JPS62296152A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain a stable electrophotographic sensitive body having excellent sensitivity, dark attenuation characteristic, electric charge acceptability and repeating characteristic by providing an intermediate layer contg. a specific resin between a conductive substrate and photosensitive layer. CONSTITUTION:The intermediate layer contg. the resin consisting of the monomer component expressed by the formula shown is provided between the conductive substrate and the photosensitive layer. In the formula, X is an atom selected from an oxygen atom, sulfur atom and nitrogen atom, and has a substituent of a hydrogen atom, alkyl group or aryl group when X is the nitrogen atom. R1, R2 are a hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group, amino group and may form a ring between R1 and R2. The content of said resin is >=10wt%, more preferably 20-90wt%. A dopant of an electron acceptive material or electron donative material may be doped into the intermediate layer. Other resins, for example, resins such as acrylic resin and methacrylic resin may be added together with said resin to the above-mentioned layer. The content thereof is preferably 10-80wt% of the entire resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor that is excellent in various properties such as sensitivity, dark decay characteristics, charge acceptance, and repeatability.

[Background of the Invention] Conventionally, the photosensitive layer used in electrophotographic photoreceptors includes S
Inorganic photoconductive materials such as E, CdS, and ZnO are widely used. On the other hand, in recent years, research has been actively conducted on the use of organic photoconductive substances in place of the inorganic photo/9-electroconductive substances. Compared to inorganic photoconductive materials, such organic photoconductive materials have advantages such as a highly flexible photosensitive layer, easy production, and the ability to obtain photoreceptors with stable electrophotographic properties at lower cost. Many proposals have been made in recent years.

Among them, a type of photoreceptor in which the photosensitive layer is functionally separated into a charge generation layer and a charge transport layer has been put into practical use because of its high sensitivity and the ability to select a variety of materials depending on the function.

However, such type A photoreceptors usually have a charge generation layer and a charge transport layer coated on a conductive substrate in order, and most of the incident light is absorbed by the charge generation layer to generate carriers. Furthermore, the structure is such that generated carriers are injected into the charge (-+ transport layer) without being deactivated by recombination or capture.

On the other hand, it is known that it is effective to provide an intermediate layer between the conductive substrate and the photosensitive layer in order to prevent deterioration of the electrical properties of the photosensitive layer and to prevent charge injection from the conductive substrate to the photosensitive layer. There is.

Examples of resins used for this intermediate layer include nitrocellulose resin (see JP-A-48-3544), polyvinyl butyral resin (see JP-A-50-28837 and JP-A-59-36258), Polyvinyl alcohol resin (see JP-A-52-100240), nylon resin soluble in alcohol solvents (JP-A-52-2563)
8 Ig), polyvinyl formal resin (see JP-A-57-90639-112), water-soluble polyvinyl butyral resin (see JP-A-58-106549), blends of polyvinyl butyral resin and phenol resin (see JP-A-58-106549), (see Japanese Patent Publication No. 59-36259) are known, and resins such as polyvinyl methyl ether, polyvinylimidazole, polyethylene oxide, polyurethane, polyamide, melamine, polyvinylpyrrolidone, cellulose ester, casein, and gelatin are also known. .

Furthermore, it is known that a donor substance or an acceptor substance is added to the intermediate layer to improve the Ti and gas characteristics of the photoreceptor (JP-A-60-140357, JP-A-59-1708.4F1). reference).

[Problems to be Solved by the Invention] However, the intermediate layer can prevent deterioration of the electrical properties of the photosensitive layer without reducing the sensitivity of the photosensitive member, and prevent charge injection from the σ-conductive substrate to the photosensitive layer. It is desirable that the device has all the various performances that enable prevention.

However, it is difficult to satisfy all of these various performances in 'f'r TF, and the reality is that this requirement cannot be met using any of the conventionally known intermediate layers. That is, for example, Japanese Patent Application Laid-Open No. 140357/1983 discloses a photoreceptor that has the function of serving as a carrier of the same polarity as the carrier that is injected from the support into the belt or as a majority carrier. Only vague details such as adding an acceptor or donor compound to the intermediate layer are disclosed as specific implementation means, making it difficult to implement in practice. Furthermore, JP-A No. 59-170845 discloses an undercoat layer using an acceptor organic substance with a soft mobility of more than a certain value. However, it has the disadvantage that it leads to a decrease in charge acceptance ability.

