JPH07199486A - Electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE:To provide a functionally separate type electrophotographic photoreceptor excellent in sensitivity, electric chargeability, stability of its electrostatic characteristic against repeated copying processes, and mechanical durability. CONSTITUTION:In an electrophotographic photoreceptor which has on an electrically conductive support a photosensitive layer comprising at least both a charge generating layer capable of generating a conductive carrier through photoabsorption and a charge transporting layer capable of transporting the conductive carrier generated at the charge generating layer, the charge generating layer contains a charge generating material, a hole transporting material, an electron transporting material and a binding resin as essential components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member used in a copying machine, a printer or the like using an electrophotographic process.

[0002]

2. Description of the Related Art The electrophotographic process uses the visualization of a latent image by electrostatic force as a basic principle. Therefore, the electrophotographic photoreceptor used in the process has good charging property and rapid surface irradiation by light irradiation. Potential decay is required. These properties required for the process are reduced to a high dark resistance which is a specific physical property value, a good quantum efficiency for generating charge carriers, and a high charge mobility.

As a material satisfying these physical property values, a photoconductor composed of an inorganic compound such as selenium, selenium-tellurium alloy, selenium arsenide, and cadmium sulfide has been conventionally used and has been used in many copying machines. . However, these materials are difficult to handle because they are used in an amorphous state with strong toxicity, and in addition, there are drawbacks such as high cost because vacuum deposition is required to a film thickness of several tens of μm.
It cannot be said that it can be said that it sufficiently satisfies the required functions of the photoconductor.

In order to improve these drawbacks, electrophotographic photoconductors (OPC) using organic materials have been actively developed and put into practical use. Most of the practically used OPCs are of the function-separated type in which a charge generation layer (CGL) having a conduction carrier generation function and a charge transport layer (CTL) having a charge transport function are laminated on a conductive support. By adopting such a function-separated structure, the selection range of materials is widened, and the CTLs which are rich in mechanical strength and capable of designing a thick film are arranged on the outermost surface, so that the CTLs in the state of being subjected to the process can be obtained. It has become possible to retain sufficient mechanical durability on the photoconductor, expanding the range of applications from analog to digital. For example, Japanese Patent Publication Sho 55-42
In Japanese Patent No. 380, a function-separated type photoconductor using chlordairon blue and a hydrazone compound is proposed, and many proposals in which various materials are combined have been made (for example, JP-A-54-150128, 56-). 80050
No., 56-80051, 56-83744, 56-
81849, 56-81850, 56-46234.
See each publication). In such a function-separated photoreceptor, the CTL can usually move only one of the conduction carrier components (holes and electrons). Under electric field, C
Of the conductive carriers generated in GL, one component is C
In order for the other component to move quickly in the TL, but the other component to effectively move in the electric field direction opposite to the one component in the CGL, the charge transfer ability of the CGL is generally low. Need to be short. That is, it is necessary to make CGL a thin film. Further, CGL also needs to absorb light efficiently in order to improve sensitivity, and it is necessary to contain a large amount of charge generating substance in CGL. The CTL is generally formed by dispersing a substance having a charge generating ability in a binder resin. A considerable technique is required to maintain the dispersion stability and form a thin film with a dispersion liquid without any defects, and the formation of the CGL thin film determines the yield of the function-separated photoreceptor. Further, in order to form a defect-free thin film, the surface property of the substrate is required to have a considerable level, which greatly affects the cost of the photoconductor. In addition, the carrier mobility of CGL affects electrophotographic characteristics, especially potential fluctuations during repeated use.
Although the function-separated type photoreceptor has excellent characteristics, it cannot be said that the subject is sufficiently satisfied, and further excellent quality characteristics are required as the range of use of OPC is expanded.

[0005]

The object of the present invention is to provide sensitivity,
To provide a function-separated type electrophotographic photosensitive member which is excellent in electrostatic property, has excellent stability in electrostatic characteristics with respect to repetition of a copying process, and has excellent mechanical durability.
Furthermore, it is to provide a function-separated type electrophotographic photoreceptor having excellent productivity.

[0006]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have dispersed a charge-generating substance, a hole-transporting substance, and an electron-transporting substance in a binder resin as a charge-generating layer. Then, a specific compound is used as the electron transporting material, and the charge generating material is further designed to be 0.1 to 40% by weight, preferably 0.3 to 25% by weight, based on the binder resin. As a result, they have found that the above object can be achieved, and have completed the present invention. That is, according to the present invention,
An electron having a photosensitive layer on a conductive support, which includes at least a charge generation layer capable of generating conductive carriers by light absorption and a charge transport layer capable of transporting conductive carriers generated in the charge generation layer. In the photographic photoreceptor, the charge generation layer has a charge generation substance as an essential component,
Provided is an electrophotographic photoreceptor, which contains a hole transport material, an electron transport material, and a binder resin.

Further, according to the present invention, there is provided an electrophotographic photoreceptor in which the electron transporting material contained in the charge generating layer is a fluorene compound represented by the following general formula 1. It

[Chemical 1] (In the formula, R ₁ represents a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, or an alkoxycarbonyl group, and x and y represent integers of 0, 1, 2, 3 or 4. However, 1 ≦ x + y ≦ 4.)

Further, according to the present invention, there is provided an electrophotographic photoconductor characterized in that the electron transporting material contained in the charge generating layer is a fluorene compound represented by the following general formula 2. It

[Chemical 2] (In the formula, R ₁ , R ₂ and R ₃ are a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted sulfonyl group. Represents a group, a substituted or unsubstituted sulfonamide group, a substituted or unsubstituted carbamoyl group, a halogen atom, a cyano group, a nitro group, may form a R ₁ ring, and X represents O or S, l, m, and n represent the integers of 1 to 4.)

Further, according to the present invention, there is provided an electrophotographic photoconductor characterized in that the electron transporting material contained in the charge generating layer is a fluorene compound represented by the following general formula 3. It

[Chemical 3] (In the formula, R ₁ represents an alkyl group. However, R ₁ may combine with each other to form a ring. Further, n represents an integer of 1, 2, 3 or 4.)

Furthermore, according to the present invention, there is provided an electrophotographic photoreceptor characterized in that the electron transporting material contained in the charge generating layer is a homophthalic acid derivative represented by the following general formula (4). Provided.

[Chemical 4] (In the formula, R ₁ is a hydrogen atom, an alkyl group, a halogen atom,
Represents a cyano group or a nitro group, R ₂ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkane group, a substituted or unsubstituted phenyl group, and Ar represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenyl group It represents an unsubstituted polycyclic aromatic group or a substituted or unsubstituted heterocyclic group. )

Furthermore, according to the present invention, the electron transporting material contained in the charge generating layer is an oxazole or thiazole compound represented by the following general formula (5). The body is provided.

