JPH07309824A - Trinitrofluorenone imine derivative and electrophotographic receptor - Google Patents

Abstract

PURPOSE:To obtain a new nitrofluorenone imine derivative capable of giving an electrophotographic receptor excellent in electron-transport property, having residual voltage suppressed at a lower level and exhibiting excellent sensitivity. CONSTITUTION:This is a compound of formula I (R<1> to R<5> are each H or an optionally substituted alkyl, an optionally substituted aryl, an alkoxy, an optionally substituted aralkyl or a halogen; wherein, R<5> is not H, an alkyl, an alkoxy nor a halogenoalkyl when all of R<2> to R<4> are H and R<1> is an alkyl, an alkoxy or a halogenoalkyl), e.g. N-(4-benzylphenyl)-2,4,7-trinitrofluorenone imine. The compound is obtained by the condensation of 2,4,7-trinitrofluorenone of formula II with an aniline derivative of formula III in a solvent optionally in the presence of an appropriate catalyst such as zinc chloride. The compound is excellent in solubility in a solvent and compatibility with a combined resin. At the same time, it is excellently matching with a charge-generating agent, and electrons are smoothly introduced. Further, the compound has excellent electron-transport property especially at a low electric field.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a trinitrofluorenone imine derivative which is particularly useful as an electron transfer material, and an electrophotographic photoreceptor used in a copying machine, a laser printer or the like.

[0002]

2. Description of the Related Art Electrophotographic photoreceptors made of various materials are used in image forming apparatuses such as copying machines using the Carlson process. One is an inorganic photoreceptor using an inorganic material such as selenium in the photosensitive layer, and the other is an organic photoreceptor using an organic material in the photosensitive layer. Extensive research has been conducted because organic photoreceptors have many advantages such as being inexpensive and having high productivity as compared with inorganic photoreceptors and being non-polluting.

As the organic photoconductor, there are many so-called function-separated type organic photoconductors in which a charge generation layer and a charge transport layer are laminated, that is, laminated photoconductors, but a charge generation agent and a charge transport agent are used as the photoconductive layer. A single-layer type organic photoconductor dispersed therein is also known. Charge transport agents used in these photoconductors are required to have high carrier mobility, but most charge transport agents with high carrier mobility have hole transporting properties, and therefore are not put to practical use. However, from the viewpoint of mechanical strength, it is limited to a negative charging type laminated organic photoreceptor having a charge transport layer as the outermost layer. However, since the negative charge type organic photoconductor uses negative corona discharge, a large amount of ozone is generated, and thus there are problems such as pollution of the environment and deterioration of the photoconductor.

Therefore, in order to eliminate such drawbacks, the use of an electron transfer agent as a charge transfer agent has been studied, and in JP-A-1-206349, a compound having a diphenoquinone structure is electrophotographic. It has been proposed to use it as an electron transfer material for photoreceptors. However, in general, conventional electron transfer agents containing diphenoquinones have poor compatibility with a binder resin and a long hopping distance, so that electron transfer in a low electric field does not easily occur, and the residual potential is considerably high. is there.

A main object of the present invention is to solve the above technical problems and to provide a novel compound suitable as an electron transport agent. Another object of the present invention is to provide a single-layer type and multi-layer type electrophotographic photoconductor in which the residual potential is suppressed to a low level and which exhibits excellent sensitivity.

[0006]

[Means and Actions for Solving the Problems] As a result of intensive studies conducted by the present inventors to solve the above problems, the general formula (1):

[0007]

[Chemical 7]

(Wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ are the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and the alkyl group, the aryl group and the aralkyl group may have a substituent. However, R ² , R ³
When R ⁴ and R ⁴ are both hydrogen atoms and R ¹ is an alkyl group, an alkoxy group or a halogenated alkyl group, R ⁵ is not a hydrogen atom, an alkyl group, an alkoxy group or a halogenated alkyl group. The present inventors have found that the trinitrofluorenone imine derivative represented by the formula (4) has a higher electron transporting ability than the conventional diphenoquinone derivative, and have completed the present invention.

That is, the compound of the present invention represented by the above general formula (1) has good solubility in a solvent and compatibility with a binder resin, and is excellent in matching with a charge generating agent. The injection is performed smoothly, and the electron transport property is excellent especially in a low electric field. Therefore, when the trinitrofluorenone imine derivative represented by the general formula (1) of the present invention is used as an electron transfer agent in an electrophotographic photoconductor, the residual potential of the photoconductor is greatly reduced, resulting in high sensitivity of the organic photosensitizer. The body can be provided. The compounds of the present invention are also safe against carcinogenicity.

The compound (1) of the present invention can be used for solar cells, EL devices and the like by utilizing its high electron transporting ability. Each group represented by the above general formula (1) will be specifically described. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, t-
Examples thereof include alkyl groups having 1 to 6 carbon atoms such as butyl, pentyl and hexyl groups.

Examples of the alkoxy group include alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, t-butoxy, pentyloxy and hexyloxy groups. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include benzyl, benzhydryl, trityl and phenethyl groups. Examples of the halogen atom include chlorine, bromine, fluorine and iodine.

Examples of the substituent which the alkyl group, aryl group and aralkyl group may have include an alkoxy group or a halogen atom when it is an alkyl group and an alkyl group or an alkoxy group when it is an aryl group or an aralkyl group. Alternatively, a halogen atom may be mentioned. The derivatives represented by the general formula (1) include, for example, the following compounds.

[0013]

[Chemical 8]

[0014]

[Chemical 9]

(In each formula, R ¹¹ and R ¹² are the same or different and each represents an alkyl group, an alkoxy group or a halogen atom. M is an integer of 0 to 4 and n is an integer of 0 to 5.) The derivative represented by the formula (1) can be synthesized by condensing 2,4,7-trinitrofluorenone and a predetermined aniline derivative in a solvent, for example, as shown in the following reaction process equation. it can. As the solvent, it is preferable to use organic acids such as acetic acid, propionic acid, butanoic acid, chloroform, tetrahydrofuran, dimethylformamide, dimethylsulfoxide and the like. If necessary, the reaction may be carried out in the presence of a suitable catalyst such as zinc chloride. The reaction is usually performed at a temperature of 30 to 170 ° C. for 2 hours.
It may be performed for 0 minutes to 4 hours.

[0016]

[Chemical 10]

(Wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ is the same as above. The electrophotographic photosensitive member of the present invention is roughly classified into a single layer type and a laminated type. The single-layer type electrophotographic photoreceptor is one in which an organic photosensitive layer is provided on a conductive substrate, and the organic photosensitive layer is a binder resin, together with at least a charge generating agent and a hole transporting agent,
It is characterized by being a single-layer type containing a trinitrofluorenone imine derivative represented by the following general formula (2) as an electron transfer agent.

[0018]

[Chemical 11]

(Wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ and R
¹⁰ is the same or different and represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and the alkyl group, the aryl group and the aralkyl group may have a substituent. In this single-layer type electrophotographic photosensitive member, the residual potential of the photosensitive member is greatly reduced, and the sensitivity can be improved. The single-layer type photoreceptor of the present invention can be applied to both positive charging and negative charging, but it is particularly preferable to use the positive charging type.

Examples of the respective substituents in the derivative of the general formula (2) are the same as the substituents in the general formula (1). The derivative of general formula (2) can be synthesized in the same manner as the derivative of general formula (1). In the organic photosensitive layer of the single-layer type electrophotographic photosensitive member, -0.8 to -1.2V is applied.
When the electron-accepting compound having the redox potential of 1 is contained, the sensitivity is further improved.

On the other hand, the laminated electrophotographic photoreceptor of the present invention is
At least a charge generation layer and a charge transport layer are provided in this order on a conductive substrate, and the charge transport layer contains a trinitrofluorenone imine derivative represented by the general formula (1) as an electron transport agent. It is characterized by This electrophotographic photosensitive member is used as a positive charging type, and the residual potential is greatly reduced, and the sensitivity can be improved.

In order to facilitate the transfer of electrons from the charge generation layer to the charge transport layer, it is preferable that the charge generation layer also contains a trinitrofluorenone imine derivative. As the trinitrofluorenone imine derivative contained in the charge generation layer, the compound represented by the general formula (2) can be preferably used. Further, in a laminated electrophotographic photoreceptor in which at least a charge generation layer and a charge transport layer are provided in this order on a conductive substrate, a trinitrofluorenone represented by the general formula (2) is used as an electron transport agent in the charge transport layer. The imine derivative is contained, and the charge generation layer contains -0.8 to -1.
It is preferable to contain an electron-accepting compound having a redox potential of 2V.

The redox potential is measured using the following materials by a three-electrode type cyclic voltammetry. Electrode: working electrode (glassy carbon electrode), counter electrode (platinum electrode) Reference electrode: silver nitrate electrode (0.1 mol / liter AgNO)
₃ -Acetonitrile solution) Measurement solution Electrolyte: t-butylammonium perchlorate
0.1 mol Measuring substance: electron transporting agent 0.001 mol Solvent: CH ₂ Cl ₂ 1 liter The above materials are prepared to prepare a measuring solution.