Therefore, the present invention has (1) good sensitivity and excellent dark decay characteristics;
To obtain an electrophotographic photoreceptor with good charge acceptability, ■ To obtain an electrophotographic photoreceptor with excellent repeatability and stable acceptance potential, residual potential, and sensitivity characteristics even after repeated charging, exposure, and removal. The purpose is to obtain.

[Means for Solving the Problems] The present inventor has conducted extensive research to solve the above problems, and as a result has arrived at the present invention.

That is, the electrophotographic photoreceptor according to the present invention is an electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, in which a monomer component represented by the following general formula (hereinafter, the present invention It is characterized by having an intermediate layer containing a resin consisting of a monomer component (monomer component).

In the general formula, X is an atom selected from an oxygen atom, an atom atom, or a nitrogen atom; when X is a nitrogen atom, a hydrogen atom, an alkyl group (e.g., methyl group, ethyl group, etc.) or an aryl group ( For example, it has a substituent such as a phenyl group.

R1 and R2 are hydrogen atoms, halogen atoms, alkyl groups (
R
A ring (for example, a 5- to 7-membered ring) may be formed between 9 and R3.

The present invention will be explained in detail below.

In the present invention, the conductive substrate includes aluminum,
Metals such as brass and stainless steel, or polyethylene terephthalate, nylon, polyarylate, polyimide,
Polymer materials such as polycarbonate, materials such as hard paper are molded into a drum shape, or they are used as sheet-like films or foils.

When using insulating materials, it is necessary to conduct conductive treatment, which requires impregnation with a conductive substance.

Methods include laminating metal foil (for example, aluminum foil), vapor deposition of metal (for example, aluminum, indium, tin oxide, yttrium, etc.), and conductive processing.

In the present invention, the intermediate layer preferably contains 10% by weight or more of a resin containing the fluorine component of the present invention (hereinafter referred to as the resin of the present invention), and more preferably 20 to 90% by weight. From the viewpoint of achieving the objectives of the present invention in improving sensitivity, dark decay, charge acceptance characteristics, and repeatability, the resin is preferably 1% by weight or more, and the composition of the intermediate layer is preferably the resin of the present invention. Then,
Film adhesion, uniform film formation, etc. may not be obtained.

Further, since the energy level of the resin of the present invention can be changed by doping, the intermediate layer may be doped with the following dopant depending on the case.

An example of a dopant that can be doped is chlorine.

Bromine, iodine, ICI, ICjL x, IBr
, PFs, AsF5°5bF2. ^gC104
, AgBF4. BFz, BC cross, BBr2゜FS
O□0O3OJ, H2SO4, IIc 0. , (
No□) (SbF5).

(NO2) (SbC sentence g), (Not) (BF
4), SOz, llN0□, FSO,H.

CF: + Electron-accepting substances such as SOJ, lithium, sodium, potassium, rubidium, cesium, ammonia,
Examples include electron-donating substances such as amines.

Various doping methods can be used depending on the type of dopant.

(i) In the case of a magnetic compound with a high vapor pressure, doping can be done by bringing the gas into contact with the intermediate layer.At this time, in order to dope efficiently, other gases are once exhausted, and then the intermediate layer is doped. Preferably, a doping gas is introduced.

(2) (NO2) (SbF 6) and (NO) (Sb
When using salts such as C1&), for example, nitromethane,
The intermediate layer can be doped by dipping the intermediate layer into a solution such as methylene chloride.

(1) Also, doping can be performed by using a conductive substrate as an electrode, immersing it in a solution containing a salt containing a dopant atom, and passing a current between it and a counter electrode.

Specific examples of the resin of the present invention include, but are not limited to, the following compounds.