[Chemical 5] (In the formula, X represents O or S, R is a substituent, n is an integer, and represents the number of substituents R. Also, R may be the same or different.)

Further, according to the present invention, there is provided a photoconductor for electrophotography, wherein the electron transporting material contained in the charge generating layer is a pyrazine compound represented by the following general formula (6). Provided.

[Chemical 6] (In the formula, X is = C (Y) (Z), = N (CN),
Further, Y and Z each represent a substituent selected from hydrogen, a cyano group, COOR, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group. R represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group. W represents a substituent selected from an alkyl group, a halogen atom, an alkoxycarbonyl group, a phenyl group, a cyano group and a nitro group. n represents an integer of 0 to 4. )

Furthermore, according to the present invention, there is provided a photoconductor for electrophotography, characterized in that the electron transporting substance contained in the charge generating layer is a pyrazine compound represented by the following general formula (7). Provided.

[Chemical 7] (In the formula, R represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.)

Furthermore, according to the present invention, there is provided an electrophotographic photoreceptor, wherein the electron transporting material contained in the charge generating layer is an anthraquinone derivative represented by the following general formula (8). To be done.

[Chemical 8]

Furthermore, according to the present invention, there is provided an electrophotographic photoreceptor, wherein the electron transporting material contained in the charge generating layer is an anthraquinone derivative represented by the following general formula 9. To be done.

[Chemical 9]

Further, according to the present invention, there is provided an electrophotographic photosensitive member characterized in that the electron transporting substance contained in the charge generating layer is a phthalimide compound represented by the following general formula 10. Provided.

[Chemical 10] (In the formula, R ₁ and R ₂ are substituted or unsubstituted alkyl groups,
A substituted or unsubstituted cycloalkane group, a substituted or unsubstituted phenyl group, X is = O, = (Y) (Z), = N (C
N) and Y and Z each represent a hydrogen atom, a substituted or unsubstituted phenyl group, a cyano group, or a substituted or unsubstituted alkoxycarbonyl group. )

According to the present invention, the charge generating substance in the charge generating layer is 0.1 to 40% by weight based on the binder resin.
There is provided an electrophotographic photoreceptor, which is preferably contained in a proportion of 0.3 to 25% by weight.

The photoconductor of the present invention has, for example, the structure shown in FIG. That is, the charge generation layer (2) capable of generating conduction carriers by light absorption is provided on the conductive substrate (3), and the conduction carriers generated in the charge generation layer can be transported thereover. A function-separated type electrophotographic photoreceptor provided with a charge transport layer (1). In the present invention, a charge generating substance, a hole transporting substance, an electron transporting substance and a binder resin are used as the essential components of the charge generating layer,
The compound represented by any one of the above general formulas (1) to (10) is used as the electron transporting material, and the charge generating material is contained in an amount of 0.1 to 40% by weight, preferably 0.1 to 40% by weight, based on the binder resin. It is contained in an amount of 0.3 to 25% by weight.

The electrophotographic photoreceptor of the present invention contains, as essential components, a hole transporting substance capable of moving holes and an electron transporting substance capable of moving electrons in the charge generating layer. The holes and electrons of the conduction carriers can move without remaining in the charge generation layer, and move rapidly in the opposite directions depending on the charging polarity. Therefore, the electrophotographic photoreceptor of the present invention is excellent in sensitivity and chargeability,
Stability of electrostatic characteristics due to repeated use in the copying process,
It has excellent mechanical durability and is suitable for low-speed to high-speed copying processes. In addition, the spectral light-sensitive area can be controlled by changing the charge-generating substance species, and a semiconductor laser beam for optical writing can be output from an analog copying machine for monochrome. It can be applied even to the used page printers and photoconductors of digital copying machines. Further, the content of the charge generating substance in the charge generating layer is 0.1 to 40% by weight, preferably 0.3 to 25% by weight based on the binder resin, and the content of the charge generating substance in the charge generating layer of the conventional function-separated type photoreceptor is By reducing the content of the charge generation material compared to the charge generation layer, the charge generation layer can be made relatively thick without impairing the characteristics, and the high surface level of the conductive substrate of the conventional function-separated photoreceptor is Since it is unnecessary and a coating film defect is less likely to occur, the productivity is increased and the manufacturing cost can be reduced. What is important is to include a hole transporting substance and an electron transporting substance in the charge generating layer, and set the content of the charge generating substance within the above range. In the charge generation layer of the conventional function-separated type photoreceptor, the charge generation substance also has a charge transfer function in the charge generation layer, but a charge generation substance capable of efficiently moving both holes and electrons is used. Since it is small, it is necessary to shorten the moving distance, and it is generally necessary to form a thin film having a thickness of several μm or less, and to relatively contain a large amount of the charge generating substance in order to improve the light absorption efficiency. When a thin film is formed, a film defect is likely to occur, and a good dispersion state of the coating liquid,
The high surface quality of the substrate and the clean manufacturing environment are required, and there is a limit to the reduction of manufacturing cost. Furthermore, since the amount of the charge generating substance is relatively large, there is a problem in mechanical strength, particularly in adhesiveness.

As described above, the function-separated type electrophotographic photoreceptor of the present invention is obtained by dispersing the charge generating substance, the hole transporting substance and the specific electron transporting substance in the binder resin as the charge generating layer. In addition, the charge generation layer can have both the charge generation function and the charge transfer (hole and electron) function, and the relative content of the charge generation substance in the charge generation layer of the conventional function-separated type photoconductor can be compared. Less, and
Since the film thickness can be increased, it has excellent sensitivity and chargeability, and also has excellent electrostatic peculiar stability and mechanical durability against repeated copying processes, and is also excellent in productivity. It is possible to obtain a photoreceptor for use.

Examples of the charge generating substance in the charge generating layer in the electrophotographic photoreceptor of the present invention include bisazo pigments, trisazo pigments, phthalocyanine pigments, perylene pigments, quinacridone pigments, polycyclic quinone pigments, indigo pigments and cyanine pigments. It can be used alone or as a mixture of several kinds. These compositions are 0.1 to 40% by weight, preferably 0.3 to 25% by weight, based on the binder resin.

