JP2741449B2 - Electrophotographic photoreceptor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor,
In particular, it relates to the organic photoconductive electrophotographic photoreceptor, and further to the film physical properties of the electrophotographic photoreceptor constituting layer.

[0002]

2. Description of the Related Art In the electrophotographic copying machine of the Carlson method, after uniformly charging the surface of a photoreceptor, the charge is erased imagewise by exposure to form an electrostatic latent image, and the electrostatic latent image is formed. Is developed with toner, and then the toner image is transferred and fixed on paper or the like.

On the other hand, the photoreceptor is subjected to removal of adhered toner, charge removal, and surface cleaning, and is repeatedly used for a long time.

Accordingly, the electrophotographic photoreceptor has not only electrophotographic characteristics such as good charging characteristics and sensitivity and low dark decay, but also printing durability and abrasion resistance in repeated use.
Good physical properties such as moisture resistance, resistance to ozone generated during corona discharge, and resistance to ultraviolet light during exposure (environmental resistance) are also required.

Conventionally, selenium,
Inorganic photoreceptors containing an inorganic photoconductive substance such as zinc oxide and cadmium sulfide as a main component of a photosensitive layer have been widely used.

In recent years, as a photosensitive layer of an electrophotographic photoreceptor, a carrier generating function and a carrier transporting function are assigned to different substances, and substances exhibiting each function are selected from a wide range in view of desired characteristics. There is a trend to commercialize high-durability organic photoconductors.

Conventionally, such a function-sharing type organic photoreceptor is mainly used for negative charging.
No. 647, a thin carrier generation layer is provided on a support, and a relatively thick carrier transport layer is provided thereon.

As a binder used for such a photoreceptor, bisphenol A type polycarbonate represented by the following structural formula exhibits excellent characteristics in terms of charging characteristics, sensitivity, residual potential, and repetition characteristics. Is well known.

[0009]

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However, as a result of investigations by the present inventors, the above bisphenol A-type polycarbonate has high crystallinity of a polymer, so that the solution is liable to gel, and
It has the disadvantage that it becomes unusable in about a day. In addition, when a film is formed by coating, crystalline polycarbonate precipitates on the film surface during the formation of the coating film, and a convex portion is apt to be generated. Therefore, the tailing of the coating film occurs, and the yield decreases, or as a photoreceptor, At the time of use, the toner adheres to the protrusions and remains without being cleaned, and image defects due to so-called poor cleaning tend to occur.

Further, an electrophotographic photosensitive member using the above bisphenol A type polycarbonate as a binder resin,
When used as a photoreceptor of an electrophotographic copying machine, it has the disadvantage that the surface of the photosensitive layer is scratched by being rubbed by a magnetic brush or a cleaning blade, and the photosensitive layer gradually wears.

On the other hand, high image quality and smooth copying workability also depend on the quality of a smooth and uniform surface having a uniform thickness of the photoreceptor. Alternatively, film surface failures such as yuzu skin, pinholes, coating streaks, and cracks (solvent cracks) due to coating and drying are serious problems in copying characteristics and production technology.

In order to solve the above-mentioned problems, a bulky group was introduced into the carbon between the phenylene rings (JP-A-60-1720).
No. 45) or introduction of a fluorine-containing substituent (JP-A-63-1988)
No. 65444), substitution of an alkyl group or a halogen atom on a phenylene ring (JP-A-63-148263), or a copolymer of a monomer having both phenylene rings substituted with a phenyl group or a cyclohexyl group (JP-A-1-269942). issue,
No. 1-269943), or the use of distyryl in combination with bisphenol Z-type polycarbonate as a carrier transporting substance (Japanese Patent Application Laid-Open No. 64-32265) has been proposed, but still has sufficient surface strength and surface smoothness. In addition, it is weak in abrasion and crack resistance, deteriorates image quality in repeated use, and has problems such as a decrease in sensitivity due to a decrease in film thickness due to abrasion.

[0014]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a high sensitivity,
And the electrophotographic photosensitive member photosensitive layer has high mechanical durability, good surface smoothness, crack resistance, good ozone resistance, image quality reduction, to provide a photoreceptor with low sensitivity decrease, and Another object is to provide a photosensitive member having good pot life (preservability) of the coating material for the photosensitive layer.

[0015]

The object of the present invention is to provide an electrophotographic photosensitive member having a photosensitive layer containing at least a charge generating substance, a charge transporting substance and a binder resin on a conductive support, wherein the photosensitive layer is It contains a copolymer containing a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II) as main components, and has the following general formulas (III), (IV), and (VII) Or (VIII)
This is achieved by an electrophotographic photoreceptor containing a compound represented by the following formula:

[0016]

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(Wherein R ₁ and R ₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group;
₃ and R ₄ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group, and l and m each represent an integer of 1 to 4. However, R ₁ and R ₂ may be bonded to each other to form a hydrocarbon ring having 4 to 10 carbon atoms. )

[0018]

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(Wherein R ₅ and R ₆ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group, and p and q each represent Represents an integer of 1 to 4.)

[0020]

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(In the formula, R ¹ represents an alkyl group, an allyl group, a phenyl group or an aralkyl group, and R ² represents a phenyl group which may have a substituent.)

[0022]

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Wherein X, Y and Z each represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenoxy group or an arylalkoxy group, and R ¹ represents a hydrogen atom, a lower alkyl group, an allyl group, a phenyl group or Represents an aralkyl group, m and l represent 1 or 2, and n represents 0 or 1.) (Wherein, Ar ₅ , Ar ₆ , and Ar ₇ are each an aryl group; at least one has a substituent; A is an alkylene group which may each have a substituent; an arylene group or a divalent heterocyclic ring) R ₁ represents hydrogen, an alkyl group which may have a substituent, an aralkyl group, or an aryl group.)

