁₄ represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different. . Aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a pyrenyl group, a 2-fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group as a condensed polycyclic group, Examples include a fluorenylidenephenyl group, a 5H-dibenzo [a, d] cycloheptenylidenephenyl group, and a non-condensed polycyclic group such as a biphenylyl group and a terphenylyl group. Heterocyclic group. As the heterocyclic group, a thienyl group,
Examples include a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.

The arylene groups represented by Ar ₁₀ , Ar ₁₁ and Ar ₁₂ include the divalent groups of the aryl groups represented by R ₁₃ and R ₁₄ , which may be the same or different.
The above-mentioned aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) an alkyl group. As the alkyl group, preferably,
C ₁ -C _12, especially C ₁ -C ₈ , more preferably C ₁ -C
₄ is a linear or branched alkyl groups, these alkyl groups may be further substituted fluorine atom, a hydroxyl group, a cyano group, C ₁ ~
A C ₄ alkoxy group, a phenyl group, or a halogen atom,
It may contain a phenyl group substituted with a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group, and a 4-phenylbenzyl group.

(3) An alkoxy group (—OR ₁₁₄ ). Examples of the alkoxy group (—OR ₁₁₄ ) include those in which R ₁₁₄ is an alkyl group defined in the above (2). Specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a t-group -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) Aryloxy group. Examples of the aryloxy group include those having a phenyl group or a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group,
Examples thereof include a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, and a 6-methyl-2-naphthyloxy group.

(5) Substituted mercapto group or arylmercapto group. Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.

(6) An alkyl-substituted amino group. Examples of the alkyl-substituted amino group include those in which the alkyl group is the alkyl group defined in the above (2). Specifically, a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, N, N -Dibenzylamino group and the like. (7) an acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

The structural parts of X ₁ and X ₂ represent a substituted or unsubstituted ethylene group or a substituted or unsubstituted vinylene group, which may be a cyano group, a halogen atom, a nitro group, the above R ₁₃ , The aryl group of R _{14 and} the alkyl group of the above (2) are exemplified.

When the diol compound having a triarylamino group represented by the following general formula (F) is polymerized by a phosgene method, a transesterification method, or the like,
It is introduced into the main chain by using a diol compound of the following general formula (B) in combination. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. Further, the structural part of X is introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group of the following general formula (F) and a bischloroformate derived from the following general formula (B). . In this case, the polycarbonate produced is an alternating copolymer.

[0075]

Embedded image Examples of the diol compound of the general formula (B) include the same diol compounds as used in producing the charge transport material of the formula (1).

[0076]

Embedded image

In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ represent a substituted or unsubstituted aryl group, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ , A
r ₁₆ is the same or different arylene group, Y ₁ , Y ₂ , Y ₃ are a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, It represents a sulfur atom or a vinylene group and may be the same or different. X, k, j
And n are the same as in equation (1).

Specific examples of the formula (6) R ₁₅ , R ₁₆ , R ₁₇ and R _{18 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following. Or different.

An aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group and a condensed polycyclic group such as a naphthyl group, a pyrenyl group, a 2-fluorenyl group, and a 9,9-dimethyl-2- group.
Fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, biphenylyl group and terphenylyl group as non-condensed polycyclic groups. Can be Heterocyclic group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.

Further, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆
Examples of the arylene group represented by are the divalent groups of the above aryl groups represented by R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ , which may be the same or different.

The above aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) an alkyl group. As the alkyl group, preferably,
C ₁ -C _12, especially C ₁ -C ₈ , more preferably C ₁ -C
₄ is a linear or branched alkyl groups, these alkyl groups may be further substituted fluorine atom, a hydroxyl group, a cyano group, C ₁ ~
A C ₄ alkoxy group, a phenyl group, or a halogen atom,
It may contain a phenyl group substituted with a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group, and a 4-phenylbenzyl group.

(3) An alkoxy group (—OR ₁₁₅ ). Examples of the alkoxy group (—OR ₁₁₅ ) include those in which R ₁₁₅ is an alkyl group defined in the above (2). Specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a t-group -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) Aryloxy group. Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. This is a C ₁ -C ₄ alkoxy group, C ₁
It may contain a C ₄ to C ₄ alkyl group or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be

The structural parts of Y ₁ , Y ₂ and Y ₃ are a single bond,
It represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, and a vinylene group, which may be the same or different.

The alkylene group includes a divalent group derived from the alkyl group shown in the above (2), and specifically, a methylene group, an ethylene group, a 1,3-propylene group, a 1,4 -Butylene group, 2-methyl-1,3-propylene group, difluoromethylene group, hydroxyethylene group, cyanoethylene group, methoxyethylene group, phenylmethylene group, 4-methylphenylmethylene group, 2,2-
Examples thereof include a propylene group, a 2,2-butylene group, and a diphenylmethylene group.

The cycloalkylene group includes 1,1-
Cyclopentylene group, 1,1-cyclohexylene group,
Examples thereof include a 1,1-cyclooctylene group.

Examples of the alkylene ether group include a dimethylene ether group, a diethylene ether group, an ethylene methylene ether group, a bis (triethylene) ether group, and a polytetramethylene ether group.

When the diol compound having a triarylamino group of the following general formula (G) is polymerized by a phosgene method, a transesterification method, or the like,
It is introduced into the main chain by using a diol compound of the following general formula (B) in combination. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. The structural part of X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group of the following general formula (G) and a bischloroformate derived from the following general formula (B). . In this case, the polycarbonate produced is an alternating copolymer.