The hole transporting substance contained in the charge generating layer of the electrophotographic photoreceptor of the present invention is a compound having a triphenylamine moiety in the molecule, a hydrazone compound, a pyrazoline compound, a triphenylmethane compound, an oxadiazole. A compound, an oxazole compound, a carbazole compound, a styryl compound, a butadiene compound, a polysilane compound, a poly-N-vinylcarbazole, a pyrene-formalin condensate and the like can be used alone or in combination. These compositions are preferably 20% by weight or more based on the total composition of the charge generation layer.

The electron transporting substance to be contained in the charge generating layer of the electrophotographic photoreceptor of the present invention is a compound represented by the above general formulas 1 to 10, and these compounds may be used alone or in combination of two or more. Can be used. These compositions are preferably 1 to 40% by weight based on the total composition of the charge generation layer. Specific examples of the fluorene compound represented by the general formula 1 are shown in Table 1 below.
What is shown in.

[0024]

[Table 1- (1)]

[0025]

[Table 1- (2)]

[0026]

[Table 1- (3)]

[0027]

[Table 1- (4)]

[0028]

[Table 1- (5)]

[0029]

[Table 1- (6)]

[0030]

[Table 1- (7)]

[0031]

[Table 1- (8)]

[0032]

[Table 1- (9)]

[0034]

[Table 1- (10)]

[0035]

[Table 1- (11)]

[0036]

[Table 1- (12)]

[0037]

[Table 1- (13)]

[0038]

[Table 1- (14)]

Further, specific examples of the fluorene compound represented by the general formula 2 include those shown in Table 2 below.

[0040]

[Table 2- (1)]

[0041]

[Table 2- (2)]

[0042]

[Table 2- (3)]

[0043]

[Table 2- (4)]

[0044]

[Table 2- (5)]

[0045]

[Table 2- (6)]

[0046]

[Table 2- (7)]

[0047]

[Table 2- (8)]

[0048]

[Table 2- (9)]

[0049]

[Table 2- (10)]

[0050]

[Table 2- (11)]

[0051]

[Table 2- (12)]

[0052]

[Table 2- (13)]

[0053]

[Table 2- (14)]

[0054]

[Table 2- (15)]

[0055]

[Table 2- (16)]

[0056]

[Table 2- (17)]

[0057]

[Table 2- (18)]

[0058]

[Table 2- (19)]

[0059]

[Table 2- (20)]

[0060]

[Table 2- (21)]

[0061]

[Table 2- (22)]

[0062]

[Table 2- (23)]

[0063]

[Table 2- (24)]

[0064]

[Table 2- (25)]

[0065]

[Table 2- (26)]

[0066]

[Table 2- (27)]

[0067]

[Table 2- (28)]

[0068]

[Table 2- (29)]

[0069]

[Table 2- (30)]

[0070]

[Table 2- (31)]

[0071]

[Table 2- (32)]

[0072]

[Table 2- (33)]

Further, specific examples of the fluorene compound represented by the general formula 3 include those shown in Table 3 below.

[0074]

[Table 3- (1)]

[0075]

[Table 3- (2)]

Specific examples of the homophthalic acid derivative represented by the general formula 4 include those listed in Table 4 below.

[0077]

[Table 4- (1)]

[0078]

[Table 4- (2)]

[0079]

[Table 4- (3)]

[0080]

[Table 4- (4)]

[0081]

[Table 4- (5)]

[0082]

[Table 4- (6)]

[0083]

[Table 4- (7)]

[0084]

[Table 4- (8)]

[0085]

[Table 4- (9)]

[0086]

[Table 4- (10)]

Specific examples of the oxazole or thiazole compound represented by the general formula 5 include those shown in Table 5 below.

[0088]

[Table 5]

Further, specific examples of the pyrazine compound represented by the general formula 6 include those shown in Table 6 below.

[0090]

[Table 6- (1)]

[0091]

[Table 6- (2)]

[0092]

[Table 6- (3)]

[0093]

[Table 6- (4)]

[0094]

[Table 6- (5)]

[0095]

[Table 6- (6)]

[0096]

[Table 6- (7)]

[0097]

[Table 6- (8)]

[0098]

[Table 6- (9)]

[0099]

[Table 6- (10)]

[0100]

[Table 6- (11)]

[0101]

[Table 6- (12)]

[0102]

[Table 6- (13)]

[0103]

[Table 6- (14)]

[0104]

[Table 6- (15)]

[0105]

[Table 6- (16)]

[0106]

[Table 6- (17)]

[0107]

[Table 6- (18)]

Further, specific examples of the pyrazine compound represented by the general formula 7 include those shown in Table 7 below.

[0109]

[Table 7- (1)]

[0110]

[Table 7- (2)]

[0111]

[Table 7- (3)]

Further, specific examples of the anthraquinone derivative represented by the general formula 8 include those shown in Table 8 below.

[0113]

[Table 8- (1)]

[0114]

[Table 8- (2)]

Further, specific examples of the anthraquinone derivative represented by the general formula 9 include those shown in Table 9 below.

[0116]

[Table 9- (1)]

[0117]

[Table 9- (2)]

[0118]

[Table 9- (3)]