[0024]

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(Wherein, R ₁ represents an aryl group which may have a substituent, and R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group , A hydroxy group, a nitro group, an allyl group, an aryl group which may have a substituent, and an aralkyl group, and n represents 0 or 1.) In the present invention, the above-mentioned general formula (II)
Is preferably the following structural unit (a), and more preferably, the general formula (I) is the following structural unit (b) and the general formula (II) is the following structural unit (a).

[0026]

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The polymerization degree of the copolymer is 10 to 5000,
Preferably it is 50-1000.

In the present invention, a copolymer containing the above-mentioned general formula (I) and general formula (II) as a main repeating unit in the structural composition (hereinafter sometimes referred to as “the copolymer of the present invention”)
Is used as a binder resin to provide an electrophotographic photoreceptor that excels in film physical properties, has excellent electrophotographic properties such as charge retention power and sensitivity residual potential, and exhibits stable properties with little fatigue deterioration even when repeatedly used. Can be created.

Further, if necessary, other binders can be mixed and used within a range that does not hinder the intended effect. The mixing ratio at this time is preferably 50 wt /% or less.

The copolymer of the present invention is easily synthesized according to a conventional method using a phenolic compound selected from the following (I ') and (II').

[0031]

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In the formula, R ₁ and R ₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group;
₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group, and l, m, p and q represents an integer of 1 to 4, respectively. However, R ₁ and R ₂ may be bonded to each other to form a hydrocarbon ring having 4 to 10 carbon atoms.

Specifically, the method for producing the copolymer of the present invention is carried out in the presence of an inert solvent such as methylene chloride, 1,2-dichloroethane or the like, by adding an aqueous alkali solution or pyridine as an acid acceptor to the phenolic compound. And the reaction is carried out while introducing phosgene.

When an aqueous alkali solution is used as the acid acceptor, the reaction rate is increased when a tertiary amine such as trimethylamine or triethylamine or a quaternary ammonium compound such as tetrabutylammonium chloride or benzyltributylammonium bromide is used as a catalyst. Increase.

If necessary, a monovalent phenol such as phenol and pt-butylphenol may be used as a molecular weight regulator. The catalyst may be added from the beginning,
Any method can be adopted, such as adding the oligomer after it has been produced and increasing the molecular weight.

In the present invention, the method of copolymerizing using two or more phenol compounds is as follows: (a) a method in which two or more phenol compounds are first reacted simultaneously with phosgene and copolymerized. ) A method in which one is first reacted with phosgene, and after a certain degree of reaction, the other is added and polymerized. (C) An optional method such as a method of separately reacting with phosgene and polymerizing can be employed.

Next, specific examples of the structures represented by the general formulas (I) and (II) will be described.

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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The following are examples of the copolymer having both structures. Copolymer no.

However, l: m is preferably in the range of 95: 5 to 5:95, more preferably 95: 5 to 5: 5.
The range is 0:50. Since B ₂ is lowered sensitivity reduction and mechanical strength at 50 mol% or more, the preferable to be less than this copolymer.

The binder which may be used in combination with the copolymer of the present invention used as the above-mentioned binder includes:
For example, the following can be mentioned. (1) Polyester (2) Methacrylic resin (3) Acrylic resin (4) Polyvinyl chloride (5) Polyvinylidene chloride (6) Polystyrene (7) Polyvinyl acetate (8) Styrene copolymer resin (for example, styrene-butadiene copolymer) (9) acrylonitrile copolymer resin (for example, vinylidene chloride-acrylonitrile copolymer, etc.) (10) vinyl chloride-vinyl acetate copolymer (11) chloride Vinyl-vinyl acetate-maleic anhydride copolymer (12) silicone resin (13) silicone-alkyd resin (14) phenolic resin (for example, phenol-formaldehyde resin, cresol-formaldehyde resin,
(15) Styrene-alkyd resin (16) Poly-N-vinyl carbazole (17) Polyvinyl butyral (18) Polyvinyl formal (19) Polyhydroxystyrene These binders may be used alone or as a mixture of two or more. Can be used in combination.

Next, formulas (III), (IV) and (VI)
Charge transport materials (CT) represented by I) and (VIII)
M) will be described.

[0047]

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In the formula, R ¹ represents an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; an allyl group; a phenyl group; an aralkyl group such as a benzyl group or a phenethyl group; and R ² represents an o-tolyl group. , M-tolyl group, p-tolyl group, p-ethylphenyl group, o-chlorophenyl group, m
-Represents a phenyl group which may be substituted with a substituent such as -chlorophenyl group, p-chlorophenyl group, p-bromophenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group.

Specific examples of the compounds represented by formula (III) are shown below, but the present invention is not limited thereto.

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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In the general formula (IV), X, Y and Z
Is a hydrogen atom; a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group; a lower alkoxy group such as a methoxy group, an ethoxy group and a butoxy group; a phenoxy group; a benzyloxy group and a phenethyloxy group R ¹ represents a hydrogen atom; a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group; an allyl group; a phenyl group;
Represents an aralkyl group such as a phenethyl group. m and l represent 1 or 2, and n represents 0 or 1.

In the above general formula (IV), X and Y represent a lower alkyl group or a lower alkoxy group, Z represents a hydrogen atom, R
Is preferably a phenyl group.

