JPH0713361A - Electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE:To secure high sensitivity and high durability and suppress the deterioration of the image quality in the actual photographing, and the sensitivity deterioraition, by allowing the binder resin of a photosensitive layer to contain the polycarbonate polymer having the specific kind of repetitive structure unit. CONSTITUTION:The binder resin in the photosensitive layer on an electric conductive substrate contains the polycarbonate polymer having the repetitive structure unit represented by the formula or the copolymer thereof. In the formula, R1-R8 is a hydrogen atom, halogen atom, substituted or nonsubstituted alkyl group having the number of carbon atoms of 1-10, cycloalkyl group, and an aryl group., and X is cyclic alkylidene group which has at least two alkyl, cycloalkyl, or aryl substituted groups, and contains the carbon atoms joined with two phenylene rings. In the formation of the photosensitive layer, the polycarbonate polymer containing the repetitive structure unit represented by the formula or the copolymer thereof is dissolved into the nonhalogen solvent and applied.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor and a method for producing the same.

[0002]

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

On the other hand, the surface of the photosensitive member is cleaned by removing adhered toner and removing electric charge, and is repeatedly used for a long period of time.

Therefore, as an electrophotographic photoreceptor, not only the electrophotographic characteristics such as excellent charging characteristics and sensitivity but also small dark decay, but also physical properties such as printing durability, abrasion resistance and scratch resistance upon repeated use. Also, it is required to have good resistance to ozone generated during corona discharge and ultraviolet rays during exposure.

Conventionally, selenium has been used as an electrophotographic photoreceptor.
Inorganic photoconductors having an inorganic photoconductive substance such as zinc oxide and cadmium sulfide as a main component of a photosensitive layer have been widely used. However, since these inorganic photoconductors are harmful to the human body, there is a problem in their disposal.

In recent years, an organic photoconductor using a non-polluting organic substance has been actively developed and put into practical use. Above all, the charge generation function and the charge transport function are shared by different substances,
A function-separated type photoconductor is promising, in which a substance exhibiting each function in accordance with desired characteristics can be selected from a wide range.

However, such an organic photoconductor is generally inferior in mechanical strength to an inorganic photoconductor, and a scratch or a scratch due to a mechanical external force such as a cleaning blade or a developing brush is generated.
There is a problem such as wear. These cause deterioration of the output image, and a stable and clear image cannot always be obtained.

The above problems are largely due to the characteristics of the binder resin contained in the outermost layer of the photoreceptor.

In recent years, various researches and developments have been carried out, and a laminated-type photoreceptor in which the functions of charge generation and charge transport are shared by the respective layers has been proposed. Conventionally, such a laminated organic photoreceptor is mainly used for negative charging, and has a structure in which a thin charge generation layer is provided on a conductive support and a relatively thick charge transport layer is provided thereon.

As a binder used in such a photoreceptor, it is well known that a bisphenol A type polycarbonate resin exhibits good characteristics in terms of charging characteristics, sensitivity, residual potential and repetitive characteristics. There is.

[0011]

However, as a result of investigations conducted by the present inventors, the bisphenol A type polycarbonate resin has a high polymer crystallinity, so that its solution easily causes gelation. It has the drawback that it cannot be used for a day. Further, when a film is formed by coating, crystalline polycarbonate is likely to be deposited on the surface of the film during the formation of a coating film to form a convex portion, which causes tailing of the coating film and reduces the yield, or When used as a body, toner adheres to the convex portions and remains without being cleaned, and image defects due to so-called poor cleaning are likely to occur.

When the electrophotographic photosensitive member using the bisphenol A type polycarbonate resin as a binder is used as a photosensitive member of an electrophotographic copying machine, the surface of the photosensitive layer is scratched by being rubbed with a magnetic brush or a cleaning blade. It has the drawback that the photosensitive layer is gradually worn away.

On the other hand, since the high image quality and the good copying workability depend on the uniformity of the film thickness and the surface uniformity of the photoconductor, the coating composition for forming the photoconductor constituting layer or the coating,
Defects in the film surface such as citrus peel, pinholes, coating streaks, and cracks (solvent cracks) caused by drying are serious problems in terms of copying characteristics and production technology.