R ₁ and R _{2 in the} general formulas 8 and 9
In the above, the alkyl group means an alkyl group such as a methyl group and a t-butyl group, a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group, a trifluoromethyl group, a bromooctyl group, 2,2,3,4,4,4. -Hexafluorobutyl group,
2,2-difluoro-2-trifluoromethyl-halogen-substituted alkyl group such as ethyl group, 2-methoxyethyl group, alkoxy-substituted alkyl group such as 2,2-diethoxyethyl group,
4-hexyloxycarbonylhexyl group, includes alkoxycarbonylalkyl groups such as butoxycarbonylmethyl group, benzyl group, cyanoalkyl group, nitroalkyl group, etc., and aromatic groups include phenyl group, pyrene group, phenanthrene group, etc. Aromatic group, 4-chlorophenyl group,
Halogen-substituted aromatic groups such as 1-bromonaphthyl group and 2-trifluoromethylanthracene group, 4-butoxyphenyl group, alkoxy-substituted aromatic groups such as 2,6-dihexaoxynaphthyl group, 3-methoxycarbonylphenyl group , 4-butoxycarbonylnaphthyl and other alkoxycarbonyl groups, 4-acetylphenyl and other acyl-substituted aromatic groups, diphenyl and other phenyl-substituted aromatic groups, and the like, and heterocyclic groups include pyrrole and carbazole. Group, indole group, pyridine group, morpholine group, thiazine group,
It includes a piperidine group, a pyrrolidine group, an imidazole group and the like. In R ₃ and R ₄ in the formula, the halogen atom includes a halogen atom such as fluorine, bromine and iodine, and the alkyl group means a methyl group, an alkyl group such as t-butyl group, a cyclohexyl group, Cycloalkyl group such as cyclopentyl group, trifluoromethyl group, bromooctyl group, 2,2,3,4,4,4-hexafluorobutyl group, 2,2-
Halogen-substituted alkyl group such as difluoro-2-trifluoromethyl-ethyl group, 2-methoxyethyl group, alkoxy-substituted alkyl group such as 2,2-diethoxyethyl group, 4-hexyloxycarbonylhexyl group, butoxycarbonylmethyl Groups such as alkoxycarbonylalkyl groups, benzyl groups, cyanoalkyl groups, nitroalkyl groups, etc., and aromatic groups include phenyl groups, pyrene groups, phenanthrene groups and other aromatic groups, 4-chlorophenyl groups, 1- Bromonaphthyl group, halogen-substituted aromatic group such as 2-trifluoromethylanthracene group, 4-butoxyphenyl group, 2,
Alkoxy-substituted aromatic groups such as 6-dihexaoxynaphthyl group, alkoxycarbonyl groups such as 3-methoxycarbonylphenyl group and 4-butoxycarbonylnaphthyl group, 4
-Acyl-substituted aromatic groups such as acetylphenyl group, phenyl-substituted aromatic groups such as diphenyl group, etc., acyl groups include acetyl group, octylcarbonyl group, etc., and alkoxy groups, methoxy groups, Ethoxy group,
A benzyloxy group and the like are included, an ester group includes a butoxycarbonyl group, a phenoxycarbonyl group, an acetoxyl group, and the like, and an amide group is an N, N-ditolylamide group, N-methyl-N-phenylamide group, N-
A butoxycarbonylamino group and the like, and the sulfonamide group means an N, N-dihexylsulfonamide group, N
-Methoxysulfonylamino group and the like. Furthermore,
In R ₅ in the formula, the alkyl group means a methyl group, t
-Alkyl group such as butyl group, cyclohexyl group, cycloalkyl group such as cyclopentyl group, trifluoromethyl group, bromooctyl group, 2,2,3,4,4,4-hexafluorobutyl group, 2,2-difluoro group -2-Halogen-substituted alkyl group such as trifluoromethyl-ethyl group, 2-methoxyethyl group, alkoxy-substituted alkyl group such as 2,2-diethoxyethyl group, 4-hexyloxycarbonylhexyl group,
Including alkoxycarbonylalkyl groups such as butoxycarbonylmethyl group, benzyl group, cyanoalkyl group, nitroalkyl group, etc., and aromatic groups include aromatic groups such as phenyl group, pyrene group, phenanthrene group, 4-chlorophenyl group. , Halogen-substituted aromatic groups such as 1-bromonaphthyl group and 2-trifluoromethylanthracene group, 4-butoxyphenyl group, alkoxy-substituted aromatic groups such as 2,6-dihexaoxynaphthyl group, 3-methoxycarbonylphenyl Group, an alkoxycarbonyl group such as a 4-butoxycarbonylnaphthyl group, an acyl-substituted aromatic group such as a 4-acetylphenyl group, and a phenyl-substituted aromatic group such as a diphenyl group.

Further, specific examples of the phthalimide compound represented by the general formula 10 are shown in Table 10 below.
The items shown in are listed.

[0121]

[Table 10- (1)]

[0122]

[Table 10- (2)]

[0123]

[Table 10- (3)]

[0124]

[Table 10- (4)]

[0125]

[Table 10- (5)]

[0126]

[Table 10- (6)]

[0127]

[Table 10- (7)]

[0128]

[Table 10- (8)]

[0129]

[Table 10- (9)]

[0130]

[Table 10- (10)]

[0131]

[Table 10- (11)]

[0132]

[Table 10- (12)]

[0133]

[Table 10- (13)]

[0134]

[Table 10- (14)]

As the binder resin for the charge generation layer of the electrophotographic photoreceptor of the present invention, butyral resin, acrylic resin, cellulose resin, silicone resin, polyester resin, polycarbonate resin, styrene resin, polyarylate resin, Phenoxy resin, urethane resin, vinylidene fluoride resin, melamine resin, alkyd resin, epoxy resin, addition resin such as phenol resin, polyaddition type resin, polycondensation type resin, and repeating units of these,
A copolymer resin containing two or more, for example, a vinyl chloride-vinyl acetate copolymer, a styrene-butadiene copolymer, a vinylidene fluoride fluoroethylene copolymer, etc. can be used. These compositions are preferably 30 to 70% by weight based on the total composition of the charge generation layer. The thickness of the charge generation layer of the electrophotographic photoreceptor of the present invention is 0.5 to 5.
0 μm, preferably 1.0 to 20 μm is suitable.

The charge-transporting layer of the present invention comprises at least a charge-transporting substance and a binder resin, and an additive can be added if necessary. As the charge transport material, a hole transport material and an electron transport material can be used. As the hole transport material, the donor compound used in the charge generation layer of the present invention can be used. Further, as the electron transporting substance, in addition to the compounds represented by the general formulas 1 to 10 used in the charge generation layer of the present invention, for example, quinone compounds, vinylidene dinitrile compounds of quinone compounds, fluorenone compounds, fluorenone compounds The vinylidene dinitrile compound, the π-electron compound having a carboxylic acid ester group, the π-electron compound having a cyano group, and the π-electron compound having a nitro group can be used as the acceptor compound. Further, as the binder resin for the charge transport layer, a polycarbonate resin, a polyarylate resin, a styrene resin, or a binder resin for the charge generation layer can be used. Charge transport The composition of the charge transport material is 25 to 400 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of the binder resin. The thickness of the charge transport layer is 5 to 60 μm, preferably 10 to 30 μm. Further, as an additive used as necessary, a defoaming agent,
Antioxidants, adhesion aids, plasticizers and the like can be mentioned.

As the conductive substrate used in the present invention,
Metal plates such as aluminum, nickel, copper, stainless steel,
Examples thereof include a metal drum or a metal foil, a plastic film coated with a thin film of aluminum, tin oxide, copper iodide, or the like, or glass.

The electrophotographic photoreceptor of the present invention can be produced by a known coating method, for example, a dipping coater, a calendar coater, a kiss coater, a gravure coater, a spin coater or a spray coater.

[0139]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereby.