The hydrazone compound represented by the general formula (IV) can be easily produced by a known method. For example, it can be produced according to the method described in JP-A-59-15251.

Specific examples of the compounds represented by formula (IV) are shown below, but the present invention is not limited thereto.

[0059]

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[0060]

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[0061] (Wherein, Ar ₅ , Ar ₆ , and Ar ₇ are each an aryl group; at least one has a substituent; A is an alkylene group which may each have a substituent; an arylene group or a divalent heterocyclic ring) R ₁ represents hydrogen, an alkyl group which may have a substituent, an aralkyl group, or an aryl group.)

Specific examples of the compounds represented by formula (VII) are shown below, but the invention is not restricted by them.

[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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(Wherein, R ₁ represents an aryl group which may have a substituent, and R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group , A hydroxy group, a nitro group, an allyl group, an aryl group which may have a substituent, and an aralkyl group, and n represents 0 or 1.) Specific examples of the compounds represented by the following general formula (VIII) Although shown, the present invention is not limited by these.

[0070]

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[0071]

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CTM usable in combination in the present invention
Although there is no particular limitation, for example, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives,
Bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline derivatives, amine derivatives, oxazolone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives,
Acridine derivative, phenazine derivative, aminostilbene derivative, poly-N-vinylcarbazole, poly-1-
Vinylpyrene and poly-9-vinylanthracene.

As the CTM used in the present invention, those which are excellent in the ability to transport holes generated upon light irradiation and which are suitable for combination with the organic pigment used in the present invention are preferable.

In the photoreceptor of the present invention, an organic pigment as shown in the following representative examples is used as a carrier generating substance (CGM). (1) Azo pigments such as monoazo pigments, bisazo pigments, triazo pigments, metal complex salt azo pigments and the like (2) Perylene pigments such as perylene anhydride and perylene imide (3) Anthraquinone derivatives, anthantrone derivatives, dibenzopyrene quinone derivatives Polycyclic quinone pigments such as pyranthrone derivatives, biolanthrone derivatives and isoviolanthrone derivatives; (4) indigo pigments such as indigo derivatives and thioindigo derivatives;
As the CGM, an organic pigment such as a fluorenone-based disazo pigment, a fluorenylidene-based disazo pigment, or a polycyclic quinone pigment is preferably used. In particular, when the following fluorenone-based disazo pigments, polycyclic quinone pigments, perylene pigments, and phthalocyanine pigments are used in the present invention, significantly improved effects are exhibited in terms of sensitivity, durability, image quality, and the like.

The fluorenone-based disazo pigment used in the present invention is represented by the following general formula [F ₁ ].

[0076]

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X ₁ and X ₂ each represent a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group,
Represents a hydroxy group or a substituted or unsubstituted amino group. p and q each represent an integer of 0, 1 or 2;
And when q is 2, X ₁ and X ₂ may be the same or different groups.

[0078] A is a group represented by the following general formula _[F 1 -1].

[0079]

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In the formula, Ar represents a fluorinated hydrocarbon group, an aromatic carbocyclic group having a substituent or an aromatic heterocyclic group. Z
Represents a nonmetallic atom group necessary for forming a substituted or unsubstituted aromatic carbocyclic ring or a substituted or unsubstituted aromatic heterocyclic ring.

M and n each represent an integer of 0, 1 or 2. However, m and n do not become 0 at the same time.

The following are specific examples of the fluorenone-based disazo pigment used in the present invention, but the invention is not limited thereto.

[0083]

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[0084]

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[0085]

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[0086]

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The fluorenone-based disazo pigment represented by the above general formula [F ₁ ] used in the present invention can be easily synthesized by a known method, for example, Japanese Patent Application No. Sho 62-304862.
No., etc.

The perylene compound used in the present invention is represented by the following general formula (P ₁ ) or (P ₂ ).

[0089]

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In the general formula (P ₁ ) or (P ₂ ), Z represents an atom group necessary for forming a substituted or unsubstituted aromatic ring.

Preferred examples of Z include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyridine ring, a pyrimidine ring, a pyrazole ring and an anthraquinone ring, and particularly preferred are a benzene ring and a naphthalene ring.

Examples of the substituent for Z include groups such as alkyl, alkoxy, aryl, aryloxy, asil, acyloxy, amino, carbamoyl, halogen, nitro, and cyano.

These perylene compounds showed a Bragg angle 2θ of 6.3 ° ± 0.2 °, 12.5 ° ± 0.2 °, 25.4 in the X-ray diffraction spectrum for Cu-Kα ray.
Those having peaks at {± 0.2} and 27.0 ± 0.2 ° are preferred.

[0094]

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The polycyclic quinone pigment used in the present invention is represented by the following general formulas [Q ₁ ] to [Q ₃ ].

[0096]

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In each formula, X represents a halogen atom, a nitro group, a cyano group, an acyl group, or a carboxy group;
And m represents an integer of 0 to 6.

Specific examples of the polycyclic quinone pigment represented by the general formulas [Q ₁ ] to [Q ₃ ] and used in the present invention are shown below, but it should not be construed that the invention is limited thereto.

Specific examples of the anthantrone pigment represented by the general formula [Q ₁ ] are as follows.

[0100]

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The compounds represented by the general formulas [Q ₁ ] to
The polycyclic quinone pigment represented by [Q ₃ ] can be easily synthesized by a known method.