In response to the above-mentioned troubles, introduction of a substituent having a fluorine atom at a carbon between phenylene rings of bisphenol type polycarbonate (JP-A-63-65444), substitution of an alkyl group or a halogen atom on the phenylene ring. (JP 63-1
48263), or a copolymer of monomers in which both phenylene rings are substituted with a phenyl group or a cyclohexyl group (JP
No. 1-269942, No. 1-269943), etc. have been proposed, but they do not have sufficient surface strength and surface smoothness, are vulnerable to abrasion and scratches, and deteriorate in image quality during repeated use. There are problems such as sensitivity deterioration due to wear reduction.

On the other hand, conventional polycarbonates which are often used as binders for photosensitive layers have often used halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and monochlorobenzene, which have high solubility, as solvents. It was

On the other hand, in recent years, voices concerning environmental protection have been increasing, and regulations on harmful substances and substances polluting the environment have been strengthened. Under such circumstances, the above-mentioned halogenated hydrocarbons may not be used in the future, or the amount thereof may be limited.

Therefore, the binder resin for the photosensitive layer includes hydrocarbons such as toluene and benzene, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol and butanol. Those having high solubility in ethers, ethers such as tetrahydrofuran, 1,4-dioxane, furan and furfural, acetals and the like are preferable.

Suitable resins for the undercoat layer and the charge generation layer have been found out and have already been put to practical use. However, when using a resin other than a polycarbonate resin that dissolves in the above solvent for the charge transport layer, low sensitivity, electrophotographic characteristics such as increase in residual potential due to repeated use, and abrasion during repeated use, Deterioration of image quality due to scratches,
There is a problem in mechanical durability such as sensitivity deterioration due to film wear,
No resin satisfying these requirements has been found.

[0019]

The object of the present invention is high sensitivity, high durability,
The purpose of the present invention is to provide a photoconductor with less deterioration in image quality and sensitivity during actual shooting. Another purpose is to provide a photoconductor prepared using a photoconductor coating liquid that does not use halogenated hydrocarbons and has little environmental pollution. is there.

[0020]

An object of the present invention is to provide an electrophotographic photosensitive member comprising a conductive layer and a photosensitive layer provided on the conductive substrate.
The binder resin of the photosensitive layer contains a polycarbonate polymer or a copolymer thereof having a repeating structural unit represented by the general formula [I] in which the structural specifications described in "Chemical formula 1" and "Chemical formula 2" are specified. The electrophotographic photoreceptor and the polycarbonate or the copolymer thereof are dissolved in a non-halogen solvent and coated, and the solution is provided by the method for producing an electrophotographic photoreceptor.

Specific examples of R _{1 to} R _{8 in} the above general formula [I] are hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, 1-methylpropyl group, 2- Methylpropyl group, t-butyl group, pentyl group,
Isopentyl group, hexyl group, isohexyl group, phenyl group, tolyl group, xylyl group, trimethylphenyl group,
Examples thereof include an ethylphenyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a fluorine atom, a chlorine atom and a bromine atom.

Specific examples of the cyclic alkylidene group in the above general formula [I] and at least two or more substituents bonded to X include methyl group, ethyl group, propyl group, isopropyl group, butyl group and 1-methyl group. Examples thereof include propyl group, 2-methylpropyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, phenyl group, tolyl group, cyclopentyl group and cyclohexyl group.

The polycarbonate composed of the repeating unit represented by the general formula [I] includes, for example, one or more dihydric phenols represented by the following general formula (A) and a carbonate precursor such as phosgene. It can be obtained by condensation polymerization in the presence of a suitable acid binder in a suitable neutral polar solvent, or by a method such as a transesterification reaction between the dihydric phenol (A) and the bisaryl carbonate.

[0024]

[Chemical 3]

As the above-mentioned acid binder, various known ones can be used, and specifically, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, organic bases such as pyridine, and mixtures thereof. Is used.