Example 1 X-type metal-free phthalocyanine (Fastogen Blu)
e 8120BS 0.3 g of Dainippon Ink Co., Ltd. 10% by weight of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.)
Tetrahydrofuran solution 30 g, triphenylamine compound 0.6 which is a hole transporting substance represented by the following chemical formula 11
g, and 0.6 g of the fluorene compound represented by the chemical formula 12 below, which is an electron-transporting substance, were added to a mill base prepared by ball milling, and the mixture was stirred to prepare a 6 wt% coating solution, and aluminum was added to a thickness of 1000 Å. Further, a 75 μm thick polyester film vapor-deposited was coated with a doctor blade, and a charge generation layer having a film thickness after drying of 5 μm was provided.

[Chemical 11]

[Chemical 12] Then, 2 g of this triphenylamine compound (Chemical Formula 11)
And 3 g of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.) and 0.002 g of phenylmethyl-polysiloxane (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 20 g of tetrahydrofuran to prepare a coating solution, which was prepared on the charge generation layer. A photoconductor for electrophotography was prepared by coating with a doctor blade and stacking a charge generation layer having a thickness of 18 μm after drying.

Example 2 An electrophotographic photoconductor was prepared under the same conditions as in Example 1 except that the fluorene compound represented by the following chemical formula 13 was used as the electron transporting material of the charge generation layer.

[Chemical 13]

Example 3 An electrophotographic photoreceptor was prepared under the same conditions as in Example 1 except that the diphenoquinone compound represented by the following chemical formula 14 was used as the electron transporting material in the charge transporting layer.

[Chemical 14]

Comparative Example 1 An electrophotographic photoreceptor was prepared under the same conditions as in Example 1 except that the triphenylamine compound represented by Chemical formula 11 and the fluorene compound represented by Chemical formula 12 were removed from the charge generation layer.

Comparative Example 2 An electrophotographic photoreceptor was prepared under the same conditions as in Example 3 except that the triphenylamine compound represented by Chemical formula 11 and the fluorene compound represented by Chemical formula 12 were removed from the charge generation layer.

The electrophotographic photosensitive member thus produced was used as an electrostatic copying paper test apparatus (SP-42 manufactured by Kawaguchi Electric Co., Ltd.).
8) is used, the photoconductors of Examples 1 and 2 and Comparative Example 1 are -6.
The photoconductors of Example 3 and Comparative Example 2 were charged with KV at +6 KV by corona discharge for 20 seconds and then dark-decayed for 20 seconds. After that, the tungsten light was irradiated with 30 tungsten light so that the illuminance on the surface of the photoconductor was 20 lux. Irradiated for 2 seconds. The measurement was performed 100 times continuously under the above conditions, the surface potential Vs (V) after 20 seconds of charging and the surface potential Vo after dark decay of 20 seconds.
(V), the exposure amount E1 / 2 required for Vo to become 1/2
(Lux seconds), the exposure amount E1 / 10 (lux seconds) required for Vo to become 1/10, and the surface potential V30 (V) after 30 seconds of exposure were measured. The results are shown in Table 11.

[Table 11]

Example 4 X-type metal-free phthalocyanine (Fastogen Blu)
e 8120BS 0.3 g of Dainippon Ink Co., Ltd. 10% by weight of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.)
Tetrahydrofuran solution 30 g, triphenylamine compound 0.6 which is a hole-transporting substance represented by the following chemical formula 15
g, and 0.6 g of a fluorene compound represented by the following chemical formula 16 which is an electron-transporting substance are added to a mill base prepared by ball milling, and the mixture is stirred to prepare a coating solution of 6% by weight, and aluminum having a thickness of 1000 Å. Further, a 75 μm thick polyester film vapor-deposited was coated with a doctor blade, and a charge generation layer having a film thickness after drying of 5 μm was provided.

[Chemical 15]

[Chemical 16] Then, 2 g of this triphenylamine compound (Chemical Formula 15)
And 3 g of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.) and 0.002 g of phenylmethyl-polysiloxane (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 20 g of tetrahydrofuran to prepare a coating solution, which was prepared on the charge generation layer. A photoconductor for electrophotography of the present invention was produced by coating with a doctor blade and laminating a charge generation layer having a thickness of 18 μm after drying.

Example 5 An electrophotographic photoconductor of the present invention was produced under the same conditions as in Example 4 except that the electron transporting material of the charge generating layer was changed to the fluorene compound represented by the chemical formula 17 below.

[Chemical 17]

Example 6 An electrophotographic photoreceptor was prepared under the same conditions as in Example 4 except that the diphenoquinone compound represented by the following chemical formula 18 was used as the electron transporting material in the charge generating layer.

[Chemical 18]

Comparative Example 3 An electrophotographic photoreceptor was prepared under the same conditions as in Example 4 except that the triphenylamine compound represented by Chemical formula 15 and the fluorene compound represented by Chemical formula 16 were removed from the charge generation layer.

Comparative Example 4 An electrophotographic photoreceptor was prepared under the same conditions as in Example 6 except that the triphenylamine compound represented by Chemical formula 15 and the fluorene compound represented by Chemical formula 16 were removed from the charge generation layer.

The electrophotographic photosensitive member thus produced was used as an electrostatic copying paper test device (SP-42) manufactured by Kawaguchi Electric Co., Ltd.
8) is used, the photosensitive members of Examples 4 and 5 and Comparative Example 3 are -6.
At KV, the photoconductors of Example 6 and Comparative Example 4 were charged by performing corona discharge for 20 seconds at +6 KV, and further darkly attenuated for 20 seconds, and thereafter, a tungsten light beam was applied to the photoconductor surface so that the illuminance was 20 lux. Irradiated for 2 seconds. The measurement was performed 100 times continuously under the above conditions, the surface potential Vs (V) after 20 seconds of charging and the surface potential Vo after dark decay of 20 seconds.
(V), the exposure amount E1 / 2 required for Vo to become 1/2
(Lux seconds) and surface potential V30 after 30 seconds exposure
(V) was measured. The results are shown in Table 12.

[Table 12]

Example 7 X-type metal-free phthalocyanine (Fastogen Blu)
e 8120BS 0.3 g of Dainippon Ink Co., Ltd. 10% by weight of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.)
Tetrahydrofuran solution 30 g, triphenylamine compound 0.6 which is a hole-transporting substance represented by the following chemical formula 19
g, and 0.6 g of the fluorene compound represented by the following chemical formula 20, which is an electron-transporting substance, are added to a mill base prepared by ball milling, and the mixture is stirred to prepare a coating solution of 6% by weight, and aluminum having a thickness of 1000 Å. Further, a 75 μm thick polyester film vapor-deposited was coated with a doctor blade, and a charge generation layer having a film thickness after drying of 5 μm was provided.

