JPH11288109A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an organic electrophotographic photoreceptor superior, especially, reproducibility of image quality and abrasion resistance, and superior in durability and photosensitivity by incorporating a polymer charge transfer material and an additive specified in structure in at least one layer of the electrophotographic photoreceptor on the surface side located farthest apart from a conductive substrate. SOLUTION: The electrophotographic photoreceptor contauns the polymer charge transfer material and the additive represented by the formula in at least one layer on the surface side located farthest apart from the conductive substrate. In the formula, each of A1 and A2 , is, independently, an H atom or an alkyl group; and A3 is a >=4C straight chain alkyl group, thus permitting the polymer charge transfer material to be fixed by chemical combination with a polymer matrix and made extremely tough against abrasion even in the case of undergoing mechanical hazard from a developing system or a cleaning system, and this additive to be high in stability in the film because the polymer charge transfer material is very high in compatibility and has a straight structure.

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 for 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 it is quickly exposed to light. It is possible to dissipate the charge.

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.

[0007] However, many charge transport materials of organic electrophotographic photoreceptors used in electrophotography 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 wear resistance deteriorate.

As a technique for improving the characteristics of the organic photoreceptor, a technique in which a binder resin of the organic photoreceptor is improved (JP-A-5-216250) and a polymer type charge transport material (JP-A-51-73888). Gazette, JP-A-54-852
7, JP-A-54-11737, JP-A-56
JP-A-150749, JP-A-57-78402, JP-A-63-285552, JP-A-1-17
No. 28, JP-A-1-19049, JP-A-3-19049
50555, JP-A-4-225014, JP-A-5-331238, etc.) have been noticed and disclosed.

Further, in addition to mechanical durability, the electrophotographic photoreceptor is deteriorated by ozone, NOx, and the like generated from various charging systems such as corona discharge. Have the problem of being triggered.

As a technique for improving the characteristics of the organic photoreceptor, a method of adding various antioxidant additives to the outermost surface layer including the charge transport layer (Japanese Patent Publication No. Sho 50-3)
3857, JP-B-51-34736, JP-A-56-130759, and JP-A-57-12244.
4, Japanese Patent Application Laid-Open No. Sho 62-105151,
-278061) and the like.

However, these photoconductors contain an additive of the general formula a in the charge transporting layer having insufficient abrasion resistance. However, its long-term sustainability is still insufficient.

From the results of the study by the present inventors, it has been found that by combining a polymer charge transport material and a phenolic antioxidant (Japanese Patent Application No. 8-151809), both abrasion resistance and image characteristics can be achieved. It became clear. However, it has been found that the incorporation of a low molecular weight antioxidant into the polymer charge transport material slightly reduces the abrasion resistance of the original polymer charge transport material.

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

[0015]

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

[0016]

Means for Solving the Problems The present inventors have intensively studied means for simultaneously realizing the image characteristics and abrasion resistance required for the electrophotographic photosensitive member, and as a result, the electrophotographic photosensitive member has been developed. The above object can be achieved by providing an electrophotographic photosensitive member containing a polymer charge transporting substance and an additive having a specific structure (general formula a) in at least one layer from the surface farthest from the conductive support. Was revealed.

This means that at least one layer from the outermost surface side of the photosensitive layer contains a polymer charge transport material.
Even when subjected to a mechanical hazard such as a developing system or a cleaning system in the electrophotographic process, the electric field transfer component is fixed by a chemical bond in the polymer matrix, so it is extremely resistant to abrasion. a) has very high compatibility with the polymer charge transport material,
In addition, since it has a long-chain structure, its stability in a film is high. For this reason, when the additive of the general formula a is contained in the polymer charge transport material, the anti-oxidation function is further imparted without impairing the abrasion resistance of the original polymer charge transport material. , Image characteristics can be maintained for a long period of time.

Furthermore, the photosensitivity of the photoreceptor can be very good by using the polymer charge transporting material having the specific structure of the present invention, which is a great factor in designing various electrophotographic image forming apparatuses. It was also found that benefits could be obtained. The electrophotographic photosensitive member used in the present invention will be described below 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 configuration, in which a charge generation layer 3 is provided on a conductive support 21.
1 and a photosensitive layer 23 composed of a charge transport layer 33 is formed. FIG. 3 is a sectional view showing still another configuration.
The undercoat layer 25 is formed between the conductive support 21 and the photosensitive layer 23. Next, the additives used in the present invention will be described.

As the additive used in the present invention, a polymer charge transporting material represented by the following general formula a is effectively used. The additives represented by the general formula a are exemplified below, and specific examples are shown.

(General formula a)

[0022]

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A ₁ and A ₂ each independently represent a hydrogen atom, an alkyl group or an aryl group. A ₃ has 4 carbon atoms
The above linear alkyl groups are shown.

Specific examples of the alkyl groups for A ₁ and A ₂ include:
Methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-
Butyl, trifluoromethyl, 2-hydroxyethyl, 2-cyanoethyl, 2-ethoxyethyl, 2
-Methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group,
4-phenylbenzyl group and the like.