As the solvent, for example, methylene chloride, chlorobenzene, xylene, etc. are used. Furthermore, in order to accelerate the condensation polymerization reaction, a catalyst such as a tertiary amine or quaternary ammonium salt such as triethylamine is added, and a molecular weight regulator such as pt-butylphenol or phenylphenol is added to adjust the degree of polymerization. It is desirable to carry out the reaction.

If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.
The reaction is usually carried out at a temperature in the range of 0 to 150 ° C, preferably 5 to 40 ° C. It is desirable to maintain the pH of the reaction system at 10 or more during the reaction.

On the other hand, in the latter transesterification method, the dihydric phenol and the bisaryl carbonate are mixed and reacted at a high temperature under reduced pressure. Reaction is usually 15
Performed in a temperature range of 0 to 350 ° C, preferably 200 to 300 ° C,
The final degree of vacuum is preferably 1 mmHg or less, and phenols derived from the bisaryl carbonate produced by the transesterification reaction are distilled out of the system. The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon, and the reaction may be carried out by appropriately adding the above-mentioned molecular weight modifier or antioxidant.

Examples of the polycarbonate copolymer used in the present invention include the above general formula [I] and the following general formula [I
I] includes a repeating structural unit.

[0030]

[Chemical 4]

R _{9 to} R ₁₆ : hydrogen atom, halogen atom, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, cycloalkyl group, aryl group.

Y represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, an aryl-substituted alkylidene group, a sulfonyl group, a sulfide group or an ether group, and two phenylene rings are directly bonded without interposing Y. You may.

As these copolymers, one kind or two or more kinds of the above dihydric phenols (A) and one or more kinds of the following divalent phenols (B) are suitable and a carbonate precursor such as phosgene. Bond polymerization in the presence of a suitable acid binder in a suitable solvent, or by a method such as transesterification of these dihydric phenols (A) and dihydric phenols (B) with bisaryl carbonate You can

[0034]

[Chemical 5]

Specific examples of the polycarbonate having a repeating unit represented by the above general formula [II] are disclosed in JP-A-50-9.
8332, 60-172045, 61-62040, JP 1-26994
2, No. 1-269943, No. 1-273046, No. 4-268365, etc.

The polycarbonate of the present invention may be a homopolymer consisting of one type of repeating unit represented by the above general formula [I], or may be composed of two or more types of the general formula [I] in any proportion. It may be a copolymer. These are 1
They may be used alone or in combination of two or more.

As another polycarbonate copolymer of the present invention, one or more kinds of repeating units represented by the general formula [I] and one or more kinds of the general formula [II] are represented. And the repeating unit Regarding the ratio of the repeating units [I] and [II], at least [I] is at least 20 mol%, preferably at least 30 mol%.

The polycarbonate and / or the polycarbonate copolymer of the present invention can be used in combination with other known binders such as other known polycarbonates as long as the object of the present invention is not impaired.

The polycarbonate of the present invention has a weight average molecular weight of 5,000 to 300,000, preferably 20,000 to 200,000.

As the solvent for the polycarbonate polymer or copolymer used in the present invention, a halogen-based solvent such as methylene chloride, ethylene chloride or chlorobenzene can be used, but a non-halogen-based solvent is particularly preferable in view of environmental issues.

As the non-halogen solvent, ketones ... Methyl ethyl ketone (MEK), methyl butyl ketone, methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), cyclohexanone, isophorone, diacetone alcohol esters ... Ethyl acetate, propyl acetate , Butyl acetate,
Isopropyl acetate, furans ... Tetrahydrofuran ethers ... Dioxane hydrocarbons ... Benzene, toluene, xylene, ethylbenzene and the like are preferable.

More preferred are MEK, toluene and ethyl acetate, but two or more of them may be mixed and used in view of coating evaporation rate, viscosity, film forming property and the like. In this case, organic solvents other than those mentioned above are also advantageously used.