[0089]

Embedded image Examples of the diol compound of the general formula (B) include the same diol compounds as used in producing the charge transport material of the formula (1).

[0090]

Embedded image In the formula, R ₁₉ and R ₂₀ represent a hydrogen atom or a substituted or unsubstituted aryl group, and R ₁₉ and R ₂₀ may form a ring. Ar ₁₇ , Ar ₁₈ and Ar ₁₉ represent the same or different arylene groups. X, k, j and n are the same as in the case of the expression (1).

Specific examples of formula (7) R ₁₉ and R _{20 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different. .

Aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group and a condensed polycyclic group such as a naphthyl group, a pyrenyl group, a 2-fluorenyl group, and a 9,9-dimethyl-2- group.
Fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, biphenylyl group and terphenylyl group as non-condensed polycyclic groups. Can be Heterocyclic group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.

When R ₁₉ and R ₂₀ form a ring, 9
-Fluorinylidene, 5H-dibenzo [a, d] cyclohebutenylidene and the like. Ar ₁₇ , Ar ₁₇
Arylene groups represented by ₁₈ and Ar ₁₉ include R ₁₉ and R
Examples include the divalent group of the aryl group represented by ₂₀ , which may be the same or different.

The above aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) an alkyl group. As the alkyl group, preferably,
C ₁ -C _12, especially C ₁ -C ₈ , more preferably C ₁ -C
₄ is a linear or branched alkyl groups, these alkyl groups may be further substituted fluorine atom, a hydroxyl group, a cyano group, C ₁ ~
A C ₄ alkoxy group, a phenyl group, or a halogen atom,
It may contain a phenyl group substituted with a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group, and a 4-phenylbenzyl group.

(3) An alkoxy group (—OR ₁₁₆ ). Examples of the alkoxy group (—OR ₁₁₆ ) include those in which R ₁₁₆ is an alkyl group defined in the above (2). Specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a t-group -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) An aryloxy group. Examples of the aryloxy group include those having a phenyl group or a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group,
Examples thereof include a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, and a 6-methyl-2-naphthyloxy group.

(5) Substituted mercapto group or arylmercapto group. Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6) an alkyl-substituted amino group. Examples of the alkyl-substituted amino group include those in which the alkyl group is the alkyl group defined in the above (2). Specifically, a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group,
And an N, N-dibenzylamino group. (7) an acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

When the diol compound having a triarylamino group represented by the following general formula (H) is polymerized by a phosgene method, a transesterification method, or the like, the diol compound represented by the following general formula (B) is used in combination with the diol compound represented by the following general formula (B). Is introduced into the main chain. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer.
The structural part of X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group of the following general formula (H) and a bischloroformate derived from the following general formula (B). . In this case, the polycarbonate produced is an alternating copolymer.

[0099]

Embedded image Examples of the diol compound of the general formula (B) include the same diol compounds as used in producing the charge transport material of the formula (1).

[0100]

Embedded image In the formula, R ₂₁ is a substituted or unsubstituted aryl group, A
r ₂₀ , Ar ₂₁ , Ar ₂₂ and Ar ₂₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the expression (1).

Specific examples of formula (8) R ₂₁ represents a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different.

Aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group and a condensed polycyclic group such as a naphthyl group, a pyrenyl group, a 2-fluorenyl group, and a 9,9-dimethyl-2- group.
Fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, biphenylyl group and terphenylyl group as non-condensed polycyclic groups. Can be Heterocyclic group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.

In addition, Ar ₂₀ , Ar ₂₁ , Ar ₂₂ and Ar ₂₃
Examples of the arylene group represented by are the divalent groups of the aryl group represented by R ₂₁ , which may be the same or different.
The above-mentioned aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group.

(2) An alkyl group. As the alkyl group,
Preferably, C ₁ -C ₁₂ especially C ₁ -C _8, more preferably a straight-chain or branched-chain alkyl group of C ₁ -C _4,
These alkyl groups may further fluorine atom, a hydroxyl group, a cyano group, an alkoxy group of C ₁ -C _4, substituted with a phenyl group, or a halogen atom, an alkyl group or a C ₁ -C ₄ alkoxy group C ₁ -C ₄ May contain a phenyl group.
Specifically, a methyl group, an ethyl group, an n-propyl group, i
-Propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl Group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.

(3) An alkoxy group (—OR ₁₁₇ ). Examples of the alkoxy group (—OR ₁₁₇ ) include those in which R ₁₁₇ is an alkyl group defined in the above (2). Specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a t-group -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) An aryloxy group. Examples of the aryloxy group include those having a phenyl group or a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group,
Examples thereof include a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, and a 6-methyl-2-naphthyloxy group.

(5) Substituted mercapto group or arylmercapto group. Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.

(6) Alkyl-substituted amino group. As the alkyl-substituted amino group, an alkyl group represented by the alkyl group defined in the above (2) is used. Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, an N, N-dibenzylamino group, and the like. (7) an acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

When the diol compound having a triarylamino group represented by the following general formula (J) is polymerized by a phosgene method, a transesterification method, or the like, the diol compound represented by the following general formula (B) is used in combination with the diol compound represented by the following general formula (B). Is introduced into the main chain. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer.
Further, this structural part X is composed of a diol compound having a triarylamino group represented by the following general formula (J) and the following general formula (B)
Is also introduced into the repeating unit by a polymerization reaction with bischloroformate derived from In this case, the polycarbonate produced is an alternating copolymer.