[Chemical 19]

[Chemical 20] Then, 2 g of this triphenylamine compound (Chemical Formula 19)
And 3 g of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.) and 0.002 g of phenylmethyl-polysiloxane (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 20 g of tetrahydrofuran to prepare a coating solution, which was prepared on the charge generation layer. A photoconductor for electrophotography was prepared by coating with a doctor blade and stacking a charge generation layer having a thickness of 18 μm after drying.

Example 8 An electrophotographic photoreceptor was prepared under the same conditions as in Example 7, except that the fluorene compound represented by the following chemical formula 21 was used as the electron transporting material in the charge generating layer.

[Chemical 21]

Example 9 An electrophotographic photoreceptor was prepared under the same conditions as in Example 7, except that the diphenoquinone compound represented by the following chemical formula 22 was used as the electron transporting material in the charge transporting layer.

[Chemical formula 22]

Comparative Example 5 An electrophotographic photoreceptor was prepared under the same conditions as in Example 7 except that the triphenylamine compound represented by Chemical formula 19 and the fluorene compound represented by Chemical formula 20 were removed from the charge generation layer.

Comparative Example 6 An electrophotographic photoreceptor was prepared under the same conditions as in Example 9 except that the triphenylamine compound represented by Chemical formula 19 and the fluorene compound represented by Chemical formula 20 were removed from the charge generation layer.

The electrophotographic photosensitive member thus produced was used as an electrostatic copying paper test apparatus (SP-42 manufactured by Kawaguchi Electric Co., Ltd.).
8) is used, the photosensitive members of Examples 7 and 8 and Comparative Example 5 are -6.
At KV, the photoreceptors of Example 9 and Comparative Example 6 were charged by performing corona discharge at +6 KV for 20 seconds and further darkly attenuated for 20 seconds, and thereafter, a tungsten light beam was applied to the photoreceptor surface so that the illuminance was 20 lux. Irradiated for 2 seconds. The measurement was performed 100 times continuously under the above conditions, the surface potential Vs (V) after 20 seconds of charging and the surface potential Vo after dark decay of 20 seconds.
(V), the exposure amount E1 / 2 required for Vo to become 1/2
(Lux seconds) and surface potential V30 after 30 seconds exposure
(V) was measured. The results are shown in Table 13.

[Table 13]

Example 10 X-type metal-free phthalocyanine (Fastogen Blu)
e 8120BS 0.3 g of Dainippon Ink Co., Ltd. 10% by weight of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.)
Tetrahydrofuran solution 30 g, triphenylamine compound 0.6 which is a hole-transporting substance represented by the following chemical formula 23:
g, and 0.6 g of a homophthalic acid derivative represented by the following chemical formula 24, which is an electron-transporting substance, are added to a mill base prepared by ball milling, and the mixture is stirred to prepare a coating solution of 6% by weight, and aluminum of 1000 Å is prepared. A 75 μm thick polyester film vapor-deposited to a thickness was applied with a doctor blade, and a charge generation layer having a thickness of 5 μm after drying was provided.

[Chemical formula 23]

[Chemical formula 24] Then, 2 g of this triphenylamine compound (Chemical Formula 23)
And 3 g of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.) and 0.002 g of phenylmethyl-polysiloxane (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 20 g of tetrahydrofuran to prepare a coating solution, which was prepared on the charge generation layer. A photoconductor for electrophotography of the present invention was produced by coating with a doctor blade and laminating a charge generation layer having a thickness of 18 μm after drying.

Example 11 An electrophotographic photoreceptor of the present invention was produced under the same conditions as in Example 10 except that the electron transporting material in the charge generation layer was changed to the homophthalic acid derivative shown in Chemical formula 25 below.

[Chemical 25]

Example 12 An electrophotographic photoreceptor was prepared under the same conditions as in Example 10, except that the diphenoquinone compound represented by the following chemical formula 26 was used as the electron transporting material in the charge generation layer.

[Chemical formula 26]

Comparative Example 7 An electrophotographic photoreceptor was prepared under the same conditions as in Example 10 except that the triphenylamine compound represented by Chemical formula 23 and the homophthalic acid derivative represented by Chemical formula 24 were removed from the charge generation layer.

Comparative Example 8 An electrophotographic photoreceptor was prepared under the same conditions as in Example 12, except that the triphenylamine compound represented by Chemical formula 23 and the homophthalic acid derivative represented by Chemical formula 24 were removed from the charge generation layer.

The electrophotographic photoconductor thus prepared was used as an electrostatic copying paper tester (SP-42) manufactured by Kawaguchi Electric Co., Ltd.
8), the photoconductors of Examples 10 and 11 and Comparative Example 7 were -6 KV, and the photoconductors of Example 12 and Comparative Example 8 were +6 KV.
Then, corona discharge was carried out for 20 seconds to charge, and dark decay was further performed for 20 seconds, and thereafter, tungsten light was irradiated for 30 seconds so that the illuminance on the surface of the photoconductor became 20 lux. Under the above conditions, continuous measurement was performed 100 times, the surface potential Vs (V) after charging for 20 seconds and the surface potential V after dark decay for 20 seconds.
o (V), the exposure amount E1 / 2 required for Vo to become 1/2
(Lux seconds) and surface potential V30 after 30 seconds exposure
(V) was measured. The results are shown in Table 14.

[Table 14]

Example 13 X-type metal-free phthalocyanine (Fastogen Blu)
e 8120BS 0.3 g of Dainippon Ink Co., Ltd. 10% by weight of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.)
Tetrahydrofuran solution 30 g, triphenylamine compound 0.6 which is a hole transporting substance represented by the following chemical formula 27
g, and 0.6 g of the thiazole compound represented by the following chemical formula 28, which is an electron-transporting substance, are added to a mill base prepared by ball milling and stirring, and a 6 wt% coating solution is prepared to prepare aluminum having a thickness of 1000 Å. Further, a 75 μm thick polyester film vapor-deposited was coated with a doctor blade, and a charge generation layer having a film thickness after drying of 5 μm was provided.

[Chemical 27]

[Chemical 28] Then, 2 g of this triphenylamine compound (Chemical Formula 27)
And 3 g of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.) and 0.002 g of phenylmethyl-polysiloxane (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 20 g of tetrahydrofuran to prepare a coating solution, which was prepared on the charge generation layer. A photoconductor for electrophotography was prepared by coating with a doctor blade and stacking a charge generation layer having a thickness of 18 μm after drying.