The concentration of the solution (% by weight of polycarbonate with respect to the solvent) is usually 1 to 30% by weight, preferably 5 to 20%
Is.

Examples of the compounds of the polycarbonate and the polycarbonate copolymer of the present invention include the following.

[0045]

[Chemical 6]

[0046]

[Chemical 7]

[0047]

[Chemical 8]

[0048]

[Chemical 9]

[0049]

[Chemical 10]

[0050]

[Chemical 11]

[0051]

[Chemical 12]

[0052]

[Chemical 13]

Examples of the binder that may be used in combination with the carbonate copolymer used as the binder include the following.

(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, styrene-methyl methacrylate copolymer, etc.) (9) Acrylonitrile copolymer resin (for example, vinylidene chloride-acrytronitrile copolymer, etc.) (10) Vinyl chloride-vinyl acetate copolymer Combined (11) Vinyl chloride-vinyl acetate-maleic anhydride copolymer (12) Silicone resin (13) Silicone-alkyd resin (14) Phenolic resin (for example, phenol-formaldehyde resin, cresol-formaldehyde resin,
Etc.) (15) Styrene-alkyd resin (16) Poly-N-vinylcarbazole (17) Polyvinyl butyral (18) Polyvinyl formal (19) Polyhydroxystyrene These binders may be used alone or as a mixture of two or more kinds. It can be used in combination with the carbonate according to the invention.

Next, the photoconductive material used in the present invention, that is, the carrier generating substance and the carrier transporting substance will be described.

In the photoreceptor of the present invention, the organic pigments shown in the following representative examples are used as the carrier generating substance (CGM).

(1) Azo pigments such as monoazo pigments, bisazo pigments, triazo pigments and metal complex salt azo pigments (2) Perylene pigments such as perylene anhydrides, perylene imides (3) Anthraquinone derivatives, anthanthrone derivatives, dibenz Polycyclic quinone pigments such as pyrenequinone derivatives, pyranthrone derivatives, violanthrone derivatives and isoviolanthrone derivatives (4) Indigoid pigments such as indigo derivatives and thioindigo derivatives (5) Phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine In the photographic photoreceptor, it is preferable to use an organic pigment such as a fluorenone-based disazo pigment, a fluorenylidene-based disazo pigment, a polycyclic quinone pigment, a metal-free phthalocyanine pigment or an oxytitanyl-phthalocyanine pigment as the CGM. In particular, when the following fluorenone-based disazo pigments, fluorenylidene-based disazo pigments, polycyclic quinone pigments, and X- and τ-type metal-free phthalocyanines are used in the present invention, markedly improved effects in terms of sensitivity, durability and image quality are exhibited. .

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

[0059]

[Chemical 14]

X ₁ and X ₂ are each a halogen atom,
It represents an alkyl group, an alkoxy group, a nitro group, a cyano group, a hydroxy group or a substituted or unsubstituted amino group. p
And q each represent an integer of 0, 1 or 2, and p and q
When is 2, X ₁ and X ₂ may be the same or different groups. A represents a group represented by the following general formula [F ₁ -1].

[0061]

[Chemical 15]

In the formula, Ar represents a fluorinated hydrocarbon group or an aromatic carbocyclic group having a substituent or an aromatic heterocyclic group. Z
Represents a group of non-metal atoms necessary for forming a substituted or unsubstituted aromatic carbocycle or a substituted or unsubstituted aromatic heterocycle. m and n each represent an integer of 0, 1 or 2. However, m and n are not 0 at the same time.

Specific examples of the fluorenone-based disazo pigment used in the present invention are shown below, but the invention is not limited thereto.

[0064]

[Chemical 16]

[0065]

[Chemical 17]

[0066]

[Chemical 18]

The fluorenone 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, the method of Japanese Patent Application No. 62-304862.

The fluorenylidene-based disazo pigment used in the present invention is represented by the following general formula [F ₂ ].