[0110]

Embedded image Examples of the diol compound of the general formula (B) include the same diol compounds as used in producing the charge transport material of the formula (1).

[0111]

Embedded image In the formula, R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅ are a substituted or unsubstituted aryl group, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ , Ar ₂₈
Represents the same or different arylene groups. X, k, j and n are the same as in the case of the expression (1).

Specific examples of the formula (9) R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ represent a substituted or unsubstituted aryl group. Specific examples thereof include the following. Or different.

Aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group and a condensed polycyclic group such as a naphthyl group, a pyrenyl group, a 2-fluorenyl group, and a 9,9-dimethyl-2- group.
Fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, biphenylyl group and terphenylyl group as non-condensed polycyclic groups. Can be Heterocyclic group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.

In addition, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ ,
And the arylene group represented by Ar ₂₈ includes R ₂₂ ,
The aryl group represented by R ₂₃ , R ₂₄ , and R ₂₅ may be the same or different. The above-mentioned aryl group and arylene group may have the following groups as substituents.

(1) A halogen atom, a trifluoromethyl group, a cyano group, and a nitro group. (2) an alkyl group. As the alkyl group, preferably,
C ₁ -C _12, especially C ₁ -C ₈ , more preferably C ₁ -C
₄ is a linear or branched alkyl groups, these alkyl groups may be further substituted fluorine atom, a hydroxyl group, a cyano group, C ₁ ~
A C ₄ alkoxy group, a phenyl group, or a halogen atom,
It may contain a phenyl group substituted with a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group, and a 4-phenylbenzyl group.

(3) An alkoxy group (—OR ₁₁₈ ). Examples of the alkoxy group (—OR ₁₁₈ ) include those in which R ₁₁₈ is an alkyl group defined in the above (2). Specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a t-group -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) An aryloxy group. Examples of the aryloxy group include those having a phenyl group or a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group,
Examples thereof include a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, and a 6-methyl-2-naphthyloxy group.

(5) Substituted mercapto group or arylmercapto group. Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.

(6) Alkyl-substituted amino group. Examples of the alkyl-substituted amino group include those in which the alkyl group is the alkyl group defined in the above (2). Specifically, a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, N, N -Dibenzylamino group and the like. (7) an acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

When the diol compound having a triarylamino group represented by the following formula (L) is polymerized by a phosgene method, a transesterification method, or the like,
It is introduced into the main chain by using a diol compound of the following general formula (B) in combination. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. The structural part X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group represented by the following general formula (L) and a bischloroformate derived from the following general formula (B). . In this case, the polycarbonate produced is an alternating copolymer.

[0121]

Embedded image Examples of the diol compound of the general formula (B) include the same diol compounds as used in producing the charge transport material of the formula (1).

[0122]

Embedded image In the formula, R ₂₆ and R ₂₇ are a substituted or unsubstituted aryl group,
Ar ₂₉ , Ar ₃₀ and Ar ₃₁ represent the same or different arylene groups. X, k, j and n are the same as in the case of the expression (1).

Specific examples of the formula (10) R ₂₆ and R _{27 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different. .

Aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group and a condensed polycyclic group such as a naphthyl group, a pyrenyl group, a 2-fluorenyl group, and a 9,9-dimethyl-2- group.
Fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, biphenylyl group and terphenylyl group as non-condensed polycyclic groups. Can be Heterocyclic group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.

The arylene groups represented by Ar ₂₉ , Ar ₃₀ and Ar ₃₁ include the divalent groups of the aryl groups represented by R ₂₆ and R ₂₇ , which may be the same or different. The above-mentioned aryl group and arylene group may have the following groups as substituents.

(1) A halogen atom, a trifluoromethyl group, a cyano group, and a nitro group. (2) an alkyl group. As the alkyl group, preferably,
C ₁ -C _12, especially C ₁ -C ₈ , more preferably C ₁ -C
₄ is a linear or branched alkyl groups, these alkyl groups may be further substituted fluorine atom, a hydroxyl group, a cyano group, C ₁ ~
A C ₄ alkoxy group, a phenyl group, or a halogen atom,
It may contain a phenyl group substituted with a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group, and a 4-phenylbenzyl group.

(3) An alkoxy group (—OR ₁₁₉ ). Examples of the alkoxy group (—OR ₁₁₉ ) include those in which R ₁₁₉ is an alkyl group defined in the above (2), and specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a t-group. -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) An aryloxy group. Examples of the aryloxy group include those having a phenyl group or a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group,
Examples thereof include a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, and a 6-methyl-2-naphthyloxy group.

(5) Substituted mercapto group or arylmercapto group. Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6) an alkyl-substituted amino group. Examples of the alkyl-substituted amino group include those in which the alkyl group is the alkyl group defined in the above (2). Specifically, a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group,
And an N, N-dibenzylamino group. (7) an acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

When the diol compound having a triarylamino group represented by the following general formula (M) is polymerized by a phosgene method, a transesterification method, or the like, the diol compound represented by the following general formula (B) is used in combination with the diol compound represented by the following general formula (B). Is introduced into the main chain. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer.
Further, this structural part X is composed of a diol compound having a triarylamino group represented by the following general formula (M) and a general formula (B)
Is also introduced into the repeating unit by a polymerization reaction with bischloroformate derived from In this case, the polycarbonate produced is an alternating copolymer.