Specific examples of the aryl groups represented by A ₁ and A ₂ include a phenyl group, a naphthyl group, a pyrenyl group, a 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, biphenylyl group, terphenylyl group, Examples include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group. Methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyanoethoxy, benzyloxy Group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.

The linear alkyl group having 4 or more carbon atoms of A ₃ preferably has 10 to 20 carbon atoms. Specific examples include an n-butyl group, an n-pentyl group,
n-hexyl group, n-peptyl 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.

The addition amount of the general formula (a) is as follows.
About 0 to 20 parts by weight is appropriate for 0 parts by weight,
Preferably, 5 to 10 parts by weight is good.

At least one layer from the outermost surface side of the organic photosensitive layer may contain two or more kinds of additives having the general formula a, and an antioxidant having another structure other than the general formula a. It may be used in combination.

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 general formulas 1 to 10 are effectively used. The polymer charge transport materials represented by the general formulas 1 to 10 are exemplified below and specific examples are shown.

(General formula 1)

[0032]

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

[0034]

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In the formula, R ₁₀₁ and R ₁₀₂ each independently represent a substituted or unsubstituted alkyl group, aryl group or halogen atom. 1, m is an integer of 0 to 4, Y is a single bond, the number 1 to 12 linear carbon atoms, branched or cyclic alkylene group, -O -, - S -, - SO -, - SO 2 - , -C
O-, -CO-O-Z-O-CO- (wherein Z represents an aliphatic divalent group) or

[0036]

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(Where a is an integer of 1 to 20, b is 1 to 2
An integer of 000, R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or aryl group. ). Where R
₁₀₁ and R ₁₀₂ and R ₁₀₃ and R ₁₀₄ may be the same or different.

Specific Examples of General Formula 1 R ₁ , R ₂ and R ₃ each independently represent a substituted or unsubstituted alkyl group or a halogen atom. Specific examples thereof include the following. It 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-chloropentyl 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, and specific examples of the alkyl group are the same as those described above for R ₁ , R ₂ and R ₃ . R ₅ , R
₆ represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.

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] A cycloheptenylidenephenyl group and a non-fused polycyclic group include 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) Examples of the alkyl group are the same as those described above for R ₁ , R ₂ and R ₃ .

(3) As the alkoxy group (-OR ₁₀₅ ), R ₁₀₅ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.

(4) The aryloxy group includes a phenyl group and 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. 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) 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) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, an N, N-dibenzylamino group, and the like. (7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X is a main chain of a diol compound having a triarylamino group represented by the following general formula (A) when the diol compound is polymerized by a phosgene method, a transesterification method, or the like. Introduced inside. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. 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 (A) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0047]

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The following are specific examples of the diol compound of the general formula (B). 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,
Examples thereof include aliphatic diols such as polyethylene glycol and polytetramethylene ether glycol, and cyclic aliphatic diols such as 1,4-cyclohexanediol, 1,3-cyclohexanediol, and cyclohexane-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,
4'-dihydroxydiphenylsulfoxide, 4,4 '
-Dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide,
4,4'-dihydroxydiphenyl oxide, 2,2-
Bis (4-hydroxyphenyl) hexafluorobroban, 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.

(General formula 2)

[0051]

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In the formula, R ₇ and R ₈ are substituted or unsubstituted aryl groups, and Ar ₁ , Ar ₂ and Ar ₃ are the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1.

Specific Examples of General Formula 2 R ₇ and R _{8 each} represent a substituted or unsubstituted aryl group.
Specific examples thereof include the following, which may be the same or different. 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 / 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, or a non-fused polycyclic group;

[0054]

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Here, W is —O—, —SO—, —SO ₂
-, -CO- and the following divalent groups.

[0056]

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Is represented by Heterocyclic groups include thienyl, benzothienyl, furyl, benzofuranyl,
A carbazolyl group;

The arylene groups represented by Ar ₁ , Ar ₂ and 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 as substituents. Further, these substituted groups are represented as specific examples of R ₁₀₆ , R ₁₀₇ and R _{108 in} the above general formula.

(1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) The alkyl group is preferably a C ₁ -C _12, especially a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group. atom, a hydroxyl group, a cyano group, an alkoxy group of C ₁ -C _4, containing a phenyl group, or a halogen atom, C ₁ -C ₄ alkyl or C ₁ -C ₄ phenyl group substituted with an alkoxy group Is also good. Specifically, a methyl group,
Ethyl group, 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) As the alkoxy group (—OR ₁₀₉ ), R ₁₀₉ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.

(4) The aryloxy group includes a phenyl group and 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, phenoxy, 1-naphthyloxy, 2-naphthyloxy, 4-methylphenoxy, 4-methoxyphenoxy, 4-chlorophenoxy, 6-methyl-
And a 2-naphthyloxy group.

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

(6)

[0064]

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In the formula, R ₁₁₀ and R ₁₁₁ are each independently (2)
Wherein the aryl group includes, for example, a phenyl group, a biphenyl group, and a naphthyl group, which are a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen. An atom may be contained as a substituent. Further, a ring may be formed together with a carbon atom on the aryl group. Specifically, a diethylamino group, an N-methyl-N-phenylamino group, an N, N-diphenylamino group, an N, N-di (p-tolyl) amino group, a dibenzylamino group, a piperidino group, a morpholino group, And a euroridyl group. (7) An alkylenedioxy group or an alkylenedithio group such as a methylenedioxy group or a methylenedithio group.