[0069]

[Chemical 19]

Z: the following two groups which are substituted or unsubstituted; an atomic group necessary for constituting an aromatic carbocycle or an aromatic heterocycle Y: a hydrogen atom, a hydroxy group, a carboxy group, or an ester group thereof, a sulfo group Group, substituted or unsubstituted two groups described below; carbamoyl group, sulfamoyl group R ₁ : hydrogen atom, substituted or unsubstituted four groups described below; alkyl group, amino group, carbamoyl group, carboxy group or ester group thereof Or a cyano group Ar: a substituted or unsubstituted aryl group R ₂ : a substituted or unsubstituted three groups described below; an alkyl group, an aralkyl group or an aryl group.

Specific examples of the disazo pigment represented by the above general formula [F ₂ ] which is effective in the present invention include those represented by the following structural formulas, which should be used in the present invention. The disazo pigment is not limited.

[0072]

[Chemical 20]

[0073]

[Chemical 21]

[0074]

[Chemical formula 22]

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

[0076]

[Chemical formula 23]

In each formula, X represents a halogen atom, a nitro group, a cyano group, an acyl group or a carboxy group, and n is 0 to 0.
The integer of 4 and m represent the integer of 0-6.

Specific examples of the polycyclic quinone pigments represented by the above general formulas [Q ₁ ] to [Q ₃ ] used in the present invention are shown below, but the invention is not limited thereto.

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

[0080]

[Chemical formula 24]

Specific examples of the dibenzpyrenequinone pigment represented by the general formula [Q ₂ ] are as follows.

[0082]

[Chemical 25]

Specific examples of the compound of the pyranthrone pigment represented by the general formula [Q ₃ ] are as follows.

[0084]

[Chemical formula 26]

The above-mentioned general formula [Q ₁ ] used in the present invention:
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, photoconductive metal-free phthalocyanine and all of its derivatives can be used.
Type, β type, τ, τ ′ type, η, η ′ type, X type, and
The crystal form and its derivatives described in 62-103651 can be used. In particular, it is desirable to use the τ, X, K / R-X type. U.S. Pat. No. 3, regarding X-type metal-free phthalocyanine,
357,989, and the τ-type metal-free phthalocyanine is described in JP-A-58-182639. K / R-X
The mold is CuKα, 1.541Å as described in JP-A-62-103651.
At the Bragg angle (2θ ± 0.2 degrees) with respect to X-rays, it has major peaks at 7.7, 9.2, 16.8, 17.5, 22.4, 28.8 degrees, and a peak intensity ratio of 16.8 degrees to a peak intensity of 9.2 degrees. The phthalocyanine is characterized by having a peak intensity ratio of 0.8 to 1.0 and a peak intensity ratio of 28.8 degrees to 22.4 degrees of 0.4 or more. Carrier Transport Material (CTM) that can be used in the present invention
As, is not particularly limited, for example, oxazole derivative, oxadiazole derivative, thiazole derivative, thiadiazole derivative, triazole derivative, imidazole derivative, imidazolone derivative, imidazolidine derivative,
Bisimidazolidine derivative, styryl compound, hydrazone compound, pyrazoline derivative, amine derivative, oxazolone derivative, benzothiazole derivative, benzimidazole derivative, quinazoline derivative, benzofuran derivative,
Examples include acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene and the like.

Examples of the dispersion medium of the organic pigment used in the present invention include hydrocarbons such as hexane, benzene, toluene, xylene, methylene chloride, methylene bromide, 1,2-dichloroethane, syn-tetrachloroethane and 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,
Alcohols such as ethylene glycol, methyl cellosolve, ethyl cellosolve, and cellosolve acetate, and derivatives thereof,
Ethers such as tetrahydrofuran, 1,4-dioxane, furan and furfural, acetals, amines such as pyridine and butylamine, diethylamine, ethylenediamine and isopropanolamine, nitrogen compounds such as amides such as N, N-dimethylformamide and fatty acids. And phenols, sulfur such as carbon disulfide and triethyl phosphate, phosphorus compounds and the like.