Calculation of redox potential: As shown in FIG.
The relationship between the index voltage (V) and the current (μA) is obtained, E ₁ and E ₂ shown in the figure are measured, and the redox potential is obtained by the following calculation formula. Redox potential = (E ₁ + E ₂ ) / 2 (V) The compounds represented by the general formulas (1) and (2) in the present invention have good solubility in a solvent and compatibility with a binder resin. In addition, it is excellent in matching with the charge generating agent, electrons are smoothly injected, and the electron transporting property is particularly excellent in a low electric field.

Therefore, the single-layer type positive charging photoreceptor of the present invention is
Electrons released from the charge generating agent in the exposure step are smoothly injected into the electron transfer agent represented by the general formulas (1) and (2), and then the electrons are transferred between the electron transfer agents to transfer the electrons to the photosensitive layer. The positive charges (+) that have been transferred to the surface of the photosensitive layer and are charged on the surface of the photosensitive layer are canceled. On the other hand, holes (+) are injected into the hole transport material, move to the surface of the conductive substrate without being trapped in the middle, and cancel the negative charge (-) on the surface of the conductive substrate. In this way, the sensitivity of the positive charging type photoconductor is considered to be improved. When the single-layer type photoreceptor is used with negative charging, the sensitivity is similarly improved only by reversing the direction of charge transfer.

Further, in the laminated positive charging photoreceptor of the present invention,
Electrons released from the charge generating agent in the charge generating layer in the exposure step are smoothly injected into the electron transferring agent represented by the general formulas (1) and (2) in the charge transferring layer, and then the electron transferring agent The electrons move in the charge transport layer due to the transfer of the electrons in, reach the surface of the photosensitive layer, and cancel the positive charge (+) charged in advance on the surface of the photosensitive layer. On the other hand, holes (+) move directly from the charge generation layer to the surface of the conductive substrate, and cancel the negative charge (-) on the surface of the conductive substrate. It is considered that the sensitivity of the multi-layer type charging photoreceptor is improved in this way.

The charge generating agent that absorbs light by exposing the photosensitive member produces ion pairs [holes (+) and electrons (-)]. In order for the generated ion pairs to become free carriers and effectively cancel the surface charge, it is preferable that the ion pair recombine and disappear. When an electron-accepting compound having a redox potential of −0.8 to −1.2 V is present, LUMO (means the highest energy level in the molecular orbitals occupied by electrons in the molecule). , The excited electron is usually an electron of this level.) Since the energy level of the electron is lower than that of the charge generating agent, the electron moves to the electron-accepting compound during the generation of the ion pair, and the ion pair becomes the carrier. It becomes easy to separate into. That is, the electron-accepting compound acts on the charge generation to improve the generation efficiency.

On the other hand, in order to have high sensitivity, it is necessary that carrier traps due to impurities do not occur when the free carriers move. Usually, a trap due to a small amount of impurities exists in the moving process of the free carrier, and the free carrier moves while repeating trap-detrap. Therefore, when the free carriers fall to a level where they cannot be untrapped, they become carrier traps and their movement is stopped.

As will be apparent from the examples described below, the electrophotographic photosensitive materials of Comparative Examples 14 and 20 using the electron-accepting compound a exhibiting a value larger than the range of the redox potential of the electron-accepting compound of the present invention. It can be seen that the body is inferior in residual potential and photosensitivity as compared with the electrophotographic photoreceptors of the present invention shown in Examples. This has a redox potential of −0.
In the case of an electron-accepting compound having a voltage higher than 8 V, the separated free carriers are dropped to a level that cannot be detrapped, resulting in carrier traps.

On the contrary, the redox potential is -1.2 V.
In the case of a smaller electron-accepting compound, the energy level of LUMO is higher than that of the charge generating agent, and when the ion pair is generated, the electron does not move to the electron-accepting compound, which does not improve the charge generation efficiency. It is considered to be a thing. As the hole-transporting agent, a conventionally known hole-transporting substance is used, for example, 2,5-di (4-methylaminophenyl), 1,
Oxadiazole compounds such as 3,4-oxadiazole, styryl compounds such as 9- (4-diethylaminostyryl) anthracene, carbazole compounds such as polyvinylcarbazole, organic polysilane compounds, 1-phenyl-3- (p -Pyrazoline compounds such as dimethylaminophenyl) pyrazolin, hydrazone compounds, triphenylamine compounds, indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds , Nitrogen-containing cyclic compounds such as triazole compounds, condensed polycyclic compounds, and the like.

These charge transport materials may be used alone or in admixture of two or more. Further, when using a charge transport material having film-forming properties such as polyvinylcarbazole, the binder resin is not always necessary. In the present invention, among the hole transporting agents, the ionization potential is 4.8 to
It is preferable to use the one of 5.6 eV and the electric field strength of 3
Those having a mobility of 1 × 10 ⁻⁶ cm ² / V · sec or more at × 10 ⁵ V / cm are particularly preferable. Specifically, alkyl-substituted triphenylamine derivatives are preferable.

The value of the ionization potential is measured by using an atmospheric photoelectron analyzer (AC-1 manufactured by Riken Keiki Co., Ltd.). In the present invention, by using a hole transfer agent having an ionization potential within the above range, the residual potential can be further lowered and the sensitivity can be improved. The reason is not clear, but it is considered as follows.

That is, the easiness of injecting the charge from the charge generating agent to the hole transferring material is closely related to the ionization potential of the hole transferring material, and the ionization potential of the hole transferring material is higher than the above range. If it is large, the degree of charge injection from the charge generating agent to the hole transporting agent will be low, or the degree of transfer of holes between the hole transporting agents will be low, resulting in a decrease in sensitivity. Is recognized.

On the other hand, in a system in which a hole transfer material and an electron transfer material coexist, it is necessary to pay attention to the interaction between them and more specifically to the formation of a charge transfer complex. When such a complex is formed between the two, recombination occurs between the holes and the electrons, and the mobility of the charge is lowered as a whole. When the ionization potential of the hole transfer material is smaller than the above range, the tendency to form a complex with the electron transfer material increases, and electron-hole recombination occurs, resulting in an apparent quantum yield. Is likely to decrease, resulting in a decrease in sensitivity.

Therefore, a bulky substituent such as an aryl group or an aralkyl group is introduced into the N-trinitrofluorenylidene-aniline derivative represented by the general formulas (1) and (2). It is preferable to suppress the formation of a complex with the hole transport agent due to steric hindrance. The hole transporting agent used in the present invention is not particularly limited, but for example, 1,1-bis (4-diethylaminophenyl) -4,4-diphenyl-1,3-butadiene, N, N'-bis (2,4-dimethylphenyl) -N, N'-diphenylbenzidine, 3,3'-dimethyl-N, N, N ', N'-tetrakis-4-methylphenyl (1,1'- Biphenyl) -4,4'-diamine, N-ethyl-3-carbazolylaldehyde-N,
N'-diphenylhydrazone, 4- [N, N-bis (p
-Toluyl) amino] -β-phenylstilbene and the like.

The electron-accepting compound is not particularly limited as long as it is a compound having an electron-accepting property and an oxidation-reduction potential of -0.8 to -1.2 V, and examples thereof include benzoquinone compounds and naphthoquinone compounds. Anthraquinone type, diphenoquinone type, malononitrile, thiopyran type compound, 2,
4,8-trinitrothioxanthone, 3,4,5,7-
Examples thereof include fluorenone compounds such as tetranitro-9-fluorenone, dinitroanthracene, dinitroacridine, nitroanthraquinone and dinitroanthraquinone. Of these, the diphenoquinone type has a quinone type oxygen atom excellent in electron-accepting property bonded to the end of the molecular chain, and since there is a conjugated double bond over the entire long molecular chain, the transfer of electrons within the molecule also occurs. It is particularly preferable because it has the advantage that it is easy and the transfer of electrons is easy. Further, each electron-accepting compound described above contributes to the generation of charges.

Examples of the benzoquinone compounds include p-benzoquinone, 2,6-dimethyl-p-benzoquinone and 2,6-di-t-butyl-p-benzoquinone. Further, as the diphenoquinone compound,
Examples include derivatives represented by the following general formulas (4) to (7).

[0038]

[Chemical 12]

[0039]

[Chemical 13]

(In each formula, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷
And R ¹⁸ are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a cycloalkyl group, or an amino group which may have a substituent. ) Examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, pentyl and hexyl groups, and examples of the alkoxy group include methoxy, ethoxy and propoxy groups. ,
An alkoxy group having 1 to 6 carbon atoms such as t-butoxy, pentyloxy and hexyloxy groups, an aryl group such as a phenyl group and a naphthyl group, and an aralkyl group such as benzyl, benzhydryl, trityl and phenethyl. Groups, etc., as the cycloalkyl group,
Examples thereof include cycloalkyl groups having 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The amino group which may have a substituent includes, for example, an amino group, monomethylamino, dimethylamino, monoethylamino,
Examples include diethylamino.