Example 14 An electrophotographic photoreceptor was prepared under the same conditions as in Example 13 except that the electron transporting material in the charge generating layer was changed to the oxazole compound represented by the following formula 29.

[Chemical 29]

Example 15 An electrophotographic photoreceptor was prepared under the same conditions as in Example 13 except that the diphenoquinone compound represented by the following chemical formula 30 was used as the electron transporting material in the charge transporting layer.

[Chemical 30]

Comparative Example 9 An electrophotographic photoreceptor was prepared under the same conditions as in Example 13 except that the triphenylamine compound represented by Chemical formula 27 and the thiazole compound represented by Chemical formula 28 were removed from the charge generation layer.

Comparative Example 10 An electrophotographic photoreceptor was prepared under the same conditions as in Example 15 except that the triphenylamine compound represented by Chemical formula 27 and the thiazole compound represented by Chemical formula 28 were removed from the charge generation layer.

The electrophotographic photosensitive member thus produced was used as an electrostatic copying paper test device (SP-42 manufactured by Kawaguchi Electric Co., Ltd.).
8) is used, the photoreceptors of Examples 13 and 14 and Comparative Example 9 are -6KV, and the photoreceptors of Example 15 and Comparative Example 10 are + 6K.
Corona discharge at V for 20 seconds to charge, then 20
It was dark-decayed for 2 seconds, and thereafter, tungsten light was irradiated for 30 seconds so that the illuminance on the surface of the photoconductor became 20 lux. The measurement was performed 100 times continuously under the above conditions, and the surface potential Vs (V) after charging for 20 seconds, the surface potential Vo (V) after dark decay for 20 seconds, and the exposure amount E1 required for Vo to become 1/2 /
Surface potential V30 after exposure for 2 seconds (lux seconds) and 30 seconds
(V) was measured. The results are shown in Table 15.

[Table 15]

Example 16 X-type metal-free phthalocyanine (Fastogen Blu)
e 8120BS 0.3 g of Dainippon Ink Co., Ltd. 10% by weight of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.)
Tetrahydrofuran solution 30 g, triphenylamine compound 0.6 which is a hole transporting substance represented by the following chemical formula 31
g and 0.6 g of the pyrazine compound represented by the following Chemical Formula 32, which is an electron transporting substance, were added to a mill base prepared by ball milling, and the mixture was stirred and stirred at 6% by weight.
The coating liquid was prepared, and aluminum was vapor-deposited on a polyester film having a thickness of 1000 Å to a thickness of 75 µm by a doctor blade to form a charge generation layer having a thickness of 5 µm after drying.

[Chemical 31]

[Chemical 32] Then, 2 g of this triphenylamine compound (Chemical Formula 31)
And 3 g of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.) and 0.002 g of phenylmethyl-polysiloxane (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 20 g of tetrahydrofuran to prepare a coating solution, which was prepared on the charge generation layer. A photoconductor for electrophotography of the present invention was produced by coating with a doctor blade and laminating a charge generation layer having a thickness of 18 μm after drying.

Example 17 An electrophotographic photoconductor of the present invention was produced under the same conditions as in Example 16 except that the electron transporting material of the charge generating layer was changed to the pyrazine compound represented by the following chemical formula 33.

[Chemical 33]

Example 18 An electrophotographic photoconductor was prepared under the same conditions as in Example 16 except that the diphenoquinone compound represented by the following chemical formula 34 was used as the electron transporting material in the charge generation layer.

[Chemical 34]

Comparative Example 11 An electrophotographic photoreceptor was prepared under the same conditions as in Example 16 except that the triphenylamine compound represented by Chemical formula 31 and the pyrazine compound represented by Chemical formula 32 were removed from the charge generation layer.

Comparative Example 12 An electrophotographic photoreceptor was prepared under the same conditions as in Example 18, except that the triphenylamine compound represented by Chemical formula 31 and the pyrazine compound represented by Chemical formula 32 were removed from the charge generation layer.

The electrophotographic photosensitive member thus produced was used as an electrostatic copying paper test apparatus (SP-42) manufactured by Kawaguchi Electric Co., Ltd.
8) is used, the photoconductors of Examples 16 and 17 and Comparative Example 11 are -6 KV, and the photoconductors of Example 18 and Comparative Example 12 are +6.
Corona discharge at KV for 20 seconds to charge, then 2
It was dark-decayed for 0 second, and thereafter, a tungsten light was irradiated for 30 seconds so that the illuminance on the surface of the photoreceptor was 20 lux.
The measurement was performed 100 times continuously under the above conditions, and the surface potential Vs (V) after charging for 20 seconds, the surface potential Vo (V) after dark decay for 20 seconds, and the exposure amount E required for Vo to become 1/2
Surface potential V3 after exposure for 1/2 (lux seconds) and 30 seconds
0 (V) was measured. The results are shown in Table 16.

[Table 16]

Example 19 X-type metal-free phthalocyanine (Fastogen Blu)
e 8120BS 0.3 g of Dainippon Ink Co., Ltd. 10% by weight of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.)
Tetrahydrofuran solution 30 g, triphenylamine compound 0.6 which is a hole-transporting substance represented by the following formula 35
g, and 0.6 g of the pyrazine compound represented by the following formula 36, which is an electron transporting substance, are added to a mill base prepared by ball milling, and the mixture is stirred to give 6 wt%.
The coating liquid was prepared, and aluminum was vapor-deposited on a polyester film having a thickness of 1000 Å to a thickness of 75 µm by a doctor blade to form a charge generation layer having a thickness of 5 µm after drying.

[Chemical 35]

[Chemical 36] Then, 2 g of this triphenylamine compound (Chemical Formula 35)
And 3 g of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.) and 0.002 g of phenylmethyl-polysiloxane (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 20 g of tetrahydrofuran to prepare a coating solution, which was prepared on the charge generation layer. A photoconductor for electrophotography was prepared by coating with a doctor blade and stacking a charge generation layer having a thickness of 18 μm after drying.

Example 20 An electrophotographic photoconductor was prepared under the same conditions as in Example 19 except that the electron transporting material of the charge generating layer was changed to the pyrazine compound represented by the following Chemical formula 37.

[Chemical 37]

Example 21 An electrophotographic photoreceptor was prepared under the same conditions as in Example 19 except that the diphenoquinone compound represented by the following chemical formula 38 was used as the electron transporting material in the charge transporting layer.

[Chemical 38]

Comparative Example 13 An electrophotographic photoreceptor was prepared under the same conditions as in Example 19 except that the triphenylamine compound represented by Chemical formula 35 and the pyrazine compound represented by Chemical formula 36 were removed from the charge generation layer.