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

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 dianhydride,
Mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, paranitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, bulmannyl, Dichlorodicyanoparabenzoquinone, anthraquinone, dinitroanthraquinone, 2,7-dinitrofluorenone, 2,4,7-trinitrofluorenone,
2,4,5,7-Tetranitrofluorenone, 9-fluorenylidene [dicyanomethylene malonodinitrile], polynitro-9
-Fluorenylidene- [dicyanomethylene malonodinitrile], picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid,
Examples include 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, mellitic acid, and other compounds having a high electron affinity. Further, the addition ratio of the electron-accepting substance is a weight ratio of the organic pigment used in the present invention: the electron-accepting substance = 100: 0.01-200, preferably 100: 0.1-1.
00.

The addition ratio of the electron-accepting substance to the layer is, by weight ratio, total CTM: electron-accepting substance = 100: 0.01-100,
It is preferably 100: 0.1 to 50.

In addition, organic amines 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-59-218447 and JP-A-62-8160.

In addition, the photoreceptor of the present invention may further contain an ultraviolet absorber or the like for the purpose of protecting the photosensitive layer, if necessary, and may also contain a dye for correcting color sensitivity. In the protective layer according to the present invention, the workability and physical properties are improved (crack prevention,
If necessary, a thermoplastic resin is added for the purpose of imparting flexibility, etc.
It is possible to contain less than 50 wt%.

Further, 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 copolymer, casein, polyamide, N-alkoxymethylated nylon, starch and the like are used.

As the electroconductive support used in the construction of the electrophotographic photosensitive member of the present invention, the following are mainly used, but the electroconductive support is not limited thereto.

1) Metal plate such as aluminum plate and stainless plate.

2) A thin metal layer of aluminum, palladium, gold or the like provided on a support such as paper or plastic film by laminating or vapor deposition.

3) A layer of a conductive compound such as a conductive polymer, indium oxide or tin oxide is applied or vapor-deposited on a support such as paper or a plastic film. The photoconductor of the present invention is a photoconductor comprising a laminate of a charge generation layer (CGL) containing CGM as a main component and a charge transport layer (CTL) containing CTM according to the present invention as a main component on a conductive support. Provide layers. This photosensitive layer may be provided via an intermediate layer provided on the conductive support. Thus, when the photosensitive layer has a two-layer structure, an electrophotographic photoreceptor having the best electrophotographic characteristics can be obtained. In the present invention,
Fine particle-shaped CGM in the CTL containing CTM as a main component
A photosensitive layer in which is dispersed may be provided directly on the conductive support or via an intermediate layer.

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

Further, CGL which constitutes a photosensitive layer having a two-layer structure
Can be formed by the following method directly on the conductive support or on the surface of which an intermediate layer such as an adhesive layer or a blocking layer is provided, if necessary.

(1) Vacuum evaporation method (2) Method of applying a solution of CGM dissolved in a suitable solvent (3) CGM is made into fine particles in a dispersion medium by a ball mill, a sand grinder or the like, and if necessary, a binder. A method of applying a dispersion obtained by mixing and dispersing with.

Specifically, specifically, a vapor deposition method such as vacuum vapor deposition, sputtering, CVD or a coating method such as dipping, spraying, blade or roll method may be used.

The thickness of the CGL thus formed is preferably 0.01 μm to 5 μm, more preferably
It is 0.05 μm to 3 μm.

The thickness of the CTL can be changed if necessary, but is usually preferably 5 μm to 30 μm. This CT
The composition ratio in L 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, but in the case of forming a photosensitive layer in which fine particle CGM is dispersed,
It is preferable to use the binder in an amount of 5 parts by weight or less with respect to 1 part by weight of CGM.

When the CGL is a dispersion type binder in the binder, it is preferable to use 5 parts by weight or less of the binder with respect to 1 part by weight of the CGM.

The photoconductor of the present invention has the above-mentioned constitution, and is excellent in charging property, sensitivity property and image forming property as will be apparent from the examples described later. In particular, even when it is subjected to a repetitive transfer type electrophotographic method, it has little fatigue deterioration and excellent durability.

[0106]

EXAMPLES Examples of the present invention will be specifically described below.