Specific examples of the diphenoquinone compounds represented by the formulas (4) to (7) include, for example, 3,5-dimethyl-
3 ', 5'-dit-butyldi-4,4'-diphenoquinone, 3,3'-dimethyl-5,5'-dit-butyl-
4,4'-diphenoquinone, 3,5'-dimethyl-3,
Examples thereof include 5'-di-t-butyl-4,4'-diphenoquinone. The diphenoquinone-based compound having these substituents is preferable because the symmetry of the molecule is low, the interaction between the molecules is small, and the solubility is excellent. Also,
Examples of the diphenoquinone compound represented by the formula (4) include 3,3 ', 5,5'-tetramethyl-4,4'-diphenoquinone, 3,3', 5,5'-tetraethyl-
4,4'-diphenoquinone, 3,3 ', 5,5'-tetra-t-butyl-4,4'-diphenoquinone and the like can be mentioned. These diphenoquinone compounds can be used alone or in combination of two or more.

Examples of the charge generating agent used in the present invention include selenium, selenium-tellurium, amorphous silicon, pyrylium salts, azo pigments, ansanthuron pigments, phthalocyanine pigments, perylene pigments, naphthalocyanine pigments, Examples thereof include indigo pigments, triphenylmethane pigments, slene pigments, toluidine pigments, pyrazoline pigments, quinacridone pigments and dithioketopyrrolopyrrole pigments. These charge generating agents may be used alone or in combination of two or more so as to have an absorption wavelength in a desired region. At that time, in connection with the use of a hole transfer agent having an ionization potential of 4.8 to 5.6 eV, a charge generation agent having an ionization potential balanced with the hole transfer agent, specifically, Has an ionization potential of 4.8 to 6.
It is desirable to use 0 eV, particularly 5.0 to 5.8 eV in order to reduce the residual potential and improve the sensitivity.
Examples of particularly suitable charge generating agents include phthalocyanine-based pigments such as X-type metal-free phthalocyanine and oxotitanyl phthalocyanine, or perylene-based pigments.

Among them, the phthalocyanine pigment is 70
It is suitable as a charge generating material for a photoconductor having sensitivity in a wavelength region of 0 nm or more. That is, the phthalocyanine-based pigment is excellent in matching with the compounds represented by the general formulas (1) and (2) (electron transfer agent). It has high sensitivity and therefore can be suitably used for a digital optical image forming apparatus using a light source having a wavelength of 700 nm or more.

Further, as the perylene pigment, a general formula:

[0045]

[Chemical 14]

A compound represented by the formula (in the formula, R ^a , R ^b , R ^c and R ^d are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or an aryl group) is preferably used. . This perylene-based pigment is suitable as a charge generating material for a photoreceptor having sensitivity in the visible region. That is, the perylene pigment (3) has the general formula (1), (2)
Since it is excellent in matching with the compound (electron transfer agent) represented by, the electrophotographic photosensitive member using both of them has high sensitivity in the visible region, and therefore an analog optical system using a light source having a wavelength in the visible region. Can be suitably used for the image forming apparatus.

As the binder resin for dispersing the above components, various resins conventionally used in organic photosensitive layers can be used, for example, a styrene polymer,
Styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylic copolymer, styrene-acrylic acid copolymer, polyethylene, ethylene-vinyl acetate copolymer, chlorinated polyethylene, poly Vinyl chloride, polypropylene, ionomer, vinyl chloride-vinyl acetate copolymer, polyester,
Alkyd resin, polyamide, polyurethane, polycarbonate, polyarylate, polysulfone, diallyl phthalate resin, ketone resin, polyvinyl butyral resin,
Thermoplastic resin such as polyether resin, polyester resin, silicone resin, epoxy resin, phenol resin,
Examples thereof include urea resins, melamine resins, other crosslinkable thermosetting resins, and photocurable resins such as epoxy acrylate and urethane-acrylate. These binder resins can be used alone or in combination of two or more. Suitable resins are styrene polymers, acrylic polymers, styrene-acrylic copolymers, polyesters, alkyd resins, polycarbonates, polyarylates and the like.

In order to obtain a single-layer type electrophotographic photosensitive member, a trinitrofluorenone imine derivative represented by the general formula (2) is used as an electron transferring agent together with a charge generating agent, a hole transferring agent, a binder resin and the like. A coating solution dissolved or dispersed in a suitable solvent,
It may be applied on the conductive substrate by a means such as application and dried. In order to obtain a laminated type electrophotographic photoreceptor, first, on a conductive substrate, a charge generating layer containing a charge generating agent is formed by means such as vapor deposition or coating, and then on this charge generating layer, a general formula ( A charge-transporting layer may be formed by applying a coating solution containing the trinitrofluorenone imine derivative represented by 1) or (2) and a binder resin by means such as coating and drying.

In the case of a single-layer type photoreceptor, the binder resin 10
The charge generating agent is added in an amount of 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, based on 0 part by weight,
The electron transfer agent containing the trinitrofluorenone imine derivative represented by (2) is 5 to 100 parts by weight, preferably 10 to
It is mixed in a ratio of 80 parts by weight. In addition, the hole transport material is 1
The amount is 0 to 500 parts by weight, preferably 25 to 200 parts by weight. Further, it is suitable that the total amount of the hole transfer agent and the electron transfer agent is 20 to 500 parts by weight, preferably 30 to 200 parts by weight, based on 100 parts by weight of the binder resin. When the single-layer type photosensitive layer contains an electron-accepting compound, the electron-accepting compound is added in an amount of 0.1 to 40 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the binder resin. It is appropriate to do.

The thickness of the single-layer type photosensitive layer is 5 to 100.
μm, preferably 10 to 50 μm. In the multi-layer type photoreceptor, the charge generating agent and the binder resin constituting the charge generating layer can be used in various ratios, but the charge generating agent is added in an amount of 5 to 1000 with respect to 100 parts by weight of the binder resin. It is suitable to blend in a weight ratio of 30 to 500 parts by weight. When the charge-generating layer contains an electron-accepting compound, the electron-accepting compound is contained in an amount of 0.1 to 40 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the binder resin.
It is suitable to blend in parts by weight. When the charge generation layer contains a trinitrofluorenone imine derivative (2), the derivative (2) is contained in an amount of 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts by weight of the binder resin. It is suitable to blend in.

The electron-transporting agent and the binder resin constituting the charge-transporting layer can be used in various proportions within the range that does not hinder the transport of charge and the range that does not crystallize. In order to easily transport the generated charge, the general formula (1) or 100 parts by weight of the binder resin may be used.
It is suitable to blend the trinitrofluorenone imine derivative represented by (2) in an amount of 10 to 200 parts by weight, preferably 20 to 100 resin. When the charge-transporting layer contains an electron-accepting compound, the electron-accepting compound is added in an amount of 0.1 to 40 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the binder resin. Appropriate.

The thickness of the laminated type photosensitive layer is about 0.01 to 5 μm, preferably 0.1 to 3 μm for the charge generation layer.
The charge transport layer has a thickness of 2 to 100 μm, preferably 5 to 50 μm. In the case of a single-layer type photoreceptor, between the conductive base and the photosensitive layer, and in the case of the multilayer type photoreceptor, between the conductive base and the charge generation layer, the conductive base and the charge transport layer. Between or between the charge generation layer and the charge transport layer,
A barrier layer may be formed in a range that does not impair the characteristics of the photoreceptor. Further, a protective layer may be formed on the surface of the photoconductor.

In the single-layer type and the multi-layer type photosensitive layers, various additives known per se, such as an antioxidant, a radical scavenger, a singlet quencher, are added to the extent that they do not adversely affect the electrophotographic characteristics. A deterioration inhibitor such as an ultraviolet absorber, a softening agent, a plasticizer, a surface modifier, a bulking agent, a thickener, a dispersion stabilizer, a wax, an acceptor, a donor and the like can be added.

In the present invention, as the antioxidant, a sterically hindered phenolic antioxidant is preferably used as the binder resin 100.
When it is added in an amount of 0.1 to 50 parts by weight with respect to parts by weight, the durability of the photosensitive layer can be significantly improved without adversely affecting the electrophotographic characteristics. The following compounds are exemplified as such antioxidants. 2,6-di-t-butyl-p-cresol

[0055]

[Chemical 15]

[0056]

[Chemical 16]

[0057]

[Chemical 17]

[0058]

[Chemical 18]

[0059]

[Chemical 19]

[0060]

[Chemical 20]

[0061]

[Chemical 21]

(In each formula, tBu represents a t-butyl group.) In order to improve the sensitivity of the photosensitive layer, a known sensitizer such as terphenyl, halonaphthoquinones, and acenaphthylene is used as a charge generating agent. You may use together with. In addition to the compound represented by the above general formula, other conventionally known electron transfer agents may be contained in the photosensitive layer. Examples of such an electron transfer agent include benzoquinone type, diphenoquinone type,
Malononitrile, thiopyran compounds, tetracyanoethylene, 2,4,8-trinitrothioxanthone, 3,
Fluorenone compounds such as 4,5,7-tetranitro-9-fluorenone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone,
Examples thereof include dinitroanthraquinone, succinic anhydride, maleic anhydride, and dibromomaleic anhydride.

As the conductive substrate used in the photoreceptor of the present invention, various conductive materials can be used. For example, aluminum, iron, copper, tin, platinum, silver, vanadium, molybdenum, chromium. , Cadmium, titanium,
Examples include simple metals such as nickel, palladium, indium, stainless steel, and brass, plastic materials in which the above metals are vapor-deposited or laminated, and glass coated with aluminum iodide, tin oxide, indium oxide, or the like.