As the metal-free phthalocyanine pigment usable in the present invention, all metal-free phthalocyanine having photoconductivity and derivatives thereof can be used.
Type, .beta. Type, .tau., .Tau. 'Type, .eta., .Eta.' Type, X type, and the crystal forms and derivatives thereof described in JP-A-62-103651. In particular, it is desirable to use the τ, X, K / RX type. X-type metal-free phthalocyanine is described in U.S. Pat. No. 3,357,989, and τ-type metal-free phthalocyanine is described in JP-A-58-182639. K / R-X type is disclosed in JP-A-62-10365.
As described in No. 1, at a Bragg angle (2θ ± 0.2 degrees) with respect to X-rays of CuKα and 1.541 °, 7.
7, 9.2, 16.8, 17.5, 22.4, 28.8
The peak intensity ratio of 16.8 degrees to the peak intensity of 9.2 degrees is 0.8-1.0, and 28.8 degrees to 22.4 degrees. A phthalocyanine having a peak intensity ratio of 0.4 or more.

The oxytitanyl phthalocyanine used in the present invention is represented by the following general formula [TP].

[0104]

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In the formula, X ₁ , X ₂ , X ₃ and X ₄ each independently represent H, Cl or Br, and n, m, l and k each independently represent a number from 0 to 4.

Of the oxytitanyl phthalocyanines used in the present invention, particularly preferred are Y-type oxytitanyl phthalocyanine (Y-TiOPc), titanyl chlorophthalocyanine (TiOPcCl) and mixtures thereof.

As these oxytitanyl phthalocyanines, those having different crystal types disclosed in the following patents are known. For example, JP-A-61-239248,
Nos. 62-670943, 62-272272, 63-116158 and 64-17066.

The dispersion medium of the organic pigment used in the present invention includes, for example, hydrocarbons such as hexane, benzene, toluene and xylene, methylene chloride, methylene bromide, 1,2-dichloroethane, syn-tetrachloroethane, cis -1,2-dichloroethylene, 1,
1,2-trichloroethane, 1,1,1-trichloroethane, 1,2-dichloropropane, chloroform, bromoform, halogenated hydrocarbons such as chlorobenzene, acetone, methyl ethyl ketone, ketones such as cyclohexanone, ethyl acetate, Esters such as butyl acetate, methanol, ethanol, propanol, butanol, cyclohexanol, heptanol, ethylene glycol,
Alcohols such as methyl cellosolve, ethyl cellosolve, cellosolve acetate and derivatives thereof, tetrahydrofuran,
Nitrogen compounds such as ethers and acetals such as 1,4-dioxane, furan and furfural, amines such as pyridine, butylamine, diethylamine, ethylenediamine and isopropanolamine; amides such as N, N-dimethylformamide; fatty acids and phenols And sulfur and phosphorus compounds such as carbon disulfide and triethyl phosphate.

In the present invention, the photosensitive layer may contain one or more electron-accepting substances for the purpose of improving sensitivity, reducing residual potential to fatigue during repeated use, and the like.

Examples of the electron-accepting substance that can be used here include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, and 3-nitrophthalic anhydride. Acid, 4-nitrophthalic anhydride, pyromellitic anhydride, melitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, paranitrobenzo Nitrile, picryl chloride, quinone chlorimide, chloranil, bloomanyl, dichlorodicyanoparabenzoquinone, anthraquinone, dinitroanthraquinone, 2,7-dinitrofluorenone, 2,4,7-
Trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, 9-fluorenylidene [dicyanomethylenemalonodinitrile], polynitro-9-fluorenylidene- [dicyanomethylenemalonodinitrile], picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid,
3,5-dinitrobenzoic acid, pentafluorobenzoic acid,
5-nitrosalicylic acid, 3,5-dinitrosalicylic acid,
Examples thereof include phthalic acid, merit acid, and other compounds having a high electron affinity. The addition ratio of the electron accepting substance is as follows: the organic pigment used in the present invention: electron accepting substance = 100: 0.01 to 200, preferably 1 in weight ratio.
00: 0.1 to 100.

The proportion of the electron-accepting substance added to such a layer is expressed by weight: total CTM: electron-accepting substance = 100: 0.01.
１００100, preferably 100: 0.1〜50.

Further, an organic amine can be added to the photosensitive layer of the present invention for the purpose of improving the charge generation function of CGM, and it is particularly preferable to add a secondary amine. These compounds are described in JP-A-59-21847 and JP-A-62-81.
No. 60.

In the photosensitive layer of the present invention, an antioxidant can be added for the purpose of preventing ozone deterioration.

Typical examples of such antioxidants are shown below, but are not limited thereto. Group I; hindered phenols; Group II; paraphenylenediamines; Group III; hydroquinones; Group IV; Organosulfur compounds; Group V; Organophosphorus compounds.

These compounds are described, for example, in JP-A-63-18
No. 354.

These compounds are known as antioxidants for rubbers, plastics, oils and the like, and commercially available products can be easily obtained.

The addition amount of the antioxidant is 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, particularly preferably 5 to 25 parts by weight, per 100 parts by weight of CTM.

The photoreceptor of the present invention may further contain, if necessary, an ultraviolet absorber or the like for the purpose of protecting the photosensitive layer, or may contain a dye for correcting color sensitivity.

In the photosensitive member of the present invention, an intermediate layer can be provided between the conductive substrate and the photosensitive layer, if necessary. The intermediate layer functions as an adhesive layer or a blocking layer, and in addition to the binder resin, for example, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride Copolymers, casein, N-alkoxymethylated nylon, starch and the like are used.