Example 1 30 g of polyamide resin CM-8000 (manufactured by Toray Industries, Inc.) was put into a mixed solution of 900 ml of methanol and 100 ml of 1-butanol, and the mixture was heated to 50 ° C.
It melted by heating. This solution was dip-coated on an aluminum drum substrate having an outer diameter of 80 mm and 355.5 mm to form a 0.3 μm intermediate layer. Next, 10 g of polyvinyl butyral resin S-REC BM-S (manufactured by Sekisui Chemical Co., Ltd.) was dissolved in 1000 ml of methyl ethyl ketone, and the exemplified compound (F
₁ -23) was mixed with 30g, was dispersed for 20 hours using a sand mill. Using this solution, dip coating on the intermediate layer, 0.5
A μm thick CGL was formed.

Next, CTM (T-1) 150 having the following structural formula
g and 200 g of the exemplified compound (A9) as a CTL binder were dissolved in 1000 ml of methyl ethyl ketone.

[0109]

[Chemical 27]

Using this solution, dip coating was performed on the CGL, followed by drying at 100 ° C. for 60 minutes to obtain a CT film having an average film thickness of 22 μm.
L was formed.

In this way, a laminated photoreceptor sample 1 comprising the intermediate layer, CGL and CTL was obtained.

Example 2 In Example 1, the CTL binder was used as an example compound (A
A laminated photoreceptor sample 2 was obtained in the same manner except that the procedure 3) was performed.

Example 3 In Example 1, the CTL binder was used as an example compound (A
A laminated photoreceptor sample 3 was obtained in the same manner except that the procedure 1) was performed.

Example 4 In Example 1, the CTL binder was used as an example compound (A
Laminated photoreceptor sample 4 was obtained in the same manner except that the procedure 6) was used.

Example 5 In Example 1, the CTL binder was used as an example compound (A
A laminated photoconductor sample 5 was obtained in the same manner except that the step 2) was performed.

Example 6 Polyamide resin laccamide 5003 (manufactured by Dainippon Ink and Chemicals, Inc.)
15 g was put into a mixed solution of 800 ml of methanol and 200 ml of 1-butanol, and dissolved by heating at 50 ° C. Outer diameter using this liquid
Dip coating was performed on an 80 mm, 355.5 mm aluminum drum substrate to form a 0.5 μm intermediate layer.

Next, silicone resin KR-5240 (solid content
20%) (produced by Shin-Etsu Chemical Co., Ltd.) 10 g of methyl ethyl ketone 700 m
l, was dissolved in a mixed solvent of cyclohexanone 300 ml, which in the exemplified compound as a CGM (Q ₁ -3) were mixed with 10 g, it was dispersed for 20 hours using a sand mill. This solution was applied onto the intermediate layer by dip coating to form a 1.0 μm thick CGL.

Next, CTM (T-2) 150 having the following structural formula
g and 150 g of the exemplified compound (A15) as a CTL binder were dissolved in 1000 ml of ethyl acetate.

[0119]

[Chemical 28]

Using this solution, dip coating was performed on the CGL, followed by drying at 100 ° C. for 60 minutes to obtain a CT film having an average film thickness of 20 μm.
L was formed.

Thus, a laminated photoreceptor sample 6 including the intermediate layer, CGL and CTL was obtained.

Example 7 In Example 6, the CTL binder was used as an exemplified compound (A1).
A laminated photoreceptor sample 7 was obtained in the same manner except that the step 2) was performed.

Example 8 In Example 6, the CTL binder was used as an exemplified compound (A1).
A laminated photoreceptor sample 8 was obtained in the same manner except that step 6) was performed.

Example 9 In Example 6, the CTL binder was used as an exemplified compound (A1).
A laminated photoreceptor sample 9 was obtained in the same manner except that the above step 4) was performed.