The conductive substrate may be in the form of a sheet, a drum or the like, as long as the substrate itself has conductivity or the surface of the substrate has conductivity. Further, it is preferable that the conductive substrate has sufficient mechanical strength when used. The photosensitive layer according to the present invention is manufactured by coating a coating solution prepared by dissolving or dispersing a resin composition containing each of the above components in a solvent on a conductive substrate and drying the coating solution.

That is, the above-mentioned charge generating agent, charge transporting agent, binder resin and the like are used together with an appropriate solvent by a known method such as a roll mill, a ball mill, an attritor, a paint shaker or an ultrasonic disperser. The coating liquid may be prepared by dispersing and mixing, and the coating liquid may be coated and dried by a known means. As the solvent for forming the coating liquid, various organic solvents can be used, for example, alcohols such as methanol, ethanol, isopropanol and butanol, aliphatic hydrocarbons such as n-hexane, octane and cyclohexane, benzene, Aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride and chlorobenzene, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, cyclohexanone, etc. Examples thereof include ketones, esters such as ethyl acetate and methyl acetate, dimethylformaldehyde, dimethylformamide, dimethylsulfoxide and the like. These solvents can be used alone or in combination of two or more.

Further, in order to improve the dispersibility of the charge transport material or the charge generating material and the smoothness of the surface of the photosensitive layer, a surface active agent, a leveling agent or the like may be used.

[0067]

EXAMPLES The electrophotographic photoreceptor of the present invention will be described below with reference to Synthesis Examples, Examples and Comparative Examples. Synthesis Example 1 Production of N- (2-biphenylyl) -2,4,7-trinitrofluorenone imine 2,4,7-Trinitrofluorenone 2.7 g (8.5
7 mmol) and 1.45 g of 2-aminobiphenyl (8.
57 mmol) was dissolved in 50 ml of acetic acid and reacted at 110 ° C. for 2 hours. After the reaction, it was added to 300 ml of water, and the precipitated crystals were washed with water. After drying the crystals, silica gel column chromatography (chloroform: hexane = 1: 2)
And eluate) to give a dark red powder of the title compound (a compound of the general formula (a) wherein n and m are 0).
Got

The melting point of this product was 205 ° C. The infrared absorption spectrum of this product is shown in FIG.
The spectra are shown in FIG. 3, respectively. (Evaluation of Electron Transportability) The electron transportability of the compound obtained in Synthesis Example 1 was evaluated by the TOF method. As a result, this compound had a field strength of 3 × 10 ⁵ V / cm and a value of 8.05 × 10 ⁻⁷ cm ² /
It showed a mobility of V · sec and was found to have a high electron transporting ability. Example 1 The compound obtained in Synthesis Example 1 was used as an electron transfer agent, and X-type metal-free phthalocyanine (Ip =
5.38 eV), and N, N,
N ', N'-tetrakis (4-methylphenyl) -3,
3'-Dimethylbenzidine (Ip = 5.56 eV) was used. In addition, polycarbonate was used as a binder resin, and these materials were mixed and dispersed in a predetermined amount of dichloromethane with a ball mill at the following blending ratios to prepare a single-layer type photosensitive layer coating solution. Then, this coating solution was applied on an aluminum foil with a wire bar and dried with hot air at 100 ° C. for 60 minutes to prepare a single-layer type electrophotographic photosensitive member having a film thickness of 15 to 20 μm.

(Component) (Parts by Weight) Charge Generating Agent 1 Hole Transporting Agent 60 Electron Transporting Agent 40 Binder Resin 100 Comparative Example 1 Single-layer electron as in Example 1 except that no electron transporting agent is contained. A photographic photoreceptor was produced. Comparative Example 2 2,6 instead of the compound obtained in Synthesis Example 1 as an electron transfer agent
A single-layer type electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that -dimethyl-2 ', 6'-di-t-butyl-4,4'-diphenoquinone was used. Example 2 100 parts by weight of the same compound used in Example 1 as a charge generating agent, 100 parts by weight of polyvinyl butyral resin as a binder resin, and a predetermined amount of tetrahydrofuran as a solvent were mixed and dispersed in a ball mill to form a charge generating layer. To prepare a coating solution. This coating solution was applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of about 1 μm.

On the other hand, 100 parts by weight of the compound obtained in Synthesis Example 1 as an electron transfer agent, 100 parts by weight of a polycarbonate resin as a binder resin and a predetermined amount of toluene as a solvent were mixed and dispersed by a ball mill to prepare a coating liquid for a charge transport layer. Was prepared. This coating solution was applied onto the charge generation layer with a wire bar, and then dried with hot air at 100 ° C. for 60 minutes to form a charge transport layer having a film thickness of 20 μm, and a positive charging type laminated photoreceptor was produced. . (Evaluation of Electrophotographic Photoreceptor) An electrostatic copying tester (EPA-8100 manufactured by Kawaguchi Denki Co., Ltd.) was used to apply an applied voltage to the photoreceptor of each sample to positively charge it, and a white halogen light was used as a light source. The electrophotographic characteristics were measured using monochromatic light having a wavelength of 780 nm (half-value width of 20 nm) taken out using a bandpass filter. The results are shown in Table 1.

In the table below, V1 represents the initial surface potential of the photoconductor when the photoconductor is charged by applying a voltage, and V2 represents the surface potential 0.8 seconds after the start of exposure as the residual potential. It was measured. E1 / 2 is the half exposure amount when the initial surface potential V1 is attenuated to 1/2.

[0072]

[Table 1]

From Table 1, it can be seen that the photoconductors of Examples 1 and 2 have high sensitivity because the residual potential is lowered. Example 3 The compound obtained in Synthesis Example 1 was used as the electron transfer agent, and the perylene pigment (Ip = 5.50 eV) in which R ^{a to} R ^d in the general formula (3) were all methyl groups was used as the charge generating agent. ) Is used as a hole transporting agent, and p-N, N-diethylbenzaldehyde diphenylhydrazone (Ip = 5.20e) is used.
V) was used. In addition, polycarbonate was used as a binder resin, and these materials were mixed and dispersed in a predetermined amount of dichloromethane with a ball mill at the following blending ratios to prepare a single-layer type photosensitive layer coating solution. Then, after applying this coating solution on an aluminum foil with a wire bar,
It was dried with hot air for 0 minutes to prepare a single-layer type electrophotographic photoreceptor for the visible region having a film thickness of 15 to 20 μm.

(Component) (Parts by Weight) Charge Generating Agent 1 Hole Transporting Agent 60 Electron Transporting Agent 40 Binder Resin 100 Example 4 (Layered Type) The same compound as used in Example 3 was used as a charge generating agent. By weight, 100 parts by weight of polyvinyl butyral resin as a binder resin and a predetermined amount of tetrahydrofuran as a solvent were mixed and dispersed by a ball mill to prepare a coating liquid for charge generation layer. This coating solution was applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of about 1 μm.

On the other hand, 100 parts by weight of the compound obtained in Synthesis Example 1 as an electron transfer agent, 100 parts by weight of a polycarbonate resin as a binder resin, and a predetermined amount of toluene as a solvent were mixed and dispersed by a ball mill to prepare a coating liquid for a charge transport layer. Was prepared. This coating solution is applied onto the charge generation layer with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge transport layer having a film thickness of 20 μm. Was produced. Comparative Example 3 2,6 instead of the compound obtained in Synthesis Example 1 as an electron transfer agent
A single-layer type electrophotographic photoreceptor for visible region was prepared in the same manner as in Example 3 except that -dimethyl-2 ', 6'-di-t-butyl-4,4'-diphenoquinone was used. Comparative Example 4 A single-layer type electrophotographic photosensitive member for visible region was produced in the same manner as in Example 3 except that the electron transporting agent was not contained. Comparative Example 5 (Layered Type) 2,6 in place of the compound obtained in Example 4 as an electron transfer agent
A positively chargeable visible region laminated photoreceptor was prepared in the same manner as in Example 4, except that -dimethyl-2 ', 6'-di-t-butyl-4,4'-diphenoquinone was used. (Evaluation of Electrophotographic Photosensitive Member) Electrophotographic characteristics were measured in the same manner as above except that white halogen light was used as a light source. The results are shown in Table 2.

[0076]

[Table 2]

It can be seen from Table 2 that the photoconductors of Examples 3 and 4 have a high residual sensitivity when used in an analog optical image forming apparatus using a light source in the visible region, because the residual potential is lowered. You can see that it has. Synthesis Example 2 Production of N- (4-benzylphenyl) -2,4,7-trinitrofluorenone imine 2.62 g (8.
31 mmol) and p-aminodiphenylmethane 1.53
g (8.35 mmol) was dissolved in 50 ml of acetic acid and
The reaction was carried out at 10 ° C for 2 hours. After the reaction, it was added to 300 ml of water, and the precipitated crystals were washed with water. The crystals were dried and then purified by silica gel column chromatography (eluted with chloroform: hexane = 1: 2) to give the title compound as a dark red powder (m and n in the general formula (c) are both 0). Compound (1.3 g, yield 32%) was obtained.