As the conductive support used in the construction of the electrophotographic photosensitive member of the present invention, the following are mainly used, but the present invention is not limited thereto. 1) Metal plates such as aluminum plates and stainless plates. 2) A thin metal layer of aluminum, palladium, gold or the like provided on a support such as paper or plastic film by lamination or vapor deposition. 3) A layer in which a layer of a conductive compound such as a conductive polymer, indium oxide, or tin oxide is provided by coating or vapor deposition on a support such as paper or a plastic film.

The photoreceptor of the present invention is shown in FIGS.
As shown in (1), a photosensitive layer 4 composed of a laminate of CGL2 containing CGM as a main component and CTL3 containing CTM as a main component is provided on the conductive support 1. As shown in FIGS. 1C and 1D, the photosensitive layer 4 may be provided via an intermediate layer 5 provided on the conductive support 1. Thus, when the photosensitive layer 4 has a two-layer structure, an electrophotographic photosensitive member having the best electrophotographic characteristics can be obtained. Further, in the present invention, as shown in FIGS. 1E and 1F, the photosensitive layer 4 formed by dispersing the fine particle CGM 7 in the layer 6 containing CTM as a main component is placed on the conductive support 1. May be provided directly or via the intermediate layer 5.

Further, a protective layer 8 may be provided on the photosensitive layer 4 if necessary.

Here, when the photosensitive layer 4 has a two-layer structure, C
Which of GL2 and CTL3 is to be the upper layer is determined by selecting either positive or negative charging polarity. That is, in the case of forming a negatively charged photosensitive layer, it is advantageous to use CTL3 as an upper layer, because CTM in the CTL3 is a substance having a high transporting ability for holes.

The CGL constituting the photosensitive layer 4 having a two-layer structure
2 can be formed directly on the conductive support 1 or the CTL 3 or, if necessary, after providing an intermediate layer such as an adhesive layer or a blocking layer, by the following method. (1) Vacuum evaporation method (2) Method of applying a solution in which CGM is dissolved in an appropriate solvent (3) CGM is made into fine particles in a dispersion medium by a ball mill, sand grinder, or the like, and mixed and dispersed with a binder as necessary. A method of applying a dispersion obtained by the above method.

That is, specifically, a vapor deposition method such as vacuum evaporation, sputtering, or CVD, or a coating method such as dipping, spray, blade, or roll method is arbitrarily used.

The thickness of CGL2 thus formed is preferably 0.01 μm to 5 μm, and more preferably 0.05 μm to 3 μm.

Although the thickness of the CTL 3 can be changed as required, it is usually preferably 5 μm to 40 μm.
The composition ratio of the CTL 3 is preferably 0.1 to 5 parts by weight of the binder with respect to 1 part by weight of the CTM of the present invention. It is preferable to use the binder in a range of 5 parts by weight or less with respect to parts.

When the CGL is of a dispersion type in a binder, the binder is preferably used in an amount of 5 parts by weight or less based on 1 part by weight of the CGM.

The photoreceptor of the present invention has the above-described structure, and has excellent charging characteristics, sensitivity characteristics, and image forming characteristics, as will be apparent from the examples described later. In particular, even when subjected to a repetitive transfer type electrophotographic system, it has little fatigue deterioration and excellent durability.

[0130]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of Photoreceptor Sample 1) 30 g of a polyamide resin CM-8000 (manufactured by Toray Industries, Inc.) was charged into a mixed solvent of 900 ml of methanol and 100 ml of 1-butanol, and dissolved by heating at 50 ° C. This liquid was used to dip-coat on an aluminum drum having an outer diameter of 80 mm and a length of 355.5 mm to form an intermediate layer having a thickness of 0.5 μm.

[0132] Next, a polyvinyl butyral resin S-LEC BX-1 (manufactured by Sekisui Chemical Co., Ltd.) 5 g of methyl ethyl ketone 700 ml, was dissolved in a mixed solvent of cyclohexanone 300 ml, this CGM (Exemplified Compound _F 1 -23) 10
g was mixed and dispersed for 10 hours using a sand mill. Using this solution, dip coating was performed on the intermediate layer, and 0.3 μm
A thick charge generation layer (CGL) was formed.

[0133] Then, CTM (Exemplified Compound _T 1 -1) 20
0 g and a copolymer exemplified compound B- as a CTL binder
200 g of 1 (l: m = 80: 20) was dissolved in 1000 ml of 1,2-dichloroethane. Using this solution, dip coating was performed on the charge generation layer, followed by drying at 100 ° C. for 1 hour to form a charge transport layer (CTL) having a thickness of 20 μm. Thus, a laminated photoreceptor sample 1 including the intermediate layer, the charge generation layer, and the charge transport layer was obtained.

[0134] In the photosensitive member sample 1 Preparation (Preparation of photosensitive member samples 2,3), _T 1 -5 shown the CTM in Tables _1, T 1 -13 photoreceptor samples 2 and in the same manner except that the 3 was produced.

(Preparation of Photoreceptor Sample 4) An intermediate layer was formed on an aluminum drum in the same manner as in the preparation of Photoreceptor Sample 1. 10 g of polyvinyl butyral resin Esrec BX-1 was added to 1,2-dichloroethane 100
0 ml, and CGM (Exemplified Compound P-1) 5
0 g was mixed and dispersed using a sand mill for 20 hours.
Using this solution, dip coating was performed on the intermediate layer,
An m-thick charge generating layer was formed.