Example 10 The same procedure as in Example 1 was performed until the formation of the intermediate layer. Next, polyvinyl butyral resin S-REC BX-1 (manufactured by Sekisui Chemical Co., Ltd.) (2.5 g) was dissolved in 1000 ml of methyl isobutyl ketone, and 10 g of the exemplified compound (F ₂ -8) as CGM was mixed therein, and a sand mill was used for 10 hours. Dispersed. This solution is applied onto the above intermediate layer by dip coating to form a 0.5 μm thick CGL.
Was formed.

Next, in the same manner as in Example 6, except that the exemplified compound (B4) was used as the CTL binder, CT was performed in the same manner.
L was formed.

In this way, a laminated photoreceptor sample 10 including the intermediate layer, CGL and CTL was obtained.

Example 11 In Example 10, the CTL binder was used as an example compound (B
A laminated photoreceptor sample 11 was obtained in the same manner except that the step 7) was performed.

Comparative Example Comparative Example (1) A laminated photoreceptor comparative sample (1) was obtained in the same manner as in Example 1 except that the polycarbonate resin having the following structural formula was used as the CTL binder.

[0130]

[Chemical 29]

Comparative Example (2) A laminated photoreceptor comparative sample (2) was obtained in the same manner as in Example 6 except that the polycarbonate resin having the following structural formula was used as the CTL binder.

[0132]

[Chemical 30]

-Evaluation of coating liquid-MEK10 of polycarbonate used in Examples and Comparative Examples
The presence or absence of turbidity was visually confirmed when the weight% solution was left at room temperature (23 ° C) for 1 week. Yes (x), no (○).

The results are shown together with the photoreceptor evaluation result table.

-Measurement of Viscosity- A 7.5% by weight MEK solution of the polycarbonate of the present invention was used at room temperature (23 ° C) using a B-type viscometer immediately after preparation and left at room temperature (23 ° C) for 1 month. The subsequent viscosity was measured and evaluated by the ratios shown below. The results are shown together with the photoreceptor evaluation results.

Vis ratio = viscosity after 1 month / viscosity after preparation-Evaluation of photoconductor-The photoconductor samples obtained in Examples 1 to 11 and Comparative Examples (1) and (2) were subjected to "U-Bix4045". (Manufactured by Konica Corp.), a 100,000-copy actual shooting test was performed, and the presence or absence of image defects before and after the actual shooting test, changes in surface potential, and film thickness loss were examined.

Black paper potential Vb: Surface potential for a document having a reflection density of 1.3 White paper potential Vw: Surface potential for a document having a reflection density of 0.0 Residual potential Vr: Surface potential after static elimination 100,000 copies completed for film wear due to surface friction After that, the film thickness of the photoconductor was measured and compared with the initial stage.

The results are shown in Table 1 below.

[0139]

[Table 1]

[0140]

EFFECT OF THE INVENTION It is possible to obtain a photoconductor having high sensitivity, high durability, and high practicality, and moreover, a production method free from environmental pollution can be obtained.

Claims (2)

[Claims] 1. An electrophotographic photoreceptor comprising a photosensitive layer provided on a conductive substrate, wherein the binder resin of the photosensitive layer has a polycarbonate polymer having a repeating structural unit represented by the following general formula [I] or a copolymer thereof. An electrophotographic photoreceptor containing a polymer. [Chemical 1] Wherein, R ₁ to R ₈ represents a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, three groups of the aryl group. X represents a cyclic alkylidene group having at least two or more alkyl, cycloalkyl and aryl substituents and containing a carbon atom bonded to two phenylene rings. ] 2. When forming a photosensitive layer by coating a solution containing at least a photoconductive material and a binder on a conductive substrate, a repeating structural unit represented by the following general formula [I] is used as the binder. A method for producing an electrophotographic photoreceptor, which comprises dissolving a polycarbonate polymer containing the same or a copolymer thereof in a non-halogen solvent and applying the solution. [Chemical 2] [In the formula, R _{1 to} R ₈ represent three groups of a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and an aryl group. Further, X represents a cyclic alkylidene group which has at least two or more alkyl, cycloalkyl and aryl substituents and which is formed by containing carbon atoms bonded to two phenylene rings. ]