The melting point of this product was 189 ° C. The infrared absorption spectrum of this product is shown in FIG. (Evaluation of Electron Transportability) The electron transportability of the compound obtained in Synthesis Example 2 was evaluated by the TOF method. As a result, this compound, in the electric field strength ^{3 × 10 5 V / cm 7.40} × 10 -7 cm 2 /
It showed a mobility of V · sec and was found to have a high electron transporting ability. Example 5 The compound obtained in Synthesis Example 2 was used as an electron transfer agent, and X-type metal-free phthalocyanine (Ip =
5.38 eV) and using p-N,
N-diethylbenzaldehyde diphenylhydrazone (Ip = 5.20 eV) was used. In addition, polycarbonate was used as a binder resin, and these materials were mixed and dispersed in a predetermined amount of dichloromethane with a ball mill at the following blending ratios to prepare a single-layer type photosensitive layer coating solution. Then, this coating solution is applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to give a film thickness of 15 to 2
A 0 μm single-layer type electrophotographic photosensitive member was produced.

(Component) (Parts by Weight) Charge Generating Agent 1 Hole Transporting Agent 60 Electron Transporting Agent 40 Binder Resin 100 Example 6 Instead of the compound used in Synthesis Example 5 as a charge generating agent, oxotitanyl phthalocyanine (Ip = A single-layer type electrophotographic photosensitive member was produced in the same manner as in Example 5 except that 5.32 eV) was used. Comparative Example 6 2,6 instead of the compound obtained in Example 2 as an electron transfer agent
A single-layer type electrophotographic photosensitive member was produced in the same manner as in Example 5 except that -dimethyl-2 ', 6'-di-t-butyl-4,4'-diphenoquinone was used. Comparative Example 7 A single-layer type electrophotographic photosensitive member was produced in the same manner as in Example 5 except that the electron transfer agent was not contained. Example 7 As a charge generating agent, 100 parts by weight of the same compound as used in Example 5, 100 parts by weight of polyvinyl butyral resin as a binder resin, and a predetermined amount of tetrahydrofuran as a solvent were mixed and dispersed in a ball mill to form a charge generating layer. To prepare a coating solution. This coating solution was applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of about 1 μm.

On the other hand, 100 parts by weight of the compound obtained in Synthesis Example 2 as an electron transfer agent, 100 parts by weight of a polycarbonate resin as a binder resin, and a predetermined amount of toluene as a solvent were mixed and dispersed by a ball mill to prepare a coating liquid for a charge transport layer. Was prepared. This coating solution was applied onto the charge generation layer with a wire bar, and then dried with hot air at 100 ° C. for 60 minutes to form a charge transport layer having a film thickness of 20 μm, and a positive charging type laminated photoreceptor was produced. . Comparative Example 8 2,6 instead of the compound obtained in Synthesis Example 2 as the electron transfer agent
A positively chargeable laminated photoreceptor was prepared in the same manner as in Example 7, except that -dimethyl-2 ', 6'-di-t-butyl-4,4'-diphenoquinone was used. (Evaluation of Electrophotographic Photosensitive Member) In the same manner as in Example 1, the electrophotographic characteristics were measured using monochromatic light having a wavelength of 780 nm (half-value width of 20 nm). The results are shown in Table 3.

[0081]

[Table 3]

From Table 3, it can be seen that the photoconductors of Examples 5 to 7 have high sensitivity because the residual potential is lowered. Example 8 The compound obtained in Synthesis Example 2 was used as an electron transfer agent, and a perylene pigment (Ip = 5.50 eV) in which R ^{a to} R ^d in the general formula (3) were all methyl groups was used as a charge generating agent. ) Is used as a hole transporting agent, and p-N, N-diethylbenzaldehyde diphenylhydrazone (Ip = 5.20e) is used.
V) was used. In addition, polycarbonate was used as a binder resin, and these materials were mixed and dispersed in a predetermined amount of dichloromethane with a ball mill at the following blending ratios to prepare a single-layer type photosensitive layer coating solution. Then, after applying this coating solution on an aluminum foil with a wire bar,
It was dried with hot air for 0 minutes to prepare a single-layer type electrophotographic photoreceptor for the visible region having a film thickness of 15 to 20 μm.

(Components) (Parts by Weight) Charge Generating Agent 1 Hole Transfer Agent 60 Electron Transfer Agent 40 Binder Resin 100 Example 9 100 parts by weight of the same compound used in Example 8 as a charge generating agent 100 parts by weight of polyvinyl butyral resin as a coating resin and a predetermined amount of tetrahydrofuran as a solvent were mixed and dispersed by a ball mill to prepare a coating solution for a charge generation layer. This coating solution was applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of about 1 μm.

On the other hand, 100 parts by weight of the compound obtained in Synthesis Example 2 as an electron transfer agent, 100 parts by weight of a polycarbonate resin as a binder resin, and a predetermined amount of toluene as a solvent were mixed and dispersed in a ball mill to prepare a coating liquid for a charge transport layer. Was prepared. This coating solution is applied onto the charge generation layer with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge transport layer having a film thickness of 20 μm. Was produced. (Evaluation of Electrophotographic Photosensitive Member) Electrophotographic characteristics were measured in the same manner as above except that white halogen light was used as a light source. The results are shown in Table 4 together with the results of Comparative Examples 3 to 5 above.

[0085]

[Table 4]

From Table 4, since the residual potentials of the photoconductors of Examples 8 and 9 were lowered, high sensitivity was obtained when used in an image forming apparatus of an analog optical system using a light source in the visible region. You can see that it has. Synthesis Example 3 Production of N- (2-benzylphenyl) -2,4,7-trinitrofluorenone imine 3.1 g (10 mmol) of 2,4,7-trinitrofluorenone and 2.4 g of 2-benzylaniline (13) Was dissolved in 50 ml of acetic acid and reacted at 110 ° C. for 2 hours. After the reaction, it was added to 300 ml of water, and the precipitated crystals were washed with water. The crystals were dried and then purified by silica gel column chromatography (eluted with chloroform: hexane = 1: 2) to give 2.8 g of the title compound (a compound in which m and n in the general formula (d) are both 0) ( Yield 58%) was obtained.

The melting point of this product was 151 ° C. The infrared absorption spectrum of this product is shown in FIG. (Evaluation of electron transporting ability) The electron transporting ability of the compound obtained in Synthesis Example 3 was evaluated by the TOF method. As a result, this compound was 7.90 × 10 ⁻⁷ cm ² / with an electric field strength of 3 × 10 ⁵ V / cm.
It showed a mobility of V · sec and was found to have a high electron transporting ability. Example 10 The compound obtained in Synthesis Example 3 was used as an electron transfer agent, and X-type metal-free phthalocyanine (Ip =
5.38 eV) and using p-N, N as a hole transfer material.
-Diethylbenzaldehyde diphenylhydrazone (I
p = 5.20 eV) was used. In addition, polycarbonate was used as a binder resin, and these materials were mixed and dispersed in a predetermined amount of dichloromethane with a ball mill at the following blending ratios to prepare a single-layer type photosensitive layer coating solution. Then, this coating solution is applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to give a film thickness of 15 to 20.
A single-layer type electrophotographic photosensitive member having a thickness of μm was produced.

(Component) (Parts by Weight) Charge Generating Agent 1 Hole Transporting Agent 60 Electron Transporting Agent 40 Binder Resin 100 Example 11 Instead of the compound used in Example 10 as a charge generating agent, oxotitanyl phthalocyanine (Ip = (5.32 eV)
A single-layer type electrophotographic photosensitive member was produced in the same manner as in Example 10 except that was used. Example 12 100 parts by weight of the same compound used in Example 10 as a charge generating agent, 100 parts by weight of polyvinyl butyral resin as a binder resin, and a predetermined amount of tetrahydrofuran as a solvent were mixed and dispersed in a ball mill to form a charge generating layer. To prepare a coating solution. This coating solution was applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of about 1 μm.

On the other hand, 100 parts by weight of the compound obtained in Synthesis Example 3 as an electron transfer agent, 100 parts by weight of a polycarbonate resin as a binder resin and a predetermined amount of toluene as a solvent were mixed and dispersed in a ball mill to prepare a coating liquid for a charge transport layer. Was prepared. This coating solution was applied onto the charge generation layer with a wire bar, and then dried with hot air at 100 ° C. for 60 minutes to form a charge transport layer having a film thickness of 20 μm, and a positive charging type laminated photoreceptor was produced. . (Evaluation of Electrophotographic Photosensitive Member) Wavelength of 780
The electrophotographic characteristics were measured using monochromatic light of nm (half-value width of 20 nm). The results are shown in Table 5 together with the results of Comparative Examples 6 to 8.

[0090]

[Table 5]

From Table 5, the photoreceptors of Examples 10 to 12 are
Since the residual potential is lowered, it can be seen that it has high sensitivity. Example 13 A compound obtained in Synthesis Example 3 was used as an electron transfer agent, and a perylene pigment (Ip = 5.50 eV) in which R ^{a to} R ^d in the general formula (3) were all methyl groups was used as a charge generating agent. ) Is used as a hole transporting agent, and p-N, N-diethylbenzaldehyde diphenylhydrazone (Ip = 5.20e) is used.
V) was used. In addition, polycarbonate was used as a binder resin, and these materials were mixed and dispersed in a predetermined amount of dichloromethane with a ball mill at the following blending ratios to prepare a single-layer type photosensitive layer coating solution. Then, after applying this coating solution on an aluminum foil with a wire bar,
It was dried with hot air for 0 minutes to prepare a single-layer type electrophotographic photoreceptor for the visible region having a film thickness of 15 to 20 μm.