X is a diol compound having a triarylamino group represented by the following general formula (C), which is polymerized by a phosgene method, a transesterification method, or the like. Introduced inside. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. 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 (C) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0067]

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The diol compound of the general formula (B) has the general formula 1
And the same.

(General formula 3)

[0070]

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In the formula, R ₉ and R ₁₀ represent a substituted or unsubstituted aryl group, and 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 general formula 1.

Specific examples of general 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. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group as a condensed polycyclic 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, biphenylyl group as a non-condensed polycyclic 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. Ar ₄ , Ar ₅ , and Ar
Examples of the arylene group represented by 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) The alkyl group is preferably a C ₁ -C _12, especially a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group. atom, a hydroxyl group, a cyano group, an alkoxy group of C ₁ -C _4, containing a phenyl group, or a halogen atom, C ₁ -C ₄ alkyl or C ₁ -C ₄ phenyl group substituted with an alkoxy group Is also good. Specifically, a methyl group,
Ethyl group, 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, pendyl group, 4-chlorobenzyl group, 4-methylpentyl group, 4-methoxypentyl group, 4-phenylbenzyl group and the like.

(3) As the alkoxy group (—OR ₁₁₂ ), R ₁₁₂ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.

(4) The aryloxy group includes a phenyl group and 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. 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) 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) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). 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; specifically, an acetyl group;
Examples include a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X is the main chain of the diol compound having a triarylamino group represented by the following general formula (D) when the diol compound having the triarylamino group is polymerized by a phosgene method, a transesterification method, or the like. Introduced inside. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. 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 (D) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0080]

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The diol compound of the general formula (B) has the general formula 1
And the same. General formula 4

[0082]

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In the formula, R ₁₁ and R ₁₂ are substituted or unsubstituted aryl groups, Ar ₇ , Ar ₈ and Ar ₉ are the same or different arylene groups, and s is an integer of 1 to 5. X, k, j and n are the same as in the case of general formula 1.

Specific examples of general 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. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group as a condensed polycyclic 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, biphenylyl group as a non-condensed polycyclic 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. Ar ₇ , Ar ₈ and Ar ₉
In The arylene group represented include divalent aryl group represented by R ₁₁ and R _{1 2,} 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 and nitro group. (2) The alkyl group is preferably a C ₁ -C _12, especially a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group. atom, a hydroxyl group, a cyano group, an alkoxy group of C ₁ -C _4, containing a phenyl group, or a halogen atom, C ₁ -C ₄ alkyl or C ₁ -C ₄ phenyl group substituted with an alkoxy group Is also good. Specifically, a methyl group,
Ethyl group, 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-chloropentyl group, 4-methylpentyl group, 4-methoxypentyl group, 4-phenylpentyl group and the like.

(3) As the alkoxy group (—OR ₁₁₃ ), R ₁₁₃ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylpentyloxy group, and a trifluoromethoxy group.

(4) Examples of the aryloxy group include a phenyl group and 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. 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) 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) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, an N, N-dibenzylamino group, and the like.

(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group and a benzoyl group.

X is a main chain of a diol compound having a triarylamino group represented by the following general formula (E) when the diol compound having the triarylamino group is polymerized by a phosgene method, a transesterification method, or the like. Introduced inside. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. 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 (E) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0092]

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The diol compound of the general formula (B) is represented by the general formula 1
And the same. General formula 5

[0094]

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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 are a substituted or unsubstituted ethylene group, or Represents a substituted or unsubstituted vinylene group. X,
k, j and n are the same as in the case of the general formula 1.

Specific examples of the general 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. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group as a condensed polycyclic 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, biphenylyl group as a non-condensed polycyclic 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. Ar ₁₀ , Ar ₁₁ and Ar
Examples of the arylene group represented by 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 and nitro group. (2) The alkyl group is preferably a C ₁ -C _12, especially a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group. atom, a hydroxyl group, a cyano group, an alkoxy group of C ₁ -C _4, containing a phenyl group, or a halogen atom, C ₁ -C ₄ alkyl or C ₁ -C ₄ phenyl group substituted with an alkoxy group Is also good. Specifically, a methyl group,
Ethyl group, 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) As the alkoxy group (one OR ₁₁₄ ), R ₁₁₄ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.

(4) The aryloxy group includes a phenyl group and 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. 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. .

(5) 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) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). In particular. Dimethylamino group, diethylamino group, N-methyl-N-propylamino group. And an N, N-dipendylamino group.

(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group and a malonyl group. And a benzoyl group. X ₁ and X _{2 each} represent a substituted or unsubstituted ethylene group or a substituted or unsubstituted vinylene group. As the substituent, a cyano group, a halogen atom,
Examples include a nitro group, an aryl group of R ₁₃ and R ₁₄ , and an alkyl group of (2).