[0131]

Embedded image Examples of the diol compound of the general formula (B) include the same diol compounds as used in producing the charge transport material of the formula (1).

In the photoreceptor of the present invention shown in FIGS. 1 to 3, the conductive support (21) has a volume resistance of 10 ¹⁰ Ω.
Those exhibiting the following conductivity, for example, aluminum, nickel, chromium, nichrome, copper, silver, gold, platinum, iron and other metals, tin oxide, oxides such as indium oxide, in the form of a film or a cylinder by evaporation or sputtering. Coated with plastic, paper or the like, or a plate of aluminum, aluminum alloy, nickel, stainless steel, etc. I. , I. I. For example, pipes that have been surface-treated by cutting, superfinishing, polishing, or the like can be used after forming into a tube by a method such as extrusion or drawing.

The photosensitive layer (23) in the present invention may be of a single-layer type or a laminated type. For convenience of explanation, the photosensitive layer (23) will be described first. First, the charge generation layer (31) will be described. The charge generation layer (31) is a layer containing a charge generation substance as a main component, and may optionally use a binder resin. As the charge generation substance, an inorganic material and an organic material can be used. Examples of the inorganic material include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compound, and amorphous silicon. As amorphous silicon, a material obtained by terminating a dangling bond with a hydrogen atom or a halogen atom, or a material doped with a boron atom, a phosphorus atom, or the like is preferably used.

On the other hand, as the organic material, a known material can be used. For example, metal phthalocyanine, phthalocyanine pigments such as metal-free phthalocyanine, azulhenium salt pigment, methine squaric acid pigment, azo pigment having a carbazole skeleton, azo pigment having a triphenylamine skeleton, azo pigment having a diphenylamine skeleton, dibenzothiophene skeleton Azo pigment having a fluorenone skeleton, azo pigment having an oxadiazole skeleton, azo pigment having a bisstillene skeleton, azo pigment having a distyryl oxadiazole skeleton, azo pigment having a distyryl carbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinone imine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, i Jigoido based pigments, and bisbenzimidazole pigments. These charge generating substances can be used alone or as a mixture of two or more.

As the binder resin used as needed for the charge generation layer (31), polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral,
Polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinyl carbazole, polyacrylamide and the like are used. These binder resins can be used alone or as a mixture of two or more. As the binder resin for the charge generation layer, in addition to the binder resin described above, the polymer charge transport materials of the above formulas (1) to (10) are preferably used. Is mentioned.

(A) Polymer having carbazole ring in main chain and / or side chain For example, poly-N-vinyl carbazole,
Compounds described in JP-A-82056, JP-A-54-9632, JP-A-54-11737 and JP-A-4-183719 are exemplified. (B) Polymer having a hydrazone structure in the main chain and / or side chain. For example, JP-A-57-78402, JP-A-3-5-5
Compounds described in JP-A No. 0555/1999 and the like are exemplified. (C) Polysilylene polymer For example, JP-A-63-285552,
Compounds described in, for example, JP-A No. 19497 and JP-A-5-70595 are exemplified. (D) Polymer having a tertiary amine structure in the main chain and / or side chain, for example, N, N-bis (4-methylphenyl) -4-aminopolystyrene, JP-A-1-13061, JP-A-1-13061 -19049, JP-A 1-1728,
JP-A-1-105260, JP-A-2-16733
No. 5, JP-A-5-66598, JP-A-5-4
Compounds described in JP-A-03350 are exemplified. (E) Other polymers For example, a formaldehyde condensation polymer of nitropyrene, JP-A-51-73888, JP-A-56-15074
Compounds described in, for example, Japanese Patent Application Publication No. 9-No. 9 are exemplified. The polymer having an electron donating group used in the present invention includes not only the above-mentioned polymer, but also a copolymer of a known monomer, a block polymer, a graft polymer, a star polymer, and, for example, It is also possible to use a crosslinked polymer having an electron donating group as disclosed in JP-A-3-109406. Further, a low molecular charge transport material may be added as needed.

The low-molecular-weight charge transporting material which can be used in combination with the charge generating layer (31) includes a hole transporting material and an electron transporting material. Examples of the electron transporting substance include chloranil, bromanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone,
2,4,5,7-tetranitro-9-fluorenone,
2,4,5,7-tetranitroxanthone, 2,4,8
-Trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4one,
1,3,7-trinitrodibenzothiophene-5,5-
An electron-accepting substance such as dioxide is exemplified. These electron transport materials can be used alone or as a mixture of two or more. Examples of the hole transporting substance include the electron donating substances shown below and are preferably used. For example, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, 9- (p-diethylaminostyrylanthracene), 1,1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline Phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives and the like. These hole transport materials can be used alone or
It can be used as a mixture of more than one species.

The method for forming the charge generation layer (31) includes:
A vacuum thin film preparation method and a casting method from a solution dispersion system are mainly mentioned. As the former method, a vacuum evaporation method, a glow discharge polymerization method, an ion plating method, a sputtering method, a reactive sputtering method, a CVD method, or the like is used, and the above-mentioned inorganic material and organic material can be formed favorably.

In order to form a charge generating layer by the casting method described below, the above-mentioned inorganic or organic charge generating substance is used together with a binder resin, if necessary, using a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, butanone or the like. It can be formed by dispersing with a ball mill, an attritor, a sand mill, or the like, diluting the dispersion liquid appropriately, and applying. The coating can be performed by a dip coating method, a spray coating method, a bead coating method, or the like. The thickness of the charge generation layer provided as described above is appropriately about 0.01 to 5 μm, and preferably 0.05 to 2 μm.