(Component) (Parts by Weight) Charge Generating Agent 1 Hole Transporting Agent 60 Electron Transporting Agent 40 Binder Resin 100 Example 14 (Layered) The same perylene pigment used in Example 13 was used as the charge generating agent. 100 parts by weight, 100 parts by weight of polyvinyl butyral resin as a binder resin, and a predetermined amount of tetrahydrofuran as a solvent were mixed and dispersed in a ball mill to prepare a coating liquid for charge generation layer. This coating solution was applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of about 1 μm.

On the other hand, 100 parts by weight of the compound obtained in Synthesis Example 3 as an electron transfer agent, 100 parts by weight of a polycarbonate resin as a binder resin and a predetermined amount of toluene as a solvent were mixed and dispersed in a ball mill to prepare a coating liquid for charge transport layer. Was prepared. This coating solution is applied onto the charge generation layer with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge transport layer having a film thickness of 20 μm. Was produced. (Evaluation of Electrophotographic Photosensitive Member) Electrophotographic characteristics were measured in the same manner as above except that white halogen light was used as a light source. The results are shown in Table 6 together with the results of Comparative Examples 3 to 5.

[0094]

[Table 6]

From Table 6, the photoreceptors of Examples 13 and 14 are
Since the residual potential is low, when used in an analog optical image forming device that uses a light source in the visible region,
It can be seen that it has high sensitivity. Synthesis Example 4 Production of N- (3-biphenylyl) -2,4,7-trinitrofluorenone imine 2.4,7-Trinitrofluorenone 3.15 g (1
0.0 mmol) and 2.00 g of m-aminodiphenyl
(11.8 mmol) was dissolved in 50 ml of acetic acid,
The reaction was carried out at 0 ° C for 2 hours. After the reaction, the mixture was poured into 400 ml of distilled water, and the precipitated crystals were washed with water. After drying the crystals,
Silica gel column chromatography (chloroform:
Purified by elution with hexane = 1: 2) to give the title compound (a compound in which n and m are 0 in the general formula (b)).
45 g (yield 50%) was obtained.

The melting point of this product was 247 ° C. The infrared absorption spectrum of this product is shown in FIG. (Evaluation of electron transporting ability) The electron transporting ability of the compound obtained in Synthesis Example 4 was evaluated by the TOF method. As a result, this compound showed that the electric field strength was 3 × 10 ⁵ V / cm and 7.26 × 10 ⁻⁷ cm ² /
It showed a mobility of V · sec and was found to have a high electron transporting ability. Example 15 The compound obtained in Synthesis Example 4 was used as the electron transfer agent, and the perylene pigment (Ip = 5.50 eV) in which R ^{a to} R ^d in the general formula (3) were all methyl groups was used as the charge generating agent. ) Is used as a hole transporting agent, and p-N, N-diethylbenzaldehyde diphenylhydrazone (Ip = 5.20e) is used.
V) was used. In addition, polycarbonate was used as a binder resin, and these materials were mixed and dispersed in a predetermined amount of dichloromethane with a ball mill at the following blending ratios to prepare a single-layer type photosensitive layer coating solution. Then, after applying this coating solution on an aluminum foil with a wire bar,
It was dried with hot air for 0 minutes to prepare a single-layer type electrophotographic photoreceptor for the visible region having a film thickness of 15 to 20 μm.

(Component) (Parts by Weight) Charge Generating Agent 1 Hole Transporting Agent 60 Electron Transporting Agent 40 Binder Resin 100 Example 16 (Layered Type) The same perylene pigment used in Example 15 was used as the charge generating agent. 100 parts by weight, 100 parts by weight of polyvinyl butyral resin as a binder resin, and a predetermined amount of tetrahydrofuran as a solvent were mixed and dispersed in a ball mill to prepare a coating liquid for charge generation layer. This coating solution was applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of about 1 μm.

On the other hand, 100 parts by weight of the compound obtained in Synthesis Example 4 as an electron transfer agent, 100 parts by weight of a polycarbonate resin as a binder resin and a predetermined amount of toluene as a solvent were mixed and dispersed by a ball mill to prepare a coating liquid for a charge transport layer. Was prepared. This coating solution is applied onto the charge generation layer with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge transport layer having a film thickness of 20 μm. Was produced. (Evaluation of Electrophotographic Photosensitive Member) Electrophotographic characteristics were measured in the same manner as above except that white halogen light was used as a light source. The results are shown in Table 7 together with the results of Comparative Examples 3-5.

[0099]

[Table 7]

From Table 7, the photoconductors of Examples 15 and 16 are
Since the residual potential is low, when used in an analog optical image forming device that uses a light source in the visible region,
It can be seen that it has high sensitivity. Synthesis Example 5 Production of N- (2-fluorophenyl) -2,4,7-trinitrofluorenone imine 2.4,7-Trinitrofluorenone 3.15 g (1
0.00 mmol) and 1.44 g of o-fluoroaniline
(13 mmol) and dissolve in 50 ml of acetic acid, 110 ℃
And reacted for 2 hours. After the reaction, the mixture was poured into 300 ml of water, and the precipitated crystals were washed with water. The crystals were dried and purified by silica gel column chromatography (eluted with chloroform: hexane = 1: 2) to give the title compound (the above-mentioned general formula
1.8 g of a compound in which m is 0 in (e) (yield 4
4%).

The melting point of this product was 203 ° C. The infrared absorption spectrum of this product is shown in FIG. 7. (Evaluation of electron transport ability) The electron transport ability of the compound obtained in Synthesis Example 5 was evaluated by the TOF method. As a result, this compound had a field intensity of 3 × 10 ⁵ V / cm, and was 8.17 × 10 ⁻⁷ cm ² /
It showed a mobility of V · sec and was found to have a high electron transporting ability.

The charge generating agent, hole transporting agent and electron transporting agent used in the following Examples and Comparative Examples are as follows. Charge Generating Agent I: X-type metal-free phthalocyanine (Ip = 5.
38eV) II: Oxotitanyl phthalocyanine (Ip = 5.3
2eV) III: In general formula (3), R ^{a to} R ^d are both perylene-based pigments, and Ip is an abbreviation for ionization potential (hereinafter,
the same). Hole transport material (1) N, N, N ', N'-tetrakis (4-methylphenyl) -3,3'-dimethylbenzidine (Ip = 5.5
6eV) (2) N, N'-bis (2,4-dimethylphenyl)-
N, N'-diphenylbenzidine (Ip = 5.43e
V) Electron transfer agent A: compound obtained in Synthesis Example 5 B: 2,6-dimethyl-2 ', 6'-di-t-butyl-
4,4'-Diphenoquinone Examples 17 to 19, 21 to 22 The charge generating agents, hole transporting agents, and electron transporting agents shown in Table 8 were used in the proportions shown below. Polycarbonate was used as the binder resin, and these materials were mixed and dispersed in a predetermined amount of dichloromethane in a ball mill at the following blending ratios to prepare a single-layer type photosensitive layer coating solution. Then, after applying this coating solution on the aluminum foil with a wire bar,
Dry with hot air at 100 ° C for 60 minutes to obtain a film thickness of 15 to 20 μm
A single-layer type electrophotographic photoreceptor of was prepared.

(Component) (Parts by Weight) Charge Generating Agent 1 Hole Transporting Agent 60 Electron Transporting Agent 40 Binder Resin 100 Comparative Example 9 The same as Example 17 except that the above compound B was used as the electron transporting agent. As a result, a single-layer type electrophotographic photosensitive member was produced. Comparative Example 10 A single-layer type electrophotographic photosensitive member was produced in the same manner as in Example 17, except that the electron transfer agent was not contained. Examples 20 and 23 100 parts by weight of the compound shown in Table 8 as a charge generating agent, 100 parts by weight of polyvinyl butyral resin as a binder resin, and a predetermined amount of tetrahydrofuran as a solvent were mixed and dispersed in a ball mill to prepare a coating solution for a charge generating layer. Was prepared. This coating solution was applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of about 1 μm.

On the other hand, 100 parts by weight of the compound A as an electron transfer agent and polycarbonate resin 1 as a binder resin.
00 parts by weight and a predetermined amount of toluene as a solvent were mixed and dispersed by a ball mill to prepare a charge transport layer coating solution. This coating solution was applied onto the charge generation layer with a wire bar, and then dried with hot air at 100 ° C. for 60 minutes to form a charge transport layer having a film thickness of 20 μm, and a positive charging type laminated photoreceptor was produced. . (Evaluation Method of Electrophotographic Photosensitive Member) In the same manner as described above, the electrophotographic characteristics were measured using white halogen light as a light source. The results are shown in Table 8 together with the results of Comparative Examples 1, 2, 5 and 8.