X is the main chain of the diol compound having a triarylamino group represented by the following general formula (F) when the diol compound is polymerized by a phosgene method, a transesterification method or the like. Introduced inside. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. 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 (F) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0104]

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The diol compound of the general formula (B) has the general formula 1
And the same. General formula 6

[0106]

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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 A
r ₁₆ is the same or different arylene group, 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, 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 the case of the general formula 1.

Specific Examples of General Formula 6 R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different. 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. As the heterocyclic group, a thienyl group, a benzothienyl group, a furyl group,
Examples include a benzofuranyl group and a carbazolyl group.

Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar
As the arylene group represented by _16, it includes divalent groups of the aryl group represented by R _15, R _16, R ₁₇ and R _18, 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) The alkyl group is preferably a C ₁ -C _12, especially a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group. atom, a hydroxyl group, a cyano group, an alkoxy group of C ₁ -C _4, containing a phenyl group, or a halogen atom, C ₁ -C ₄ alkyl or C ₁ -C ₄ phenyl group substituted with an alkoxy group Is also good. Specifically, a methyl group,
Ethyl group, 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) As the alkoxy group (-OR ₁₁₅ ), R ₁₁₅ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.

(4) The aryloxy group includes a phenyl group and a naphthyl group as the aryl group. this is. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -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

Y ₁ , Y ₂ and Y ₃ represent 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, or a vinylene group. It may be the same or different. The alkylene group represents a divalent group derived from the alkyl group shown in the above (2). Specifically, methylene, ethylene, 1,3-propylene, 1,4-butylene, 2-methyl-1,3
-Propylene group, difluoromethylene group, hydroxyethylene group, cyanoethylene group, methoxyethylene group, phenylmethylene group, 4-methylphenylmethylene group,
Examples thereof include a 2,2-propylene group, a 2,2-butylene group, and a diphenylmethylene group.

Examples of the cycloalkylene group include a 1,1-cyclopentylene group, a 1,1-cyclohexylene group,
Examples thereof include a 1-cyclooctylene group. Examples of the alkylene ether group include a dimeterene ether group, a diethylene ether group, an ethylene methylene ether group, a bis (triethylene) ether group, and a polytetramethylene ether group.

X is the main chain of a diol compound having a triarylamino group represented by the following general formula (G) when the diol compound having the triarylamino group is polymerized by a phosgene method, a transesterification method, or the like. Introduced inside. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. 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 (G) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0116]

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The diol compound of the general formula (B) has the general formula 1
And the same. General formula 7

[0118]

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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 represented by general formula 1
Is the same as

Specific Examples of General 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. . As the aromatic hydrocarbon group, a phenyl group, a naphthyl group as a condensed polycyclic 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, biphenylyl group as a non-condensed polycyclic 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. When R ₁₉ and R ₂₀ form a ring, 9-fluorinylidene and 5H-dibenzo [a,
d] Cyclohebutenylidene and the like. Also, A
The arylene groups represented by r ₁₇ , Ar ₁₈ and Ar ₁₉ include the divalent groups of the aryl groups represented by R ₁₉ and R ₂₀ , 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 and nitro group. (2) The alkyl group is preferably a C ₁ -C _12, especially a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group. atom, a hydroxyl group, a cyano group, an alkoxy group of C ₁ -C _4, containing a phenyl group, or a halogen atom, C ₁ -C ₄ alkyl or C ₁ -C ₄ phenyl group substituted with an alkoxy group Is also good. Specifically, a methyl group,
Ethyl group, 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) As the alkoxy group (-OR ₁₁₆ ), R ₁₁₆ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylpentyloxy group, and a trifluoromethoxy group.

(4) The aryloxy group includes a phenyl group and 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. 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) 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) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, an N, N-dibenzylamino group, and the like. (7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X is the main chain of a diol compound having a triarylamino group represented by the following general formula (H) when the diol compound having the triarylamino group is polymerized by a phosgene method, a transesterification method, or the like. Introduced inside. In this case, the produced polycarbonate grease becomes a random copolymer or a block copolymer. 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 (H) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0128]

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The diol compound of the general formula (B) has the general formula 1
And the same. (General formula 8)

[0130]

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In the formula, R ₂₁ represents a substituted or unsubstituted aryl group, and Ar ₂₀ , Ar ₂₁ , Ar ₂₂ and Ar ₂₃ represent the same or different arylene groups. X, k, j and n are represented by the general formula 1
Is the same as

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. As the aromatic hydrocarbon group,
Phenyl 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- Examples of the dibenzo [a, d] cycloheptenylidenephenyl group include biphenylyl and terphenylyl groups as non-condensed polycyclic groups.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group. Examples of the arylene group represented by Ar ₂₀ , A ₂₁ , Ar ₂₂ and Ar ₂₃ include the divalent group 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) A halogen atom, a trifluoromethyl group, a cyano group, and a nitro group. (2) The alkyl group is preferably a C ₁ -C _12, especially a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group. atom, a hydroxyl group, a cyano group, an alkoxy group of C ₁ -C _4, containing a phenyl group, or a halogen atom, C ₁ -C ₄ alkyl or C ₁ -C ₄ phenyl group substituted with an alkoxy group Is also good. Specifically, a methyl group,
Ethyl group, 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) As the alkoxy group (—OR ₁₁₇ ), R ₁₁₇ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.