Next, the charge transport layer (33) will be described. The charge transport layer (33) is a layer mainly composed of the polymer charge transport substance and the general formula (a). The polymer charge transport substance and the silicone oil are dissolved or dispersed in an appropriate solvent, and this is applied. It can be formed by drying. As the polymer charge transporting material, the above-mentioned known materials can be used, and the polymer charge transporting materials of the above formulas (1) to (10) are particularly preferably used to achieve the object of the present invention. Also, if necessary, other than a polymer charge transporting substance and silicone oil, a suitable binder resin, a low molecular charge transporting substance,
An appropriate amount of a plasticizer, an antioxidant, a leveling agent and the like can be added.

As the binder resin that can be used in combination with the charge transport layer (33), polycarbonate (bisphenol A)
Type, bisphenol Z type), polyester, methacrylic resin, acrylic resin, polyethylene, vinyl chloride, vinyl acetate, polystyrene, phenolic resin, epoxy resin, polyurethane, polyvinylidene chloride, alkyd resin, silicone resin, polyvinyl carbazole, polyvinyl butyral, polyvinyl Formal, polyacrylate, polyacrylamide, phenoxy resin and the like are used. These binders can be used alone or as a mixture of two or more.

As the low-molecular charge transporting substance that can be used in combination with the charge transporting layer (33), the same substances as described in the description of the charge generating layer (31) can be used. Charge transport layer (3
The film thickness of 3) is suitably about 5 to 100 μm, and preferably about 10 to 40 μm.

In the present invention, the charge transport layer (33)
A plasticizer may be added therein. As the plasticizer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are,
The amount used is 0 to 100 parts by weight of the binder resin.
About 30 parts by weight is appropriate.

In the present invention, the charge transport layer (33)
An antioxidant may be added therein. Examples of the antioxidant include phenol compounds, bisphenol compounds, paraphenylenediamines, hydroquinones, organic sulfur compounds, and organic phosphorus compounds. These compounds are known as antioxidants for rubber, plastics, oils and the like, and commercially available products can be easily obtained.

As the leveling agent, silicone oils such as dimethyl silicone oil and methyl phenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain are used. On the other hand, about 0 to 1 part by weight is appropriate.

Next, the case where the photosensitive layer (23) has a single-layer structure will be described. When a single-layer photosensitive layer is provided by a casting method, it can be formed by dissolving or dispersing a charge generating substance, a low molecular weight compound, a high molecular charge transporting substance, and silicone oil in an appropriate solvent, and applying and drying this. The aforementioned materials can be used as the charge generating substance and the charge transporting substance.

Further, a plasticizer can be added as required. Further, as the binder resin that can be used as necessary, in addition to using the binder resin described above for the charge transport layer (33) as it is, in addition to the charge generation layer (3)
The binder resins mentioned in 1) may be mixed and used.
The thickness of the single-layer photoreceptor is suitably about 5 to 100 μm, and preferably about 10 to 40 μm.

The electrophotographic photosensitive member used in the present invention includes:
An undercoat layer (2) is provided between the conductive support (21) and the photosensitive layer (23) (the charge generation layer (31) in the case of a laminated type).
5) can be provided. The undercoat layer (25) is provided for the purpose of improving adhesiveness, preventing moiré, improving coatability of the upper layer, reducing residual potential, and the like. The undercoat layer (25) generally contains a resin as a main component,
Considering that these resins are coated on the photosensitive layer with a solvent, it is desirable that these resins have high resistance to dissolution in general organic solvents. Such resins include polyvinyl alcohol, casein, water-soluble resins such as sodium polyacrylate, copolymerized nylon, alcohol-soluble resins such as methoxymethylated nylon, polyurethane, melamine resin, alkyd-melamine resin, epoxy resin, and the like. Curable resins that form a three-dimensional network structure are exemplified. Also, titanium oxide, silica, alumina,
Fine powders such as metal oxides such as zirconium oxide, tin oxide, and indium oxide, or metal sulfides and metal nitrides may be added. These undercoat layers can be formed using an appropriate solvent and a coating method as in the case of the above-described photosensitive layer.

Further, as the undercoat layer of the present invention, a metal oxide layer formed by using a silane coupling agent, a titanium coupling agent, a chromium coupling agent or the like, for example, by a sol-gel method or the like is also useful. . In addition, the undercoat layer of the present invention is provided with Al ₂ O ₃ by anodic oxidation, an organic substance such as polyparaxylylene (parylene), SiO,
An inorganic material such as SnO ₂ , TiO ₂ , ITO, or CeO ₂ provided by a vacuum thin film manufacturing method can also be used favorably. The thickness of the undercoat layer is suitably from 0 to 5 μm.

FIG. 4 is an example of a schematic cross-sectional view of the electrophotographic photosensitive member of the present invention and an electrophotographic process using the same.
In the figure, reference numeral (101) denotes an electrophotographic photosensitive member of the present invention, which is charged by a charging charger (102), then subjected to image exposure (103), and developed (104).
To form a toner image. The toner image is transferred to a transfer member (105) such as paper by a transfer charger (106), and passes through a fixing unit (109) to form a hard copy. Electrophotographic photoreceptor (10
1) The residual toner on the cleaning unit (107)
And the residual charge is removed by a discharge lamp (108), and the process proceeds to the next electrophotographic cycle. Here, the image exposure (103) is analog image exposure for irradiating the reflected light of the copy original via a lens or a mirror, or an electric signal from a computer or the like, or a CCD for the copy original.
Any of digital image exposure for reproducing an electric signal or the like read and converted by an image sensor such as a laser beam or an LED array as an optical image may be used.