[0105]

[Table 8]

From Table 8, the electrophotographic photosensitive members of the examples have high sensitivity because the residual potential is lowered by containing the specific electron transferring material having an excellent electron transferring property. I understand. Example 24 N- (2-isopropylphenyl) as an electron transport agent
-2,4,7-trinitrofluorenone imine (wherein R ¹ is an isopropyl group and R ^{2 to} R ⁵ are all hydrogen atoms in the general formula (1)) is used, and the above general formula is used as a charge generating agent. A perylene pigment (Ip = 5.50 eV) in which all of R ^{a to} R ^d in the formula (3) are methyl groups is used, and p-N, N-diethylbenzaldehyde diphenylhydrazone (Ip = 5.20 eV) was used. In addition, polycarbonate was used as a binder resin, and these materials were mixed and dispersed in a predetermined amount of dichloromethane with a ball mill at the following blending ratios to prepare a single-layer type photosensitive layer coating solution. Then, this coating solution was applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to prepare a single-layer type electrophotographic photosensitive member for visible region having a film thickness of 15 to 20 μm.

(Components) (Parts by Weight) Charge Generating Agent 1 Hole Transporting Agent 60 Electron Transferring Agent 40 Binder Resin 100 Example 25 100 parts by weight of the same compound used in Example 24 as a charge generating agent 100 parts by weight of polyvinyl butyral resin as a coating resin and a predetermined amount of tetrahydrofuran as a solvent were mixed and dispersed by a ball mill to prepare a coating solution for a charge generation layer. This coating solution was applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of about 1 μm.

On the other hand, 100 parts by weight of the compound used in Example 24 as an electron transfer agent, 100 parts by weight of a polycarbonate resin as a binder resin, and a predetermined amount of toluene as a solvent were mixed and dispersed in a ball mill to prepare a coating liquid for charge transport layer. Was prepared. This coating solution is applied onto the charge generation layer with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge transport layer having a film thickness of 20 μm. Was produced. (Evaluation of Electrophotographic Photosensitive Member) In the same manner as described above, electrophotographic characteristics were measured using white halogen light as a light source. The results are shown in Table 9 together with the results of Comparative Examples 3, 4 and 5.

[0109]

[Table 9]

From Table 9, the photoreceptors of Examples 24 and 25 are
Since the residual potential is low, when used in an analog optical image forming device that uses a light source in the visible region,
It can be seen that it has high sensitivity. The charge generating agent, hole transporting agent and electron transporting agent used in the following Examples and Comparative Examples are as follows. Charge Generating Agent : The same I and II as the above are used. Hole Transporting Agent : The same (1) and (2) as the above are used. The electron transporting agents CG are shown in Table 10.

[0111]

[Table 10]

Examples 26 to 32 The compounds shown in Table 11 were used as the charge generating agent, hole transporting agent and electron transporting agent in the proportions shown below. As the binder resin, polycarbonate is used, and these materials are mixed and dispersed in a predetermined amount of dichloromethane with a ball mill,
A single layer type photosensitive layer coating solution was prepared. Then, this coating solution is applied onto an aluminum foil with a wire bar, and then 10
It was dried with hot air at 0 ° C. for 60 minutes to prepare a single-layer type electrophotographic photoreceptor having a film thickness of 15 to 20 μm.

(Component) (Parts by Weight) Charge Generating Agent 1 Hole Transporting Agent 60 Electron Transporting Agent 40 Binder Resin 100 Comparative Example 11 100 parts by Weight of the Compound I as a Charge Generating Agent and Polyvinyl Butyral Resin as a Binder Resin And 100 parts by weight of tetrahydrofuran as a solvent were mixed and dispersed in a ball mill in a predetermined amount to prepare a charge generation layer coating liquid. This coating solution was applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of about 1 μm.

On the other hand, 100 parts by weight of the compound C as an electron transfer agent and polycarbonate resin 1 as a binder resin.
00 parts by weight and a predetermined amount of toluene as a solvent were mixed and dispersed by a ball mill to prepare a charge transport layer coating solution. This coating solution was applied onto the charge generation layer with a wire bar, and then dried with hot air at 100 ° C. for 60 minutes to form a charge transport layer having a film thickness of 20 μm, and a positive charging type laminated photoreceptor was produced. . (Evaluation Method of Electrophotographic Photoreceptor) Electrophotographic characteristics were measured using white halogen light as a light source in the same manner as described above. The results are shown in Table 11 together with the results of Comparative Examples 1 and 2.

[0115]

[Table 11]

From Table 11, the electrophotographic photoreceptors of Examples are
Since the residual potential is lowered by containing the specific electron transfer agent having an excellent electron transfer property, it can be seen that it has high sensitivity. Test Example The electron transfer properties of the electron transfer agent of the present invention and a conventional diphenoquinone derivative were compared. The samples used are as follows.

Sample 1: Example 26 except that a compound in which R ¹ and R ⁵ are methyl groups and the other substituents R ^{2 to} R ⁴ are hydrogen atoms in the general formula (1) was used as an electron transfer agent. A single-layer type photoreceptor was prepared in the same manner as in. Sample 2: A single-layer type photoreceptor was prepared in the same manner as in Example 26 except that the diphenoquinone derivative represented by H was used as the electron transfer agent.

Sample 3: A single-layer type photoreceptor was prepared in the same manner as in Example 26 except that the electron transfer agent was not added. With respect to the photoconductors of Samples 1 to 3, the exposure amount, that is, the change in the surface potential of the photoconductor with respect to the change in the light energy was measured by "FPA-8100" manufactured by Kawaguchi Electric Co.
The result is shown in FIG. It can be seen from FIG. 8 that the sample 1 using the electron transfer material according to the present invention has high photoconductor characteristics and is also excellent in electron transfer property in a low electric field.

Materials used in the following Examples and Comparative Examples
Is as follows:Charge generator : Uses the same I and II as above Hole transport material : Use the same (1) and (2) as aboveElectron accepting compound a: 2,5-dichloro-p-benzoquinone (redox charge
Position: -0.51V) b: p-benzoquinone (oxidation-reduction potential: -0.81V) c: 2,6-di-t-butyl-p-benzoquinone (oxidation reduction)
Original potential: -1.30 V) d: 3,3'-dinitrodiphenyl sulfone (oxidation reduction)
Original potential: -1.23V) e: 3,5-dimethyl-3 ', 5'-di-t-butyl-
4,4'-diphenoquinone (redox potential: -0.86
V) f: 3,5-dimethoxy-3 ', 5'-di-t-butyl-
4,4'-diphenoquinone (redox potential: -0.87
V) g: 3,3 ', 5,5'-tetra-t-butyl-4,4'
-Diphenoquinone (redox potential: -0.94V)Electron transport agent M: 3,5-dimethyl-3 ', 5'-di-t-butyl-
4,4'-diphenoquinones I to L are shown in Table 12.

[0120]

[Table 12]

Examples 33 to 46, 48 to 50 and Comparative Examples 13 to 23, 25 to 32 As the charge generating agent, the hole transferring agent and the electron accepting compound, Table 1 is shown.
3 and each compound shown in Table 14 were used in the proportions (parts by weight) shown in those tables. Further, the compounds shown in Tables 13 and 14 were used as a hole transporting agent at a ratio of 50 parts by weight. Polycarbonate is used as the binder resin.
Using 0 part by weight, these materials were mixed and dispersed in a predetermined amount of dichloromethane with a ball mill to prepare a single layer type photosensitive layer coating solution. Then, this coating solution was applied on an aluminum foil with a wire bar and dried with hot air at 100 ° C. for 60 minutes to prepare a single-layer type electrophotographic photosensitive member having a film thickness of 15 to 20 μm. Comparative Example 12 100 parts by weight of the above compound I as a charge generating agent, 100 parts by weight of a polyvinyl butyral resin as a binder resin, and a predetermined amount of tetrahydrofuran as a solvent were mixed and dispersed in a ball mill to prepare a coating solution for a charge generating layer. . This coating solution was applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of 0.5 to 1 μm.

On the other hand, 100 parts by weight of the above compound I as an electron transfer agent and polycarbonate resin 1 as a binder resin.
00 parts by weight and a predetermined amount of toluene as a solvent were mixed and dispersed by a ball mill to prepare a charge transport layer coating solution. This coating solution was applied onto the charge generation layer with a wire bar, and then dried with hot air at 100 ° C. for 60 minutes to form a charge transport layer having a film thickness of 15 to 20 μm. Example 47 and Comparative Example 24 The same single-layer electrophotographic photosensitive member as that obtained in Example 33 and Comparative Example 22 was evaluated by negative charging. (Evaluation Method of Electrophotographic Photoreceptor) Electrophotographic characteristics were measured using white halogen light as a light source in the same manner as described above. The results are shown in Tables 13 and 14.