(4) The aryloxy group includes a phenyl group and 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. 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) 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) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, an N, N-dibenzylamino group, and the like. (7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X is a diol compound having a triarylamino group represented by the following general formula (J), which is polymerized by a phosgene method, a transesterification method, or the like, by using a diol compound represented by the following general formula (B) in combination with the main chain. Introduced inside. In this case, the produced polycarbonate grease becomes a random copolymer or a block copolymer. 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 (J) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0139]

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The diol compound of the general formula (B) has the general formula 1
And the same. (General formula 9)

[0141]

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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 and A
r ₂₇ and Ar ₂₈ represent the same or different arylene groups. X,
k, j and n are the same as in the case of the general formula 1.

Specific Examples of General Formula 9 R ₂₂ , R ₂₃ , R ₂₄ , and R _{25 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following. May also be different. 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.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group. Ar ₂₄ , Ar ₂₅ , Ar ₂₆ ,
Arylene groups represented by Ar ₂₇ and Ar ₂₈ include R
_The divalent groups of the above aryl groups represented by ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are mentioned, and 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 and nitro group. (2) The alkyl group is preferably a C ₁ -C _12, especially a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group. atom, a hydroxyl group, a cyano group, an alkoxy group of C ₁ -C _4, containing a phenyl group, or a halogen atom, C ₁ -C ₄ alkyl or C ₁ -C ₄ phenyl group substituted with an alkoxy group Is also good. Specifically, a methyl group,
Ethyl group, 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) As the alkoxy group (-OR ₁₁₈ ), R ₁₁₈ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.

(4) Examples of the aryloxy group include a phenyl group and 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, phenoxy, 1-naphthyloxy, 2-naphthyloxy, 4-methylphenoxy, 4-methoxyphenoxy, 4-chlorophenoxy, 6-methyl-
And a 2-naphthyloxy group.

(5) 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) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, an N, N-dibenzylamino group, and the like. (7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X is the main chain when the diol compound having a triarylamino group represented by the following general formula (L) is polymerized by a phosgene method, a transesterification method, or the like, by using the diol compound represented by the following general formula (B) in combination. Introduced inside. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. 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 produced polycarbonate becomes an alternating copolymer.

[0150]

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The diol compound of the general formula (B) has the general formula 1
And the same. General formula 10

[0152]

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In the formula, R ₂₆ and R ₂₇ represent a substituted or unsubstituted aryl group, and 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 general formula 1.

Specific examples of general 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. . Phenyl group as an aromatic hydrocarbon group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2 as a condensed polycyclic group
-A fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrysenyl group, a fluorenylidenephenyl group, a 5H-dibenzo [a, d] cycloheptenylidenephenyl group, a biphenylyl group or a terphenylyl group as a non-condensed polycyclic group. No.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group. Ar ₂₉ , Ar ₃₀ and Ar ₃₁
Examples of the arylene group represented by are 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) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) The alkyl group is preferably a C ₁ -C _12, especially a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group. atom, a hydroxyl group, a cyano group, an alkoxy group of C ₁ -C _4, containing a phenyl group, or a halogen atom, C ₁ -C ₄ alkyl or C ₁ -C ₄ phenyl group substituted with an alkoxy group Is also good. Specifically, a methyl group,
Ethyl group, 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) As the alkoxy group (-OR ₁₁₉ ), R ₁₁₉ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group. (4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. This is C ₁ -C ₄
Alkoxy group, may contain an alkyl group or a halogen atom C ₁ -C ₄ 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) 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) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, an N, N-dibenzylamino group, and the like. (7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X is a diol compound having a triarylamino group represented by the following general formula (M), which is polymerized by a phosgene method, a transesterification method, or the like. Introduced inside. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. 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 (M) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0160]

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The diol compound of the general formula (B) has the general formula 1
And the same. As the conductive support 21,
Those exhibiting a conductivity of 10 ¹⁰ Ω or less, such as aluminum, nickel, chromium, nichrome, copper, silver, gold,
Platinum, metal such as iron, oxides such as tin oxide, indium oxide, etc. coated on film or cylindrical plastic, paper, etc. by evaporation or sputtering,
Or aluminum, aluminum alloy, nickel,
Plates such as stainless steel and D. 1. , L.
l. , Extrusion, drawing, etc. after forming the tube, cutting,
A tube or the like that has been surface-treated by superfinishing, polishing, or the like can be used.

The photosensitive layer 23 in the present invention may be of a single layer type or a laminated type, but here, for convenience of explanation, the laminated type 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 use a binder resin as needed. 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, amorphous silicon, and the like. 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, known materials can be used as the organic material. For example, phthalocyanine pigments such as metal phthalocyanine and non-metal 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, a Jigoido based pigments, and bisbenzimidazole pigments. These charge generating substances can be used alone or as a mixture of two or more kinds.

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.

Further, in addition to the above-mentioned binder resin as the binder resin of the charge generation layer, the above-mentioned general formulas 1 to 1
The polymer charge transport material having a molecular weight of 0 is preferably used, and the other polymer charge transport materials include the following.