[Exemplary compounds]

(1) C5) (10)
II Specific examples of the components of the present invention include:
For example, pyrrole, 3-methylpyrrole, 3,4-dimethylpyrrole, 3-ethylpyrrole, 3,4-diethylpyrrole, 3-n-propylpyrrole, 3-n-butylpyrrole, 3-n-octylpyrrole, 3-isopropyl Pyrrole, 3-phenylpyrrole, 3-P-methylphenylpyrrole, 3-p-methodiphenylpyrrole,
3-P-7 minophenylpyrrole, 3-0-methylphenylpyrrole, tomethylpyrrole, N-ethylpyrrole.

n-butylpyrrole, N-n-octylpyrrole, N
-7enylvirol, N-P-methylphenylpyrrole, tolunitrophenylpyrrole, tolumethoxyphenylpyrrole, to-P-chlorphenylpyrrole, 3-
Pyrroles such as chlorpyrrole, 3-bromopyrrole, 3,4-dibromopyrrole: furan, 3-methylfuran, 3,4-dimethylfuran, 3-ethylfuran, 3.4
-diethylfuran, 3-n-/ropylfuran, 3-n
-Butylfuran, 3-n-octylfuran, 3-isopropylfuran, 3-phenylfuran, 3-P-methylphenylfuran, 3-p-methoxyphenylfuran, 3-
p-aminophenylfuran, 3-0-methylphenylfuran, 3-chlorofuran, 3-bromofuran, ],]
Furans of 4-dibromofuran: thiophene, comethylthiophene, 3,4-dimethylthiophene, 3-ethylthiophene, 3,4-diethylthiophene, 1-n-
Propylthiophene, 3-n-butylthiophene, 3-
n-octylthiophene, 3-isopropylthiophene, 3-phenylthiophene, 3-p-methylphenylthiophene, 3-p-methoxyphenylthiophene, 3-
Thiophenes such as 9-aminophenylthiophene, 3-o-methylphenylthiophene, 3-chlorothiophene, 3-bromothiophene, and 3,4-dibromothiophene: isointole, and the like.

The resin of the present invention may be a copolymer or terpolymer made of any combination of the monomer components of the present invention described above.

Although it is generally difficult to measure the degree of polymerization of the resin of the present invention, it is preferable that the resin has at least a degree of polymerization that does not substantially dissolve in a solvent.

The intermediate layer of the present invention may contain a resin other than the resin of the present invention (hereinafter referred to as a resin other than the present invention). Examples of the resin other than the present invention include acrylic resin, methacrylic resin, and hardened vinyl. Resin, vinyl resin, epoxy resin, urethane resin, Bosster resin, phenolic resin, alkyd resin, polycarbonate resin, silicone resin, melamine resin, polyvinyl formal resin, polyvinyl butyral resin, polyvinyl alcohol resin, vinyl chloride
Polymer materials such as vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, vinylidene chloride-acrylonitrile copolymer, styrene-butadiene copolymer, celluloses such as ethyl cellulose and carboxymethyl cellulose, etc. Each of them can be used alone or in combination of two or more.

The content ratio of resins other than the present invention is 10 to 10 to 100% of all resins in the intermediate layer.
80% by weight is preferred.

Methods for forming the intermediate layer include, but are not limited to, 1) direct film formation by electrolytic oxidation polymerization, 2) direct film formation by chemical oxidation polymerization, 2) polymerization of the resin of the present invention, A method (a method for forming a resin thin film containing a polymerization catalyst) is used in which the resin is applied together with another binder resin, that is, a resin other than the present invention.

Regarding the electrolytic oxidation polymerization method, for example, Macromol.

Che@, 185.1295 (1985), Bu
ll, Chew, Soc.

It is described in many documents such as Jpn, Tei, 985 (1983), and the film can be formed according to these documents. When using the electrolytic oxidation polymerization method, the conductive substrate can be used directly as an electrode for polymerization.

In this case, the electrode may be coated with a resin other than the present invention in a thin layer of less than 1 ml, and when this 7t polymerization is performed, the resin of the present invention is polymerized within the resin other than the present invention. , an intermediate layer of a composite film with satisfactory film adhesion and electrical properties can be obtained.