[0123]

[Table 13]

[0124]

[Table 14]

From Tables 13 and 14, the electrophotographic photoreceptors of Examples contained an electron-accepting compound having a predetermined redox potential and a specific electron-transporting agent having an excellent electron-transporting property. It is clear that the residual potential decreases, and the sensitivity is high. This phenomenon is observed even when the types of the charge generating agent and the hole transporting agent are different, and also in the positive charging and the negative charging. Examples 51 to 69 and Comparative Examples 33 to 41 (Positively Charged Laminar Photoreceptor) 100 parts by weight of Compound I as a charge generating agent and the addition amount (parts by weight) of the compound shown in Table 15 as an electron accepting compound. ), 100 parts by weight of polyvinyl butyral resin as a binder resin and a predetermined amount of tetrahydrofuran as a solvent were mixed and dispersed by a ball mill to prepare a coating solution for the charge generation layer. This coating solution was applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of 0.5 to 1 μm.

On the other hand, 100 parts by weight of the compound shown in Table 15 as the electron transfer agent, the addition amount (part by weight) of the compound shown in Table 15 as the electron accepting compound shown in the same table, and 100 parts by weight of the polycarbonate resin as the binder resin. Then, a predetermined amount of toluene as a solvent was mixed and dispersed by a ball mill to prepare a coating liquid for the electron transport layer. After applying this coating liquid on the charge generation layer with a wire bar, it is dried with hot air at 100 ° C. for 60 minutes to form an electron transport layer having a film thickness of 15 to 20 μm, and a positive charging type visible region laminate. A photoconductor was prepared.

Electrophotographic characteristics were measured in the same manner as the single-layer type photoreceptor. The results are shown in Tables 15 and 16.

[0128]

[Table 15]

[0129]

[Table 16]

Examples 70 to 73 (Positively Charged Laminated Photoreceptor) 100 parts by weight of Compound I as a charge generating agent, and the addition amount (parts by weight) of the compound shown in Table 16 as an electron transfer agent in the same table, binding Polyvinyl butyral resin as resin 10
0 part by weight and a predetermined amount of tetrahydrofuran as a solvent were mixed and dispersed by a ball mill to prepare a charge generation layer coating liquid. This coating solution was applied onto an aluminum foil with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form a charge generation layer having a film thickness of 0.5 to 1 μm.

Compounds shown in Table 16 were used as electron transfer agents.
00 parts by weight, polycarbonate resin 10 as a binder resin
0 parts by weight and a predetermined amount of toluene as a solvent were mixed and dispersed in a ball mill to prepare a coating liquid for an electron transport layer. This coating solution is applied onto the charge generation layer with a wire bar and then dried with hot air at 100 ° C. for 60 minutes to form an electron transport layer having a film thickness of 15 to 20 μm. Obtained.

Electrophotographic characteristics were measured in the same manner as in the single layer type photoreceptor. The results are shown in Table 17.

[0133]

[Table 17]

It is understood from FIGS. 15 to 17 that the photoconductor using the electron transfer material according to the present invention has high sensitivity because the residual potential is lowered.

[0135]

INDUSTRIAL APPLICABILITY The electrophotographic photoreceptor of the present invention has an effect that the residual potential is remarkably lowered and a high sensitivity to electrification is obtained by using a specific electron transporting agent having an excellent electron transporting property. . Therefore, when the photoconductor of the present invention is used, the speed of a copying machine, a printer or the like can be increased.

Further, by using the hole transfer agent and the charge generating agent having the respective ionization potentials within the predetermined ranges, the residual potential is further lowered,
A photoreceptor having improved sensitivity can be obtained.

[Brief description of drawings]

FIG. 1 is a graph showing a relationship between a traction voltage (V) and a current (A) for obtaining a redox potential in the present invention.

FIG. 2 is an infrared absorption spectrum of the product obtained in Synthesis Example 1.

FIG. 3 is an NMR absorption spectrum of the product obtained in Synthesis Example 1.

FIG. 4 is an infrared absorption spectrum of the product obtained in Synthesis Example 2.

5 is an infrared absorption spectrum of the product obtained in Synthesis Example 3. FIG.

FIG. 6 is an infrared absorption spectrum of the product obtained in Synthesis Example 4.

7 is an infrared absorption spectrum of the product obtained in Synthesis Example 5. FIG.

FIG. 8 is a graph showing a change in surface potential with respect to an exposure amount of a single-layer type photoconductor in a test example.

Continuation of front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical indication location G03G 5/06 380 (31) Priority claim number Japanese Patent Application No. 6-54207 (32) Priority Day 6 (1994) March 24 (33) Priority claiming country Japan (JP) (31) Priority claiming number Japanese Patent Application No. 6-54211 (32) Priority Day Hei 6 (1994) March 24 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 6-54220 (32) Priority Day Hei 6 (1994) March 24 (33) Country of priority claim Japan (JP) (72) Inventor Keisuke Sumita Osaka Prefecture 1-22 Tamatsukuri, Chuo-ku, Osaka Mita Kogyo Co., Ltd. (72) Inventor Towakazu Uegaki 1-228 Tamatsukuri, Chuo-ku, Osaka-shi Mita Kogyo Co., Ltd. (72) Sakae Saito 1-22 Tamatsukuri, Chuo-ku, Osaka-shi, Osaka Mita Kogyo Co., Ltd. (72) Inventor Shunichi Matsumoto 1-2-2 Tamatsukuri, Chuo-ku, Osaka-shi, Osaka Mita Kogyo Co., Ltd.

Claims (15)

[Claims] 1. General formula (1): (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and the alkyl group, the aryl group And the aralkyl group may have a substituent, provided that R ² , R ³ and R ⁴ are all hydrogen atoms and R ¹ is an alkyl group, an alkoxy group or a halogenated alkyl group. ⁵ is not a hydrogen atom, an alkyl group, an alkoxy group, or a halogenated alkyl group.) A trinitrofluorenone imine derivative represented by. 2. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer is contained in a binder resin.
At least the charge-generating agent and the hole-transporting agent together with the following general formula
An electrophotographic photoreceptor, which is a single layer type containing a trinitrofluorenone imine derivative represented by (2) as an electron transfer agent. [Chemical 2] (In the formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and the alkyl group, the aryl group And the aralkyl group may have a substituent.) 3. The organic photosensitive layer is -0.8 to -1.2V.
The electrophotographic photosensitive member according to claim 2, which contains the electron-accepting compound having the redox potential of. 4. The electron transport layer is a trinitrofluorenone imine derivative represented by the following general formula (1):
Alternatively, the electrophotographic photoconductor of item 3. [Chemical 3] (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and the alkyl group, the aryl group And the aralkyl group may have a substituent, provided that R ² , R ³ and R ⁴ are all hydrogen atoms and R ¹ is an alkyl group, an alkoxy group or a halogenated alkyl group. ⁵ is not a hydrogen atom, alkyl group, alkoxy group or halogenated alkyl group.) 5. The electrophotographic photosensitive member according to claim 2, 3 or 4, wherein the charge generating agent has an ionization potential of 4.8 to 6.0 eV. 6. The electrophotographic photosensitive member according to claim 2, wherein the charge generating agent is a phthalocyanine pigment or a perylene pigment. 7. The electrophotographic photosensitive member according to claim 2, 3 or 4, wherein the hole transport material has an ionization potential of 4.8 to 5.6 eV. 8. The electrophotographic photosensitive member according to claim 2, wherein the hole transfer agent is an alkyl-substituted triphenylamine derivative. 9. The organic photosensitive layer comprises a sterically hindered phenolic antioxidant in an amount of 0.1 to 100 parts by weight of a binder resin.
The electrophotographic photosensitive member according to claim 2, 3 or 4, wherein the content is 50 parts by weight. 10. A laminated electrophotographic photosensitive member comprising at least a charge generation layer and a charge transport layer provided in this order on a conductive substrate, wherein the charge transport layer comprises an electron transfer agent represented by the following general formula (1): An electrophotographic photoreceptor containing the represented trinitrofluorenone imine derivative. [Chemical 4] (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and the alkyl group, the aryl group And the aralkyl group may have a substituent, provided that R ² , R ³ and R ⁴ are all hydrogen atoms and R ¹ is an alkyl group, an alkoxy group or a halogenated alkyl group. ⁵ is not a hydrogen atom, alkyl group, alkoxy group or halogenated alkyl group.) 11. The electrophotographic photoreceptor according to claim 10, wherein the charge generation layer contains a trinitrofluorenone imine derivative represented by the following general formula (2). [Chemical 5] (In the formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and the alkyl group, the aryl group And the aralkyl group may have a substituent.) 12. The electrophotographic photosensitive member according to claim 10, wherein the charge generating layer contains a charge generating agent having an ionization potential of 4.8 to 6.0 eV. 13. The electrophotographic photoreceptor according to claim 10, wherein the charge generating layer contains a charge generating agent selected from a phthalocyanine pigment and a perylene pigment. 14. A laminate type electrophotographic photosensitive member comprising at least a charge generating layer and a charge transporting layer provided in this order on a conductive substrate, wherein the charge transporting layer is represented by the following general formula (2): The charge generation layer contains a trinitrofluorenone imine derivative represented by -0.8 to -1.2.
An electrophotographic photoreceptor containing an electron-accepting compound having a redox potential of V. [Chemical 6] (In the formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and the alkyl group, the aryl group And the aralkyl group may have a substituent.) 15. The charge transport layer comprises -0.8 to -1.2.
The electrophotographic photosensitive member according to claim 14, which contains an electron-accepting positive compound having a redox potential of V.