[0136] Next, Exemplified Compound _T 1 -4 the CTM, C
The TL binder was used as an exemplary compound B-2 (l: m = 75: 2)
A charge transport layer was formed in the same manner as in the preparation of photoconductor sample 1 except that the sample was changed to 5) to obtain a stacked photoconductor sample 4.

(Preparation of Photoreceptor Sample 5) An intermediate layer was formed on an aluminum drum in the same manner as in the preparation of Photoreceptor Sample 1. Polycarbonate resin Iupilon Z-200 (the Mitsubishi Gas Chemical Co., Ltd.) 10 g was dissolved in 1,2-dichloroethane 1000 ml, this was mixed with CGM (Exemplified Compound _Q 1 -3) 20g, was dispersed for 24 hours using a sand mill. Using this solution, dip coating was performed on the intermediate layer to form a charge generation layer having a thickness of 1.0 μm.

[0138] Next, Exemplified Compound _T 1 -6 of CTM, C
The TL binder was used as an example compound B-7 (l: m = 85: 1)
A charge transport layer was formed in the same manner as in the preparation of photoconductor sample 1 except that the sample was changed to 5) to obtain a stacked photoconductor sample 5.

(Preparation of Photoreceptor Sample 6) An intermediate layer was formed on an aluminum drum in the same manner as in preparation of Photoreceptor Sample 1. Silicone resin KR-5240
100 g of (solid content: 20%) (manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 1000 ml of methyl ethyl ketone, and 20 g of Y-type oxytitanium phthalocyanine (Y-TiOPc) was mixed therein and dispersed using a sand mill for 4 hours. Using this solution, dip coating was performed on the intermediate layer to form a charge generation layer having a thickness of 0.5 μm.

Next, CTM was added to the exemplified compound T ₁ -9,
The TL binder was used as an exemplary compound B-12 (l: m = 70:
A charge transport layer was formed in the same manner as in the preparation of the photoreceptor sample 1 except that the sample was changed to 30) to obtain a laminated photoreceptor sample 6.

(Preparation of Photoconductor Sample 7) Exemplified compound T ₁ -12200 g as CTM and Exemplified compound B-5 (l: m = 80: 2) as a CTL binder
0) 200 g was dissolved in 1000 ml of 1,2-dichloroethane. Using this liquid, an outer diameter of 80 mm and a length of 35
After dip coating on a 5.5 mm aluminum drum, drying was performed at 100 ° C. for 1 hour to form a 20 μm thick charge transport layer.

[0142] Next, Exemplified Compound as CGL binder B-5 (l: m = 80: 20) to 200g was dissolved in 1,2-dichloroethane 1000 ml, mixed with Exemplified Compound _Q 1 _-360g to as CGM, sand mill For 24 hours. Further this solution to dissolve the exemplified compound _T 1 -12 150 g as CTM obtain a coating solution. Spray coating was performed on the charge transport layer using this liquid, and then dried at 100 ° C. for 1 hour to form a charge generation layer having a thickness of 5 μm. Thus, a laminated photoreceptor sample 7 including the charge transport layer and the charge generation layer was obtained.

[0143] it was changed to a compound comprising a structural unit represented in (photoreceptor Comparison Preparation of Sample 8, 9) photoreceptor Sample Preparation 1 CTL binder in _B 1 -1 or _B 1 -7 as respectively shown in Table 1 Except for the above, photoconductor comparative samples 8 and 9 were produced in the same manner.

(Preparation of Photoreceptor Comparative Sample 10) Example 1 Photoreceptor comparative sample 10 was prepared in the same manner as in preparation of photoreceptor sample 1, except that CTM was replaced with the following compound C-1.
Was prepared.

[0145]

Embedded image

-Evaluation of Photoconductor- The obtained photoconductor samples 1 to 5 and comparative samples 8 to 10 were mounted on a "U-Bix3035" (manufactured by Konica Corporation), and
A real copy test was performed for 10,000 copies, and the evaluation was performed by examining the presence or absence of an image defect during the real copy test, the change in the surface potential of the photoconductor before and after the real copy test, and the amount of film thickness wear. Table 1 shows the obtained results. However, the black paper potential Vb in the table is a reflection density of 1.3.
The surface potential and blank potential Vw with respect to the original document are the surface potential with respect to the original document having a reflection density of 0.0, and the residual potential Vr is the surface potential after static elimination.

The photoreceptor sample 6 was set to “U-Bix3035”
(Manufactured by Konica Corporation) (Equipped with a semiconductor laser light source) Mounted on a remodeled machine, adjusted the grid voltage so that Vb became -700 ± 10 [V], and exposed the light of 0.7 mW to the exposed surface potential. Is set to Vw, reversal development is performed at a developing bias of −600 [V], a similar actual test is performed, and a similar evaluation is performed.

The same actual photographing test was performed on the photoconductor sample 7, and the same evaluation was performed. However, "U-Bix303
5 "(manufactured by Konica Corporation) was mounted on a remodeled machine in which the polarity of charging and transfer was changed to positive, and the same actual shooting test was performed.

With respect to the thickness loss due to surface friction,
After 100,000 copies were completed, the thickness of the photoreceptor sample was measured and compared with the initial value.

Regarding the crack, the photoreceptor sample was referred to as “U-
"Bix3035" (manufactured by Konica Corp.) drum cartridge, and left for 1000 hours in a 50 ° C. constant temperature bath with the cleaning roller pressed against the photoreceptor, to examine the presence or absence of cracks every hour.

Table 1 shows the obtained results.