Acetonitrile,
Tetrahydrofuran (THF), dimethylformamide (DMF), propylene carbonate, methylformamide, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, methylene chloride, nitrobenzene, sulfolane, pyridine, ethanol, methanol, water, etc. are used.

As a supporting electrolyte, as a cation component,
Na”, K”, NtL”, (Ctl+)J”,
(C)IzC! l2) J”.

(C113C112C111)4N”, (CHflC
It has ions such as 82C)12C112)4N'', and the anion components can be BF4-, C1-, and As.

In the method of directly forming a film by chemical oxidative polymerization, a thin resin IIQ containing a polymerization catalyst is first formed on a conductive substrate,
This can be accomplished by exposing the monomer components of the present invention to a solution or steam prior to polymerization.

As a polymerization catalyst, TiO 4. TiCJ),,Ti
(OR), +.

CQ (NO3)2. NiC12, NiBr, GOCi
2. (oBr2.Fe(,Q)+N1(Co)s,
Mo(CO)*, A11lz, TiR1, FeRz
, CrR1 (in each formula, R represents an alkyl group such as a methyl group, ethyl group, or propyl group), etc. are used.

Examples of the binder resin containing a polymerization catalyst include acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, urethane resin, polyester resin, phenol resin, alkyd resin, polycarbonate resin, silicone resin, Melamine resin, polyvinyl formal resin, polyvinyl butyral resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride ugly copolymer, vinylidene chloride-acrylonitrile copolymer, styrene-butadiene copolymer Polymer materials such as coalescence, ethyl cellulose,
Examples include celluloses such as carboxymethyl cellulose, and each can be used alone or in combination of two or more.

As a method for forming a resin thin film containing a polymerization catalyst, first, a coating liquid in which a resin and a polymerization catalyst are dispersed or dissolved is prepared, and this can be applied by the method described below. Any solvent may be used as the solvent for the coating solution, but since it contains an inorganic polymerization catalyst, the following polar solvents are preferred. For example, water, methanol, ethanol, propatool, cyclohexanol. , acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethoxyethanol, l,
Examples include 2-jethoxyethane, dichloroethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrahydrofuran (THF), and dioxane.

When the substrate is in the form of a drum, dipping, spraying, extrusion, or slide hopper methods are used as the coating method, and in the case of sheet-shaped substrates, roll coating, extrusion, slide hopper, and gravure coating are used. , dip coating method, etc. are used.

In this manner, the intermediate layer of the present invention can be obtained by contacting the polymerization catalyst-containing resin g film provided on the conductive substrate with the solution or vapor of the monomer component of the present invention.

When contacted with a solution of monomers, the solvent of this solution is 1
Any material may be used as long as it does not completely dissolve the thin resin film containing the polymerization catalyst, but preferably it is a non-polar material that does not easily dissolve the resin. For example, n-pentane or n-hexane.

Examples include n-hebutane, Isopar, benzene, toluene, xylene, cyclohexane, petroleum ether, gasoline, diethyl ether, and the like. Depending on the case, these may be mixed with a relatively small amount of about 20% or less of the polar solvent described above.

When contacting it as a vapor, it may be brought into contact with 1,000 liters of air grown in a suitable container under atmospheric pressure, or
More preferably, the monomers may be evaporated and contacted in a container under reduced pressure.

For vaporization of 1,000 ml, it may be heated if necessary.

The contact time may be set to an optimum time depending on the monomer used, or the substrate or the environment (solution or monomer gas) at the time of contact may be heated in order to reduce the time in consideration of production efficiency.

In order to obtain a high-quality resin of the present invention, it is preferable to dehydrate and degas the solution in the solution method, and in the steam method, it is particularly preferable to sufficiently degas the oxygen.

The method of preparing one resin of the present invention in advance and applying it together with other resin binders includes the electropolymerization method described above, or polymerization in a solution using the polymerization catalyst described above. The resin of the present invention and the resin outside the present invention are dissolved or dispersed in the polar solvent mentioned in the explanation of the chemical oxidation type method, and applied using the coating method mentioned in the same explanation,
The intermediate layer of the present invention can be created.