(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
No. 0555 discloses a warfare compound and the like. (C) Polysilylene polymer For example, JP-A-63-285552,
Compounds described in JP-A-194497 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-1-19049, 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 JP-A 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 charge transport materials that can be used in combination with the charge generation layer 31 include a hole transport material and an electron transport 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-
Examples thereof include electron accepting substances such as trinitro-4H-indeno [1,2-b] thiophen-4one and 1,3,7-trinitrodibenzothiophene-5,5-dioxide. These electron transport materials can be used alone or as a mixture of two or more.

As the hole transporting substance, the following electron donating substances can be used, and are preferably used. For example, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, 9-
(P-diethylaminostyrylanthracene), 1,1
-Bis- (4-dibenzylaminophenyl) propane,
Styryl anthracene, styryl pyrazoline, phenylhydrazone, α-phenylstilbene derivative, thiazole derivative, triazole derivative, phenazine derivative,
Examples include acridine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives. These hole transport materials can be used alone or as a mixture of two or more.

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. For 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, and the like are used.
The above-mentioned inorganic and organic materials can be favorably formed.

In order to form a charge generation layer by the casting method described below, the above-mentioned inorganic or organic charge generation material is used together with a binder resin, if necessary, using a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane or butanone. 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 suitably about 0.01 to 5 μm, 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 a polymer charge transport material and an additive represented by the general formula a. The polymer charge transport material and the additive represented by the general formula a are dissolved or dispersed in an appropriate solvent. Then, it can be formed by coating and drying. As the polymer charge transporting material, the above-mentioned known materials can be used, and the polymer charge transporting materials represented by the general formulas 1 to 10 are particularly preferably used to achieve the object of the present invention. Further, if necessary, a polymer charge transporting material and a general formula a
In addition to the additives described above, appropriate amounts of a suitable binder resin, a low-molecular charge transport material, a plasticizer, a leveling agent, and the like can also 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, phenol 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 substance as described in the description of the charge generating layer 31 can be used. The thickness of the charge transport layer 33 is
About 5 to 100 μm is appropriate, and preferably about 10 to 100 μm.
About 40 μm is appropriate. In the present invention, a plasticizer may be added to the charge transport layer 33.

As the plasticizer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount of the plasticizer is 0 to 30 parts by weight based on 100 parts by weight of the binder resin. The degree is appropriate. As the leveling agent, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in a side chain are used. About 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, a charge-generating substance, a low-molecular-weight or high-molecular-weight charge-transporting substance and an additive of the general formula a are often dissolved or dispersed in a suitable solvent, and then coated and dried. Can be formed.
The aforementioned materials can be used for the charge generation material and the charge transport material.

Further, if necessary, a plasticizer or a leveling agent can be added. Further, as the binder resin that can be used as needed, the charge transport layer 33
In addition to using the binder resin described in the above as it is, the binder resin described in the charge generation layer 31 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 25 can be provided between the conductive support 21 and the photosensitive layer 23 (the charge generation layer 31 in the case of the laminated type). The undercoat layer 25 is provided for the purpose of improving adhesiveness, preventing moire, improving coatability of an upper layer, reducing residual potential, and the like. The undercoat layer 25 is generally made of a resin as a main component, but these resins are resins having high resistance to dissolution in general organic solvents in consideration of applying a photosensitive layer thereon using a solvent. It is desirable. Such resins include polyvinyl alcohol,
Water-soluble resins such as casein and sodium polyacrylate,
Curable resins that form a three-dimensional network structure, such as alcohol-soluble resins such as copolymerized nylon and methoxymethylated nylon, polyurethanes, melamine resins, alkyd-melamine resins, and epoxy resins. Further, a fine powder of a metal oxide such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide, or a metal sulfide or a metal nitride may be added. These undercoat layers can be formed using an appropriate solvent and a coating method as in the above-described photosensitive layer.

Further, as the undercoat layer of the present invention, a metal oxide layer formed by a sol-gel method using a silane coupling agent, a titanium coupling agent, a chromium coupling agent or the like is also useful. In addition to this, the undercoat layer of the present invention is provided with Al ₂ O ₃ by anodization, an organic substance such as polyparaxylylene (parylene), SiO, Sn, or the like.
A material provided with an inorganic substance such as O ₂ , TiO ₂ , ITO, CeO ₂ by a vacuum thin film manufacturing method can 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 an electrophotographic photosensitive member of the present invention and an electrophotographic process using the same.
In the figure, reference numeral 1 denotes an electrophotographic photosensitive member of the present invention, which is charged by a charging charger 2, receives image exposure 3, contacts a developer via a developing roller 4, and forms a toner image. The toner image is transferred to a transfer member 5 such as paper by a transfer charger 6 and passes through a fixing unit 10 to form a hard copy. The residual toner on the electrophotographic photoreceptor 1 is removed by the cleaning unit 7, and the residual charge is removed by the charge removing lamp 8, and the process proceeds to the next electrophotographic cycle.

Here, the image exposure 3 is analog image exposure for irradiating reflected light of a copy original via a lens or a mirror, or an electric signal from a computer or the like, or
It may be any of digital image exposure in which an electric signal or the like obtained by reading and converting a copy original with an image sensor such as a CCD is reproduced as an optical image by a laser beam or an LED array.