[0151]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. All parts used in the examples are parts by weight.

Example 1 A coating liquid for an undercoat layer, a coating liquid for a charge generation layer, and a coating liquid for a charge transport layer were sequentially coated and dried on an aluminum drum having a diameter of 30 mm. An undercoat layer of 0.5 μm, a charge generation layer of 0.2 μm, and a charge transport layer of 25 μm were formed to obtain an electrophotographic photoreceptor of the present invention. (Coating liquid for undercoat layer) Alkyd resin 6 parts (Beccosol 1307-60-EL, manufactured by Dainippon Ink and Chemicals) Melamine resin 4 parts (Super Beckamine G-821-60, manufactured by Dainippon Ink and Chemicals) Oxidation Titanium 40 parts Methyl ethyl ketone 200 parts

(Coating Liquid for Charge Generating Layer) Oxo titanium phthalocyanine pigment 5 parts Polyvinyl butyral (UCC: XYHL) 2 parts Tetrahydrofuran 80 parts

(Coating Solution for Charge Transport Layer) 10 parts of a polymer charge transport material having the following structure

[0155]

Embedded image 0.5 part of additive with the following structure

[0156]

Embedded image 100 parts of methylene chloride

Example 2 A polymer charge transporting material used in the charge transporting layer in Example 1 and the general formula (a) were changed to those having the following structures.
It was produced in exactly the same way. Polymeric charge transport material with the following structure

[0158]

Embedded image 0.8 parts of additive with the following structure

[0159]

Embedded image

Example 3 The polymer charge transporting material used in the charge transporting layer in Example 1 and the general formula (a) were changed to those having the following structure.
It was produced in exactly the same way. Polymeric charge transport material with the following structure

[0161]

Embedded image 0.3 parts of additive with the following structure

[0162]

Embedded image

Example 4 The polymer charge transporting material used in the charge transporting layer in Example 1 and the general formula (a) were changed to those having the following structure.
It was produced in exactly the same way. Polymeric charge transport material with the following structure

[0164]

Embedded image 0.5 part of additive with the following structure

[0165]

Embedded image

Example 5 The polymer charge transporting material used in the charge transporting layer in Example 4 and the general formula (a) were changed to those having the following structure.
It was produced in exactly the same way. Polymeric charge transport material with the following structure

[0167]

Embedded image 0.7 parts of additives with the following structure

[0168]

Embedded image

Example 6 A polymer charge transporting material used in the charge transporting layer in Example 4 and general formula (a) were changed to those having the following structure.
It was produced in exactly the same way. Polymeric charge transport material with the following structure

[0170]

Embedded image 0.5 part of additive with the following structure

[0171]

Embedded image

Example 7 A polymer charge transport material used in the charge transport layer in Example 1 and the general formula (a) were changed to those having the following structure.
It was produced in exactly the same way. Polymeric charge transport material with the following structure

[0173]

Embedded image 0.6 part of additive with the following structure

[0174]

Embedded image

Example 8 A polymer charge transport material used in the charge transport layer in Example 7 and the general formula (a) were changed to those having the following structures.
It was produced in exactly the same way. Polymeric charge transport material with the following structure

[0176]

Embedded image Additive of the following structure 0.2 parts

[0177]

Embedded image

Example 9 A polymer charge transporting material used in the charge transporting layer in Example 7 and general formula (a) were changed to those having the following structures.
It was produced in exactly the same way. Polymeric charge transport material with the following structure

[0179]

Embedded image 0.5 part of additive with the following structure

[0180]

Embedded image

Example 10 The polymer charge transporting material used in the charge transporting layer in Example 1 and the general formula (a) were changed to those having the following structures.
It was produced in exactly the same way. Polymeric charge transport material with the following structure

[0182]

Embedded image 0.5 part of additive with the following structure

[0183]

Embedded image

Comparative Example 1 The procedure of Example 1 was repeated, except that the coating solution for the charge transport layer was changed to the following. (Coating solution for charge transport layer) Bisphenol A type polycarbonate 10 parts (Teijin: Panlite C1400) Low molecular charge transport material having the following structure

[0185]

Embedded image 100 parts of methylene chloride

Comparative Example 2 Comparative Example 1 was conducted except that the additive used in Example 1 (the same amount as in Example 1) was added to the coating solution for the charge transport layer in Comparative Example 1.
It was produced in exactly the same way.

Comparative Example 3 Comparative Example 1 was repeated except that the additive used in Example 4 (the same amount as in Example 4) was added to the coating solution for the charge transport layer in Comparative Example 1.
It was produced in exactly the same way.

Comparative Example 4 Comparative Example 1 was repeated except that the additive used in Example 7 (the same amount as in Example 7) was added to the coating solution for the charge transport layer in Comparative Example 1.
It was produced in exactly the same way.

Comparative Example 5 The same procedure as in Comparative Example 1 was carried out except that the additive used in Example 10 (the same amount as in Example 10) was added to the coating solution for the charge transport layer in Comparative Example 1.

Comparative Example 6 The procedure of Example 1 was repeated, except that no additive was added to the coating solution for the charge transport layer.