The thickness of the intermediate layer of the present invention is preferably 0.05 to 20 torr, more preferably 0.05 to 20 torr. Is it l~logi+?

In the present invention, a photosensitive layer is formed on the intermediate layer. Here, the photosensitive layer includes an inorganic layer made of amorphous silicon, a layer made by dispersing a total bending powder of selenium, zinc oxide, cadmium sulfide, amorphous silicon, etc. in a binder, and a layer made of PVK (polyvinylcarbazole)-TNF.
()-linitrofluorenone), a layer consisting of a charge transfer complex such as polycarbonate-thiapyrylium salt, and a layer containing a phthalocyanine pigment, an azo pigment, etc. in each of the above layers.

Further, the photosensitive layer may be a layer that is functionally separated into a charge generation layer and a charge transport layer, and a surface protection layer may be further formed thereon.

Charge-generating substances suitable for the present invention include organic pigments that absorb visible light and generate charges, as shown in the following representative examples.

(1) Monoazo pigment, polyazo pigment, gold J:! Azo pigments such as complex azo pigments, pyrazolone azo pigments, stilbene azo pigments and thiazole azo pigments (2) Perylene pigments such as perylene acid anhydride and perylene ugly imide (3) Anthraquinone derivatives, anthorone derivatives, dibenzpyrenequinone derivatives, pyranthrone conductors,
Anthraquinone or polycyclic quinone pigments such as violanthrone derivatives and inviolanthrone derivatives (4) Indigoid pigments such as indigo derivatives and thioindigo visitants (5) Phthalocyanine pigments such as total diagonal phthalocyanine and focal phthalocyanine (5) Carbonium-based WJ pigments such as diphenylmethane pigments, triphenylmethane pigments, xanthine pigments and acridine pigments (7) Xanthine pigments such as azine pigments, oxazine pigments and thiazine pigments (8) Methylene pigments such as cyanine pigments and azomethine pigments.

(9) Quinoline pigments (10) Nitro pigments (11) Nitroso pigments (12) Benzoquinone and naphthoquinone pigments (11)
Naphthalimide pigments (14) Perinone pigments such as bisbenzimidazole derivatives, but preferably azo, phthalocyamenine or polycyclic quinone pigments having an electron-withdrawing group, with an average particle diameter of 2 m or less, especially Lp- It is preferable that the particles be dispersed and contained in the photosensitive layer as granules having a size of less than m.

Examples of azo pigments suitable for the present invention include those shown in the following exemplary compound groups [■] to [rV].

Margin below CI) CI) - N = N A N
= N -Cl) Here, Cp represents a coupler component, and all commonly known coupler components can be used.

Moreover, A represents a divalent bonding group.

Specific examples of Cp and A include the following.

(Example of ＾) and so on.

([+] Cp-N = N-A +-N :N
-A t-N :N -Cp where A, , A represents an aromatic group or a heterocyclic group. Specifically, there are the following.

R1-R4 represent hydrogen, chlorine or bromine atoms. Also, Xl is an iodine atom, NO, CN or CCHa
etc. n is an integer of 0.2.3 or 4.

υ X is a chlorine, bromine or iodine atom or a nitro group,
Indicates cyano group, acetyl group, etc. n is an integer of 0°2.3 or 4.

More specifically, the following compounds may be mentioned.

(G-1) (G-2) (G-3) 0-(J zz・〒 (G-23) (G-24) (C-25) (G-26) (G-27) (c- 28) (G-29) (G-30) (G-31) (G-32) CG-33) (G-34) The charge generation layer is formed by adding the charge generation substance to a solution of a suitable solvent or binder resin. is added to obtain a dispersion using a dispersing means such as a sand mill, a ball mill, or a sonic dispersion, and the dispersion is applied onto the intermediate layer to form a film with a predetermined thickness.

Suitable solvents used for dispersion include 1,2-dichloroethane, chloroform, 1,1.1-)IJ
ethane, dichloromethane, acetone, dioxane, methyl ethyl ketone, tetrahydrofuran.