[0152]

[Table 1]

[0153] In Example 2 (Preparation of photosensitive member samples 11 to 17) Example 1 photoconductor sample 1 produced, was prepared photoreceptor sample 11 in the same manner except that instead of Exemplified Compound _T 2 -1 the CTM. Photoconductor samples 12 to 17 were prepared in the same manner as in Preparation of photoconductor samples 2 to 7 except that CTM was changed as shown in Table 1.

[0154] In the photosensitive member sample 11 Preparation (Preparation of photoreceptor comparative sample 18, 19), to indicate the CTL binder in Tables _2, a compound consisting of the structural unit represented by _B 1 -1 or _B 1 -7 Photoconductor comparative samples 18 and 19 were prepared in the same manner, except that the sample was replaced.

(Preparation of Photoreceptor Comparative Sample 20) Example 1 Photoreceptor comparative sample 20 was prepared in the same manner as in preparation of photoreceptor sample 1, except that CTM was replaced by compound C-1 shown below.
Was prepared.

[0156]

Embedded image

The obtained photosensitive member samples 11 to 18 and comparative samples 18 to 20 were evaluated in the same manner as in Example 1. Table 2 shows the results.

[0158]

[Table 2]

[0159] In Example 3 (Preparation of photosensitive member samples 41-47) Example 1 photoconductor sample 1 produced, is to manufacture a photoconductor sample 41 in the same manner except that instead of Exemplified Compound _T 5 -5 a CTM. Photoconductor samples 42 to 47 were prepared in the same manner as in Preparation of photoconductor samples 2 to 7 except that CTM was changed as shown in Table 3.

[0160] In the photosensitive member sample 41 Preparation (Preparation of photoreceptor comparative sample 48 and 49), instead of the compound consisting of the structural unit represented by _B 1 -1 or _B 1 -7 as shown in the CTL binder in Tables 3 Photoconductor comparative samples 48 and 49 were prepared in the same manner except for the above.

(Photosensitive Member Comparative Sample 20) A photosensitive member similar to the photosensitive member comparative sample 20 in Example 2.

The same evaluation as in Example 1 was performed for each of the obtained samples. Table 3 shows the results.

[0163]

[Table 3]

Example 4 (Preparation of Photoreceptor Sample 51) Example 1 An intermediate layer and a charge generation layer were formed on an aluminum drum in the same manner as in the preparation of Photoreceptor Sample 1.

Next, CTM (exemplified compound T ₆ -3) 20
0g and Exemplified Compound B-1 (l:
m = 80: 20) 200 g of 1,2-dichloroethane 1
000 ml. Using this solution, dip coating was performed on the charge generation layer, followed by drying at 100 ° C. for 1 hour.
A charge transport layer having a thickness of 20 μm was formed. In this way,
A laminated photoreceptor sample 51 including an intermediate layer, a charge generation layer, and a charge transport layer was obtained.

[0166] In the photosensitive member sample 51 Preparation (Preparation of photosensitive member samples 52,53), _T 6 -2 to show CTM in Tables _{4, T} 6 -1 and was replaced in a similar fashion photoreceptor sample 52 , 53 were produced.

(Preparation of Photoreceptor Sample 54) An intermediate layer and a charge generation layer were formed on an aluminum drum in the same manner as in Preparation of Photoreceptor Sample 4.

Next, in the preparation of the photoreceptor sample 51, CT
A charge transport layer was formed in the same manner except that M was changed to T ₆ -4. Thus, a laminated photoreceptor sample 54 including the intermediate layer, the charge generation layer, and the charge transport layer was obtained.

(Preparation of Photoreceptor Sample 55) Example 1 An intermediate layer and a charge generation layer were formed on an aluminum drum in the same manner as in preparation of Photoreceptor Sample 5.

Next, in the preparation of the photoreceptor sample 51, CT
It was replaced with M to T ₆ -5 is to form a charge transport layer in the same manner. Thus, a laminated photoreceptor sample 55 including the intermediate layer, the charge generation layer, and the charge transport layer was obtained.

(Preparation of Photoreceptor Sample 56) An intermediate layer and a charge generation layer were formed on an aluminum drum in the same manner as in Preparation of Photoreceptor Sample 6.

Next, in the preparation of the photoreceptor sample 51, CT
It was replaced with M to T ₆ -6 is to form a charge transport layer in the same manner. Thus, a laminated photoreceptor sample 56 including the intermediate layer, the charge generation layer, and the charge transport layer was obtained.

(Preparation of Photoreceptor Sample 57) Example 1 In the preparation of Photoreceptor Sample 57, the CTM in the charge transport layer and the CTM in the charge generation layer were replaced with the exemplified compound T _1-
The charge transport layer in the same manner except that instead of the exemplified compound T ₆ -7 to 12 to obtain a laminated photoreceptor sample 57 made of the charge generating layer.

[0174] In the photosensitive member sample 51 Preparation (Preparation of photoreceptor comparative sample 58, 59), instead of the compound consisting of the structural unit represented by _B 1 -1 or _B 1 -7 as shown in the CTL binder in Tables 6 Photoreceptor comparative samples 58 and 59 were prepared in the same manner except for the above.

(Photosensitive Member Comparative Sample 20) A photosensitive member similar to the photosensitive member comparative sample 20 in Example 2.

The same evaluation as in Example 1 was performed on each of the obtained samples. Table 4 shows the results.

[0177]

[Table 4]

As is clear from Tables 1 to 4, the samples of the present invention can obtain satisfactory values in all of the change in the surface potential of the photoreceptor before and after the actual printing test, the thickness loss, the image evaluation and the crack test. I understood.