[0187]

Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted to such specific 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 electrophotographic photoreceptor of the present invention was obtained by forming a 5 μm undercoat layer, a 0.2 μm charge generation layer, and a 25 μm charge transport layer.

<Coating liquid for undercoat layer> Alkyd resin (Beccosol 1307-60-EL, manufactured by Dainippon Ink and Chemicals) 6 parts Melamine resin (Super Beckamine G-821-60, manufactured by Dainippon Ink and Chemicals) 4 parts Titanium oxide 40 parts Methyl ethyl ketone 200 parts <Coating liquid for charge generation layer> Oxotitanium phthalocyanine pigment 5 parts Polyvinyl butyral (UCC: XYHL) 2 parts Tetrahydrofuran 80 parts <Coating liquid for charge transport layer> Polymer having the following structure Charge transport material 10 parts

[0190]

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0.5 part of an additive having the following structure

[0192]

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Methylene chloride 100 parts Example 2 A polymer was prepared in exactly the same manner as in Example 1 except that the polymer charge transporting material used in the charge transporting layer in Example 1 was changed to one having the following structure.

[0194]

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Example 3 The procedure of Example 1 was repeated except that the polymer charge transporting material used in the charge transporting layer was changed to the one having the following structure.

[0196]

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Example 4 The procedure of Example 1 was repeated except that the polymer charge transport material and the additive used in the charge transport layer were changed to those having the following structure, and the amount of the additive was changed to 0.8 part. 1 was produced in exactly the same manner as 1.

[0198]

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[0199]

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Example 5 The procedure of Example 1 was repeated except that the polymer charge transporting material used in the charge transporting layer in Example 4 was changed to one having the following structure.

[0201]

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Example 6 The same procedure as in Example 1 was carried out except that the polymer charge transporting substance and the additive used in the charge transporting layer in Example 4 were changed to those having the following structures, and the amount of the additive was changed to 1 part. It was produced in exactly the same way.

[0203]

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[0204]

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Example 7 The same procedures as in Example 1 were carried out except that the polymer charge transporting material and the additive used in the charge transporting layer were changed to those having the following structures, and the amount of the additive was changed to 0.3 part. 1 was produced in exactly the same manner as 1.

[0206]

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[0207]

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Example 8 The procedure of Example 1 was repeated except that the polymer charge transport material and the additive used in the charge transport layer were changed to those having the following structures, and the amount of the additive was changed to 0.3 part. 1 was produced in exactly the same manner as 1.

[0209]

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[0210]

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Example 9 The procedure of Example 1 was repeated except that the polymer charge transport material and the additives used in the charge transport layer were changed to those having the following structures, and the amount of the additive was changed to 0.2 part. 1 was produced in exactly the same manner as 1.

[0212]

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[0213]

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Example 10 The procedure of Example 1 was repeated except that the polymer charge transporting material and the additive used in the charge transporting layer were changed to those having the following structures, and the amount of the additive was changed to 0.2 part. 1 was produced in exactly the same manner as 1.

[0215]

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[0216]

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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 (Teijin: Panlite C1400) 10 parts Low molecular charge transport material having the following structure 10 parts

[0219]

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0.5 part of the additive of Example 1 100 parts of methylene chloride Comparative Example 2 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. 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 6 (the same amount as in Example 6) 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 Comparative Example 1 was carried out except that the additive used in Example 8 (the same amount as in Example 8) 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 6 Comparative Example 1 was repeated except that the additive used in Example 9 (the same amount as in Example 9) 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 7 The procedure of Comparative Example 1 was repeated, 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.

Comparative Example 8 The procedure of Example 1 was repeated, except that no additives were added to the coating solution for the charge transport layer.

Comparative Example 9 The procedure of Example 2 was repeated, except that no additive was added to the coating solution for the charge transport layer.

Comparative Example 10 The procedure of Example 3 was repeated, except that no additive was added to the charge transport layer coating solution.

Comparative Example 11 The procedure of Example 4 was repeated, except that no additive was added to the charge transport layer coating solution.

Comparative Example 12 The procedure of Example 5 was repeated except that no additive was added to the coating solution for the charge transport layer.

Comparative Example 13 The procedure of Example 6 was repeated, except that no additive was added to the coating solution for the charge transport layer.

Comparative Example 14 The procedure of Example 7 was repeated, except that no additives were added to the charge transport layer coating solution.

Comparative Example 15 The procedure of Example 8 was repeated, except that no additives were added to the coating solution for the charge transport layer.

Comparative Example 16 The procedure of Example 9 was repeated, except that no additive was added to the charge transport layer coating solution.

Comparative Example 17 The procedure of Example 10 was repeated, except that no additives were added to the coating solution for the charge transport layer.

Comparative Example 18 The same procedure as in Example 1 was carried out except that the additive of the coating solution for a charge transport layer in Example 1 was changed to the one having the following structure.

[0237]

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Comparative Example 19 The procedure of Example 2 was repeated, except that the additive of the coating solution for the charge transport layer in Example 2 was changed to that of Comparative Example 18.