Examples include benzene, toluene, xylene, diethyl ether, and the like.

The mixing ratio of the charge generating substance and the binder resin is preferably 10 to 500 parts, more preferably 30 to 200 parts, based on 100 parts of the charge generating substance.

Charge transport materials applicable to the present invention include triazole conductors (e.g., Japanese Patent Publication No. 34-5467), oxazole derivatives (e.g., Japanese Patent Publication No. 35-1125), oxadiazole derivatives (e.g., Japanese Patent Publication No. 34-5466), and pyrazoline conductors. conductors (e.g. No. 34-10366), imidazole derivatives (e.g. No. 35-11215, No. 37-16)
No. 096), fluorenone derivatives (JP-A-52-128)
373, No. 54-110837), Carno derivative conductor (for example, No. 54-59142), and No. 58-1
Examples include substances described in No. 34642 and No. 5B-65440.

Preferred charge transport materials in the present invention include compounds represented by the following general formulas (1) to (7).

General formula (1) General formula (3) R1? General formula (5) General formula (6) General formula (7) In the above formula, RI''-RR1-R3R1, ~R□, R0
~R31-I L*~RY represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a cyano group, a dialkylamino group, a diarylamino group, a dialkylamino group, a nitro group, or a methoxy group. R6 represents an alkyl group, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent;
1 represents a hydrogen atom, an alkyl group, a cyano group, or a phenyl group which may have a substituent, R15 represents a hydrogen atom,
represents a phenyl group, a cyano group, or an alkyl group which may have a substituent, Ar+ represents al, and in the formula R1%R4°, R41 represents an alkyl group, a benzyl group, a phenyl group, or a naphthyl group (each of these represents ), R42 is a hydrogen atom,
Represents an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a dialkylamino group or a nitro group. )
, fits and Lt represent a hydrogen atom or a phenyl group. n represents 0 or a positive integer.

Margin below Specific examples include the following compounds.

The charge transport layer is formed to a predetermined thickness by dissolving the above-mentioned materials in a suitable solvent and binder resin and coating the solution on the charge generation layer. As the solvent, those used in the charge generation layer can be used.

The coating method used to form the charge generation layer and the charge transport layer is preferably a dipping method, a spray method, an extrusion method, a slide hopper method, etc. when the substrate is in the form of a drum, and when the conductive substrate is in the form of a sheet. In some cases, roll methods, extrusion or slide hopper methods are preferably employed.

As the binder resin used to form the charge generation layer and the charge transport layer, various resins can be used in combination with a charge generation substance or a charge transport substance, but generally polyester,
Resins such as polyethylene, polyamide, polycarbonate, epoxy, poly-N-vinylcarbazole, polystyrene, polyvinyl butyral, and polymethyl methacrylate are used.

Note that when forming a charge generation layer and a charge transport layer by coating on a substrate provided with an intermediate layer, it is preferable to make the charge generation layer the lower layer as described above. The thickness of the photosensitive layer may be 0.0
5-1 sql is preferable, more preferably 0.1-2 gg
+, and the charge transport layer is preferably 5 to 50JL11,
More preferably, it is 10 to 307 zm.

[Effects of the Invention] According to the present invention, as is clear from the following examples, since the resin represented by the general formula is used for the intermediate layer, the above-mentioned Φ to ■
can solve the following problems.

[Example] Preferred examples of the present invention are shown below, but the present invention is not limited thereto.

Example 1 (Electrolytic oxidative polymerization method) 10 g of distilled and purified virol and 30 g of tetrabutylammonium verchlorate were dissolved in 1 well-dehydrated acetonitrile and placed in a cylindrical container. The drum was immersed, and cylindrical copper mesh electrodes having a diameter of 80 layers were immersed on the outside thereof at intervals of 10 ffiIll.

Using the aluminum drum as an anode and the copper mesh as a cathode, a constant current of 1 mA/cm'' was applied for 200 seconds to polymerize the rolls.