[0179]

The photoreceptor of the present invention has excellent electrophotographic performance, exhibits little change in characteristics even after repeated use, and has excellent abrasion resistance, so that it has extremely high printing durability.

[Brief description of the drawings]

FIGS. 1A to 1F are cross-sectional views each showing an example of a mechanical configuration of a photoconductor of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 conductive support 2 carrier generating layer 3 carrier transporting layer 4 photosensitive layer 5 intermediate layer 6 layer containing carrier transporting substance 7 carrier generating substance 8 protective layer

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiaki Takei 2970 Ishikawacho, Hachioji-shi, Tokyo Konica Corporation (56) References JP-A-5-134428 (JP, A) JP-A-63-136051 (JP) , A)

Claims (6)

(57) [Claims] 1. An electrophotographic photosensitive member having a photosensitive layer containing at least a charge generating substance, a charge transporting substance and a binder resin on a conductive support, wherein the photosensitive layer is a structural unit represented by the following general formula (I). And the following general formula (I
An electrophotographic photoreceptor comprising a copolymer having the structural unit represented by I) as a main component and a compound represented by the following general formula (III). Embedded image (Wherein, R ₁ and R ₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group, and R ₃ and R ₄
Represents a hydrogen atom, a halogen atom, and 1 to 6 carbon atoms, respectively.
Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and l and m each represent 1
Represents an integer of ４4. However, R ₁ and R ₂ may be bonded to each other to form a hydrocarbon ring having 4 to 10 carbon atoms. ) (Wherein, R ₅ and R ₆ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group;
p and q each represent an integer of 1-4. ) (In the formula, R ¹ represents an alkyl group, an allyl group, a phenyl group, or an aralkyl group, and R ² represents a phenyl group which may have a substituent.) 2. An electrophotographic photosensitive member having a photosensitive layer containing at least a charge generating substance, a charge transporting substance and a binder resin on a conductive support, wherein the photosensitive layer is a structural unit represented by the following general formula (I). And the following general formula (I
An electrophotographic photoreceptor comprising a copolymer having the structural unit represented by I) as a main component and a compound represented by the following general formula (IV). Embedded image (Wherein, R ₁ and R ₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group, and R ₃ and R ₄
Represents a hydrogen atom, a halogen atom, and 1 to 6 carbon atoms, respectively.
Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and l and m each represent 1
Represents an integer of ４4. However, R ₁ and R ₂ may be bonded to each other to form a hydrocarbon ring having 4 to 10 carbon atoms. ) (Wherein, R ₅ and R ₆ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group,
And q each represent an integer of 1-4. ) (Wherein, X, Y and Z represent a hydrogen atom, a lower alkyl group,
Represents a lower alkoxy group, a phenoxy group or an arylalkoxy group; R ¹ represents a hydrogen atom, a lower alkyl group, an allyl group, a phenyl group, or an aralkyl group;
And 1 represents 1 or 2, and n represents 0 or 1. ) 3. An electrophotographic photosensitive member having a photosensitive layer containing at least a charge generating substance, a charge transporting substance and a binder resin on a conductive support, wherein the photosensitive layer is a structural unit represented by the following general formula (I). And the following general formula (I
An electrophotographic photoreceptor comprising a copolymer having a structural unit represented by I) as a main component and a compound represented by the following general formula (VII). Embedded image (Wherein, R ₁ and R ₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group, and R ₃ and R ₄
Represents a hydrogen atom, a halogen atom, and 1 to 6 carbon atoms, respectively.
Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and l and m each represent 1
Represents an integer of ４4. However, R ₁ and R ₂ may be bonded to each other to form a hydrocarbon ring having 4 to 10 carbon atoms. ) (Wherein, R ₅ and R ₆ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group,
And q each represent an integer of 1-4. ) (Wherein, Ar ₅ , Ar ₆ , and Ar ₇ are each an aryl group; at least one has a substituent; A is an alkylene group which may each have a substituent; an arylene group or a divalent heterocyclic ring) R ₁ represents hydrogen, an alkyl group which may have a substituent, an aralkyl group, or an aryl group.) 4. An electrophotographic photosensitive member having a photosensitive layer containing at least a charge generating substance, a charge transporting substance and a binder resin on a conductive support, wherein the photosensitive layer is a structural unit represented by the following general formula (I). And the following general formula (I
An electrophotographic photoreceptor comprising a copolymer having a structural unit represented by I) as a main component and a compound represented by the following general formula (VIII). Embedded image (Wherein, R ₁ and R ₂ represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group, respectively, and R ₃ and R ₄
Represents a hydrogen atom, a halogen atom, and 1 to 6 carbon atoms, respectively.
Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and l and m each represent 1
Represents an integer of ４4. However, R ₁ and R ₂ may be bonded to each other to form a hydrocarbon ring having 4 to 10 carbon atoms. ) (Wherein, R ₅ and R ₆ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group;
And q each represent an integer of 1-4. ) (Wherein, R ₁ represents an aryl group which may have a substituent, and R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group , A nitro group, an allyl group, an aryl group which may have a substituent, or an aralkyl group, and n represents 0 or 1.) 5. The electrophotographic photosensitive material according to claim 1, wherein the general formula (II) according to claim 1, 2, 3, or 4 is the following structural unit (a). body. Embedded image 6. The method according to claim 1, wherein the general formula (I) is a structural unit (b), and the general formula (II) is a structural unit (a). The electrophotographic photosensitive member according to claim 1, 2, 3, or 4, wherein Embedded image