Comparative Example 7 The procedure of Example 2 was repeated, except that no additive was added to the charge transport layer coating solution.

Comparative Example 8 The procedure of Example 3 was repeated, except that no additive was added to the charge transport layer coating solution.

Comparative Example 9 The procedure of Example 4 was repeated, except that no additive was added to the coating solution for the charge transport layer.

Comparative Example 10 The procedure of Example 5 was repeated, except that no additive was added to the coating solution for the charge transport layer.

Comparative Example 11 The procedure of Example 6 was repeated, except that no additives were added to the coating solution for the charge transport layer.

Comparative Example 12 The procedure of Example 7 was repeated, except that no additives were added to the charge transport layer coating solution.

Comparative Example 13 The procedure of Example 8 was repeated, except that no additives were added to the coating solution for the charge transport layer.

Comparative Example 14 The procedure of Example 9 was repeated, except that no additives were added to the charge transport layer coating solution.

Comparative Example 15 The procedure of Example 10 was repeated, except that no additive was added to the charge transport layer coating solution.

Comparative Example 16 The procedure of Example 1 was repeated except that the additive for the charge transport layer coating solution of Example 1 had the following structure.

[0201]

Embedded image

Comparative Example 17 The procedure of Example 2 was repeated except that the additive for the charge transport layer coating liquid of Example 2 was changed to the additive of Comparative Example 16.

Comparative Example 18 The procedure of Example 3 was repeated, except that the additive for the charge transport layer coating liquid of Example 3 was changed to the additive of Comparative Example 16.

Comparative Example 19 The procedure of Example 4 was repeated, except that the additive for the charge transport layer coating liquid of Example 4 was changed to the additive of Comparative Example 16.

Comparative Example 20 The procedure of Example 5 was repeated except that the additive for the charge transport layer coating liquid of Example 5 was changed to the additive of Comparative Example 16.

Comparative Example 21 The procedure of Example 6 was repeated, except that the additive of the coating solution for the charge transport layer of Example 6 was changed to the additive of Comparative Example 16.

Comparative Example 22 The procedure of Example 7 was repeated, except that the additive for the charge transport layer coating liquid of Example 7 was changed to the additive of Comparative Example 16.

Comparative Example 23 The procedure of Example 8 was repeated, except that the additive for the charge transport layer coating solution of Example 8 had the following structure.

[0209]

Embedded image

Comparative Example 24 The procedure of Example 9 was repeated, except that the additive of the charge transport layer coating solution of Example 9 was changed to the additive of Comparative Example 23.

Comparative Example 25 The additive of the charge transport layer coating liquid of Example 10 was used in Comparative Example 23.
Except for using the additive, the same procedure as in Example 10 was carried out.

After mounting the electrophotographic photosensitive members of Examples 1 to 10 and Comparative Examples 1 to 25 manufactured as described above for mounting,
The evaluation was performed as follows. (Evaluation method of actual machine running characteristics) Each of the photoconductors was subjected to a paper-passing test of up to 100,000 sheets using a commercially available electrophotographic copying machine Imagio MF200 (manufactured by Ricoh Co., Ltd.). During and after the paper passing test, the image quality characteristics of the photoreceptor and the wear of the photosensitive layer were evaluated at appropriate times. Image quality: Comprehensive evaluation of solid density, fine line reproducibility, abnormal image, etc. Abrasion: Amount of decrease in photosensitive layer thickness due to actual machine running The evaluation results are shown in Table 1. <Image quality>: Very good: Good １ ： 1: Slight image deletion occurs △ 2: Poor fine line reproducibility × 1: Image deletion occurs × 2: Fine line reproducibility poor

[0213]

[Table 1]

As is clear from Table 1, the electrophotographic photoreceptors of Examples 1 to 10 satisfying the claims of the present invention have little deterioration of image characteristics, little wear of the photosensitive layer, and high image quality. It can be seen that a hard copy can be obtained stably for a long period of time.

[0215]

As apparent from the detailed and specific explanations including Table 1, the present invention can provide an electrophotographic photosensitive member having excellent photosensitivity characteristics, abrasion resistance and image quality stability. .

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a configuration of an electrophotographic photosensitive member of the present invention.

FIG. 2 is a cross-sectional view illustrating another configuration of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a cross-sectional view showing still another configuration of the electrophotographic photosensitive member of the present invention.

FIG. 4 is a schematic view showing an example of an electrophotographic process using the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 21 conductive support 23 photosensitive layer 25 undercoat layer 31 charge generation layer 33 charge transport layer 101 photoconductor drum 102 contact charging device 103 image exposure 104 developing device 105 transfer member 106 contact transfer device 107 cleaning blade 108 discharging lamp 109 fixing device

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor: Adult Kojima 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Tetsuro Suzuki 1-3-6 Nakamagome, Ota-ku, Tokyo Share Inside Ricoh Company (72) Inventor Yota Sakon 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company Ricoh Company (72) Inventor Hiroshi Tamura 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company Ricoh Company ( 72) Inventor Eri Shiritsu Ricoh Co., Ltd. 1-3-6 Nakamagome, Ota-ku, Tokyo