Comparative Example 20 The procedure of Example 3 was repeated, except that the additive in the coating solution for the charge transport layer in Example 3 was changed to that of Comparative Example 18.

Comparative Example 21 The procedure of Example 4 was repeated, except that the additive in the coating solution for the charge transport layer in Example 4 was changed to that of Comparative Example 18.

Comparative Example 22 The procedure of Example 5 was repeated, except that the additive in the coating solution for the charge transport layer in Example 5 was changed to that of Comparative Example 18.

Comparative Example 23 The procedure of Example 6 was repeated, except that the additive of the coating solution for the charge transport layer in Example 6 was changed to the one having the following structure.

[0243]

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Comparative Example 24 The procedure of Example 7 was repeated, except that the additive in the coating solution for the charge transport layer in Example 7 was changed to that of Comparative Example 23.

Comparative Example 25 The procedure of Example 8 was repeated except that the additive for the charge transport layer coating solution in Example 8 was changed to that of Comparative Example 23.

Comparative Example 26 The procedure of Example 9 was repeated, except that the additive in the coating solution for a charge transport layer in Example 9 was changed to that of Comparative Example 23.

Comparative Example 27 The procedure of Example 10 was repeated, except that the additive in the coating solution for the charge transport layer in Example 10 was changed to that of Comparative Example 23.

After mounting the electrophotographic photosensitive members of Examples 1 to 10 and Comparative Examples 1 to 27 manufactured as described above for mounting,
The evaluation was performed as follows.

[Evaluation Method of Actual Machine Running Characteristics] Each photoconductor was subjected to a paper-passing test of up to 100,000 sheets by using a commercially available electrophotographic copying machine Imagio MF200 (manufactured by Ricoh Co., Ltd.). During and after the paper passing test, the evaluation of the image quality characteristics of the photoreceptor and the abrasion loss of the photosensitive layer were performed 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.

[0250]

[Table 1]

<Image quality> ；: very good, ：: good, Δ1: slight image deletion, Δ2: poor reproducibility of fine lines, × 1: image deletion, × 2: fine reproduction As is clear from Table 1, the electrophotographic photoreceptors of Examples 1 to 10 satisfying the claims of the present invention have less deterioration of image characteristics, less wear of the photosensitive layer, and higher image quality. It can be seen that a hard copy can be obtained stably for a long time.

[0252]

As described above, according to the present invention, it is possible to obtain 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 showing a groove 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 illustrating an example of an electrophotographic process.

DESCRIPTION OF SYMBOLS 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 Static elimination lamp 109 Fixing device

 ──────────────────────────────────────────────────続 き Continuing on 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 Satoshi Kurimoto 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 at least one layer from the surface farthest from the conductive substrate comprises a polymer charge transport material and an additive of the following general formula a. An electrophotographic photoreceptor specially trained to contain. (General formula a) A ₁ and A ₂ each independently represent a hydrogen atom, an alkyl group, or an aryl group. A ₃ represents a linear alkyl group having 4 or more carbon atoms. 2. 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 general formula 1. The photoconductor for electrophotography according to claim 1. (General formula 1) 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 represent compositions, and 0.1 ≦ k
≦ 1, 0 ≦ j ≦ 0.9, and n represents the number of repeating units.
It is an integer of 5000. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula. 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 group, -O
-, - S -, - SO -, - SO 2 -, - CO -, - CO
—O—Z—O—CO— (wherein Z represents an aliphatic divalent group) or (In the formula, a represents a reed number of 1 to 20, b represents an integer of 1 to 2000, and R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or aryl group.) Where R ₁₀₁ and R ₁₀₂ ,
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 away from the conductive substrate together with the additive of general formula a is represented by the following general formula 2. The electrophotographic photosensitive member according to claim 2. (General formula 2) In the formula, R ₇ and R ₈ represent a substituted or unsubstituted aryl group;
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 general formula 1. 4. The polymer charge transporting material contained in at least one layer from the surface farthest from the conductive substrate together with the additive of general formula a is represented by the following general formula 3. The electrophotographic photosensitive member according to claim 2. (General formula 3) 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 general formula 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 general formula a is represented by the following general formula 4. The electrophotographic photosensitive member according to claim 2. (General formula 4) 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 general formula 1. 6. 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 general formula a is represented by the following general formula 5. The electrophotographic photosensitive member according to claim 2. (General formula 5) 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 general formula 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 general formula a is represented by the following general formula 6. The electrophotographic photosensitive member according to claim 2. (General formula 6) 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, and 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 general formula 1. 8. 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 general formula a is represented by the following general formula 7. The electrophotographic photosensitive member according to claim 2. (General formula 7) In the formula, R ₁₉ and R _{20 each} 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 general formula 1. 9. 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 general formula a is represented by the following general formula 8. The electrophotographic photosensitive member according to claim 2. (General formula 8) 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 general formula 1. 10. 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 general formula a is represented by the following general formula 9. The electrophotographic photosensitive member according to claim 1. (General formula 9) 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 general formula 1. 11. 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 general formula 10. The electrophotographic photosensitive member according to claim 1. (General formula 10) 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 general formula 1.