The aluminum drum was then removed from the liquid, immersed in a methanol bath, and rotated for 30 seconds for cleaning. An intermediate layer (0.2 pm) was thus obtained.

Next, 4 g of polyvinyl formal resin (trade name: Denka Formal Ii 100, manufactured by Denki Kagaku Co., Ltd.), Ig of polyvinyl butyral resin (trade name: S-LEC BLS, manufactured by Sekisui Chemical Co., Ltd.), (G-7) 1 Og as a charge generating substance,
1,000+su of 2-dichloroethane was pulverized and dispersed in a ball mill to obtain a dispersion.

The obtained dispersion is applied onto the intermediate layer by a dip method,
It was dried at 100''C for 10 minutes to form a charge generating layer having a thickness of 0.2 l.

Furthermore, 150 g of polycarbonate resin (trade name: Panlite ni-1300, manufactured by Kijin Kasei Co., Ltd.) and 75 g of charge transport substance (a) were added to 1000 an of 1,2-dichloroethane.
The solution was dissolved in the above charge generation layer and coated on the charge generation layer by a dip coating method, and dried at 110°C for 20 minutes to form a film with a thickness of about 2I.
A charge transport layer was formed. The electrophotographic photoreceptor thus obtained is referred to as sample 1.

Example 2 In Example 1, (G-14) was used instead of (G-7) as the charge generating substance, and polyvinyl formal [Ira (manufactured by Chisso Corporation) Ig and polymethyl methacrylate were used as the binder resin. An electrophotographic photoreceptor of the present invention was obtained in the same manner except that 2 g of (PMMA) resin (Acrivet MF, manufactured by Mitsubishi Shion Co., Ltd.) was used and (d) was used as the charge transport material. This is called sample 2.

Example 3 (chemical oxidative polymerization method) Polyvinyl alcohol resin (manufactured by Kanto Kagaku Co., Ltd., saponification degree 8
665 to 89 mol%, ffi degree 500), 1 g of ferric chloride was dissolved in 1 g of pure water, and coated on an aluminum vapor-deposited polyethylene terephthalate (PET) base using a wire bar coating method to achieve a dry film thickness of 0. A coating of .4 torr was obtained.

Next, this coating film was placed in a Pelger, and the pressure was reduced to 0.01 torr using a vacuum pump, and then 10 m of virol was introduced while vaporizing through the piping attached to the Pelger, and the film was filled with roll steam to a pressure of 5 torr. . After being left in the Pel jar for 1 hour, the pyrrole vapor was again evacuated using a vacuum pump and the atmosphere was replaced with nitrogen. The Pel jar was then opened to obtain a base on which an intermediate layer (0.5 JL11) had been formed.

Next, 8 g of polyvinyl formal resin (trade name: Denka Formal #20), 2 g of polycarbonate resin (trade name: Vanlite L-1250. Teijin Kasei 5S resin),
? tt Shipping material (G-12) 10g.

100hi of 1,2-dichloroethane was ground and dispersed in a sand grinder for 4 hours to obtain a dispersion. A charge generation layer having a thickness of 0.18 l was formed on the intermediate layer using the obtained dispersion by a wire bar coating method.

Furthermore, polycarbonate resin (product name: Panlite K)
-1300) 150g, charge transport material (d) 12
0 g was dissolved in 1000 am of 1,2-dichloroethane and applied onto the charge generation layer using a roll coater coating method, and dried at 120° C. for 5 minutes to form a charge transporting layer with a film thickness of 18 pm. The electrophotographic photoreceptor thus obtained is designated as Sample 3.

Example 4 In Example 3, polyvinyl butyral resin (trade name, Denka Formal 2000) was used as the catalyst holding binder.
L) An intermediate layer was formed in the same manner except that NiCl2,4 was used as isopropanol as a polymerization catalyst, and the following steps were taken.
An electrophotographic photoreceptor of the present invention was obtained using the photosensitive layer in the same manner. This is called sample 4.

Example 5 A photoreceptor drum was obtained in exactly the same manner as in Example 1, except that the conditions were changed as shown in Table 1 when preparing the intermediate layer.