Claims (11)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, wherein a polymer charge transport material and the following general formula (a) are added to at least one layer from the surface farthest from the conductive substrate. A photoreceptor for electrophotography, comprising an agent. Embedded image A ₁ represents a linear alkyl group having 4 or more carbon atoms. 2. The polymer charge transporting substance contained in at least one layer from the surface farthest away from the conductive substrate together with the additive of the general formula (a) is represented by the following formula (1). The electrophotographic photosensitive member according to claim 1, wherein Embedded image In the formula, R ₁ , R ₂ and R ₃ are each independently a substituted or unsubstituted alkyl group or a halogen atom, R ₄ is a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₅ and R ₆ are substituted or unsubstituted. A substituted aryl group, o, p, and q each independently represent an integer of 0 to 4, k and j each represent a composition, and 0.1 ≦
k ≦ 1, 0 ≦ j ≦ 0.9, n represents the number of repeating units and is an integer of 5 to 5000. X is an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula: In the formula, R ₁₀₁ and R ₁₀₂ each independently represent a substituted or unsubstituted alkyl group, aryl group or halogen atom.
l and m are integers from 0 to 4, Y is a single bond, and has 1 to 1 carbon atoms.
2 linear, branched or cyclic alkylene groups, -O
-, - S -, - SO -, - SO 2 -, - CO -, - CO
—O—Z—O—CO— (wherein Z represents an aliphatic divalent group) or (In the formula, a represents an integer of 1 to 20, b represents an integer of 1 to 2,000, and R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or aryl group.) Here, R ₁₀₁ and R ₁₀₂ and R ₁₀₃ and R ₁₀₄ may be the same or different. 3. The polymer charge transport material contained in at least one layer from the surface farthest from the conductive substrate together with the additive of the general formula (a) is represented by the following formula (2): The electrophotographic photosensitive member according to claim 2, wherein Embedded image In the formula, R ₇ and R ₈ represent a substituted or unsubstituted aryl group, A
r ₁ , Ar ₂ and Ar ₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the above equation (1). 4. The polymer charge transporting material contained in at least one layer from the surface farthest away from the conductive substrate together with the additive of the general formula (a) is represented by the following formula (3). The electrophotographic photosensitive member according to claim 2, wherein Embedded image In the formula, R ₉ and R ₁₀ are a substituted or unsubstituted aryl group,
Ar ₄ , Ar ₅ and Ar ₆ represent the same or different arylene groups. X, k, j and n are the same as in the case of the above equation (1). 5. The polymer charge transport material contained in at least one layer from the surface farthest away from the conductive substrate together with the additive of the general formula (a) is represented by the following formula (4): The electrophotographic photosensitive member according to claim 2, wherein Embedded image In the formula, R ₁₁ and R ₁₂ are a substituted or unsubstituted aryl group,
Ar ₇ , Ar ₈ and Ar ₉ are the same or different arylene groups, s
Represents an integer of 1 to 5. X, k, j and n are the same as in the case of the above equation (1). 6. The polymer charge transport material contained in at least one layer from the surface farthest from the conductive substrate together with the additive of the general formula (a) is represented by the following formula (5). The electrophotographic photosensitive member according to claim 2, wherein Embedded image In the formula, R ₁₃ and R ₁₄ are a substituted or unsubstituted aryl group,
Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are the same or different arylene groups,
X ₁ and X ₂ represent a substituted or unsubstituted ethylene group or a substituted or unsubstituted vinylene group. X, k, j and n are the same as in the case of the above equation (1). 7. The polymer charge transport material contained in at least one layer from the surface farthest from the conductive substrate together with the additive of the general formula (a) is represented by the following formula (6). The electrophotographic photosensitive member according to claim 2, wherein Embedded image In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are a substituted or unsubstituted aryl group, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆ are the same or different arylene groups, Y ₁ , Y ₂ and Y ₃ are A single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, and a vinylene group may be the same or different. X, k, j and n are the same as in the case of the above equation (1). 8. The surface farthest away from the conductive substrate
From at least one layer together with an additive of the general formula (a)
The polymer charge transport material contained is represented by the following formula (7).
The electrophotographic photosensitive member according to claim 2, wherein
body. Embedded imageWhere R₁₉, R₂₀Is a hydrogen atom, a substituted or unsubstituted
Represents a reel group, R ₁₉And R₂₀May form a ring
No. Ar₁₇, Ar₁₈, Ar₁₉Are the same or different allylenes
Represents a group. X, k, j and n are in the case of the above equation (1)
Is the same as 9. The polymer charge transport material contained in at least one layer from the surface farthest from the conductive substrate together with the additive of the general formula (a) is represented by the following formula (8): The electrophotographic photosensitive member according to claim 2, wherein Embedded image In the formula, R ₂₁ is a substituted or unsubstituted aryl group, A
r ₂₀ , Ar ₂₁ , Ar ₂₂ and Ar ₂₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the above equation (1). 10. The polymer charge transport material contained in at least one layer from the surface farthest away from the conductive substrate together with the additive of the general formula (a) is represented by the following formula (9): The electrophotographic photosensitive member according to claim 2, wherein Embedded image In the formula, R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅ are a substituted or unsubstituted aryl group, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ , Ar ₂₈
Represents the same or different arylene groups. X, k, j and n are the same as in the case of the above equation (1). 11. The polymer charge transporting material contained in at least one layer from the surface farthest from the conductive substrate together with the additive of the general formula (a) is represented by the following formula (10): The electrophotographic photosensitive member according to claim 2, wherein Embedded image In the formula, R ₂₆ and R ₂₇ are a substituted or unsubstituted aryl group,
Ar ₂₉ , Ar ₃₀ and Ar ₃₁ represent the same or different arylene groups. X, k, j and n are the same as in the case of the above equation (1).