Table 1 (Transformed) Bu = butyl group αλ (same) Example 6 A photoreceptor was prepared in the same manner as in Example 3, except that one condition was changed as shown in Table 2 when creating the intermediate layer. Got the drums.

Table 2 Example 7 10g of distilled and purified pyrrole and 30g of tetrabutylammonium verchlorate were dissolved in 200mM of sufficiently dehydrated dimethylformamide and added to a glass beaker. After applying a constant current of 0.5 mA/cm' for 4 hours while stirring the solution, the reaction solution was poured into 19.5 mA/cm' of water. The insoluble materials were taken into consideration. The screened black powder was washed with water three times and then dried to obtain polypyrrole.

Next, polyvinyl butyral resin (S-LEC BLS
, manufactured by Block Chemical Co., Ltd.) 7.5K, the above polypyrrole 2.5
8 in 1 volume of tetrahydrofuran and dispersed for 1 hour using a sand grinder.The resulting dispersion was coated on an aluminum-deposited PET base using a roll coating method to obtain an intermediate layer of 0.3 p-ts. Got layers.

A core charge generation layer and a charge transport layer were formed thereon in exactly the same manner as in Example 2 to obtain sample 19.

Example 8 Samples 1, 3, 5. In I'l, after creating the middle layer,
The samples were left in a container filled with iodine vapor for 1 hour to form a toped intermediate layer of iodine, after which the samples 1, 3, and 5.1:1 were applied on each sample, respectively. , forming a photosensitive layer, samples 20.21.
It was set at 22.2 pieces.

Comparative Example 1 Samples 1, 2, and 3.4 were prepared by forming only the photosensitive layer without forming an intermediate layer, respectively, as comparative sample l.
, 2, 3.4.

Comparative Example 2 Samples 13 to 18 were coated in the same manner as in Example 3 without adding any catalyst to the catalyst-carrying binder to give 0.3p and rrr, respectively, and then immediately treated in the same manner as in Example 3. Comparative sample 5 is a sample with a photosensitive layer formed.
~IO.

[Evaluation 1] Each sample obtained above was evaluated as follows. In the Carlson process.

200gA (7) Under discharge conditions, linear velocity 150m+n/s
ee, stopped immediately after charging, and measured with a surface position meter, and the surface potential immediately after charging was [va], and the surface potential after being left in the dark for 5 seconds [v1]. Separately, it is stopped immediately after charging and exposed so that the blackness of one surface becomes 2 lux.
Exposure ri [E l/ until the surface potential becomes 1/2 Vi
2] CLux-sec), and further v, -V
ip=xto.

d The dark decay rate [D] was determined from the formula.

Further, a normal Carlson process was performed using Samples 1 to 23 and Comparative Sample 1-10.

The difference between the surface potential immediately after initial charging and after 10,000 times [Δ
Vbl and the change in potential between the initial stage and after 10,000 exposures [Δ゛I,1] were measured.

The above evaluation results are shown in Tables 3 and 4.

Table 3: As shown in Table 54, the photoreceptor of the present invention not only has a high acceptance potential under the same charging conditions, but also has high charge retention, high sensitivity, and excellent repeatability. I can say it.

Example 9 In Example 1, pyrrole was replaced with N-methylvirol, N
- Photoreceptors were obtained in the same manner except for phenylpyrrole, 3-chloropyrrole, 3゜4-dibromopyrrole, tophenylpyrrole, 3-p-methoxyphenylpyrrole, and 3-p-amisophenylpyrrole, and the same evaluation was carried out. As a result, the same results as in Example 1 were obtained.

Claims (1)

[Scope of Claims] An electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, comprising an intermediate layer containing a resin consisting of a monomer component represented by the following general formula between the conductive substrate and the photosensitive layer. An electrophotographic photoreceptor featuring: General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X is an atom selected from an oxygen atom, a sulfur atom, or a nitrogen atom;
It has an alkyl group or an aryl group substituent. R_1 and R_2 are substituents selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an amino group, and a ring may be formed between R_1 and R_2. ]