Comparative Example 14 An electrophotographic photoreceptor was prepared under the same conditions as in Example 21, except that the triphenylamine compound represented by Chemical formula 35 and the pyrazine compound represented by Chemical formula 36 were removed from the charge generation layer.

The electrophotographic photosensitive member thus produced was used as an electrostatic copying paper test apparatus (SP-42 manufactured by Kawaguchi Electric Co., Ltd.).
8) is used, the photoreceptors of Examples 19 and 20 and Comparative Example 13 are -6 KV, and the photoreceptors of Example 21 and Comparative Example 14 are +6.
Corona discharge at KV for 20 seconds to charge, then 2
It was dark-decayed for 0 second, and thereafter, a tungsten light was irradiated for 30 seconds so that the illuminance on the surface of the photoreceptor was 20 lux.
The measurement was performed 100 times continuously under the above conditions, and the surface potential Vs (V) after charging for 20 seconds, the surface potential Vo (V) after dark decay for 20 seconds, and the exposure amount E required for Vo to become 1/2
Surface potential V3 after exposure for 1/2 (lux seconds) and 30 seconds
0 (V) was measured. The results are shown in Table 17.

[Table 17]

Example 22 X-type metal-free phthalocyanine (Fastogen Blu)
e 8120BS 0.3 g of Dainippon Ink Co., Ltd. 10% by weight of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.)
Tetrahydrofuran solution 30 g, triphenylamine compound 0.6 which is a hole-transporting substance represented by the following formula 39
g, and 0.6 g of an anthraquinone derivative represented by the following chemical formula 40, which is an electron-transporting substance, are added to a mill base prepared by ball milling, and the mixture is stirred.
A coating solution of weight% was prepared, and aluminum was vapor-deposited on a polyester film having a thickness of 1000 .mu.m to a thickness of 75 .mu.m to apply it with a doctor blade.

[Chemical Formula 39]

[Chemical 40] Then, 2 g of this triphenylamine compound (Chemical Formula 39)
And 3 g of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.) and 0.002 g of phenylmethyl-polysiloxane (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 20 g of tetrahydrofuran to prepare a coating solution, which was prepared on the charge generation layer. A photoconductor for electrophotography of the present invention was produced by coating with a doctor blade and laminating a charge generation layer having a thickness of 18 μm after drying.

Example 23 An electrophotographic photoconductor of the present invention was prepared under the same conditions as in Example 22 except that the electron transporting material of the charge generating layer was changed to the anthraquinone derivative represented by the following chemical formula 41.

[Chemical 41]

Example 24 An electrophotographic photoreceptor was prepared under the same conditions as in Example 22 except that the diphenoquinone compound represented by the following chemical formula 42 was used as the electron transporting material in the charge generation layer.

[Chemical 42]

Comparative Example 15 An electrophotographic photoreceptor was prepared under the same conditions as in Example 22 except that the triphenylamine compound represented by Chemical formula 39 and the anthraquinone derivative represented by Chemical formula 40 were removed from the charge generation layer.

Comparative Example 16 An electrophotographic photoreceptor was prepared under the same conditions as in Example 24 except that the triphenylamine compound represented by Chemical formula 39 and the anthraquinone derivative represented by Chemical formula 40 were removed from the charge generation layer.

The electrophotographic photosensitive member thus produced was used as an electrostatic copying paper test apparatus (SP-42 manufactured by Kawaguchi Electric Co., Ltd.).
8), the photoconductors of Examples 22 and 23 and Comparative Example 15 had -6 KV, and the photoconductors of Example 24 and Comparative Example 16 had +6.
Corona discharge at KV for 20 seconds to charge, then 2
It was dark-decayed for 0 second, and thereafter, a tungsten light was irradiated for 30 seconds so that the illuminance on the surface of the photoreceptor was 20 lux.
The measurement was performed 100 times continuously under the above conditions, and the surface potential Vs (V) after charging for 20 seconds, the surface potential Vo (V) after dark decay for 20 seconds, and the exposure amount E required for Vo to become 1/2
Surface potential V3 after exposure for 1/2 (lux seconds) and 30 seconds
0 (V) was measured. The results are shown in Table 18.

[Table 18]

Example 25 X-type metal-free phthalocyanine (Fastogen Blu)
e 8120BS 0.3 g of Dainippon Ink Co., Ltd. 10% by weight of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.)
Tetrahydrofuran solution 30 g, triphenylamine compound 0.6 which is a hole-transporting substance represented by the following Chemical Formula 43.
g, and 0.6 g of a phthalimide compound represented by the following chemical formula 44, which is an electron-transporting substance, are added to a mill base prepared by ball milling, and the mixture is stirred to prepare a coating solution of 6% by weight, and aluminum is added to a thickness of 1000 Å. Further, a 75 μm thick polyester film vapor-deposited was coated with a doctor blade, and a charge generation layer having a film thickness after drying of 5 μm was provided.

[Chemical 43]

[Chemical 44] Then, 2 g of this triphenylamine compound (Chemical Formula 43)
And 3 g of Polycarbonate Z (manufactured by Teijin Chemicals Ltd.) and 0.002 g of phenylmethyl-polysiloxane (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 20 g of tetrahydrofuran to prepare a coating solution, which was prepared on the charge generation layer. A photoconductor for electrophotography was prepared by coating with a doctor blade and stacking a charge generation layer having a thickness of 18 μm after drying.

Example 26 An electrophotographic photoconductor was prepared under the same conditions as in Example 25 except that the phthalimide compound represented by the following chemical formula 45 was used as the electron transport material in the charge generation layer.

[Chemical formula 45]

Example 27 An electrophotographic photoconductor was prepared under the same conditions as in Example 25 except that the electron-transporting substance in the charge-transporting layer was changed to the diphenoquinone compound represented by the following formula 46.

[Chemical formula 46]

Comparative Example 17 An electrophotographic photoreceptor was prepared under the same conditions as in Example 25 except that the triphenylamine compound represented by Chemical formula 43 and the phthalimide compound represented by Chemical formula 44 were removed from the charge generation layer.

Comparative Example 18 An electrophotographic photoreceptor was prepared under the same conditions as in Example 27 except that the triphenylamine compound represented by Chemical formula 43 and the phthalimide compound represented by Chemical formula 44 were removed from the charge generation layer.

The electrophotographic photosensitive member thus produced was used as an electrostatic copying paper test apparatus (SP-42 manufactured by Kawaguchi Electric Co., Ltd.).
8), the photoconductors of Examples 25 and 26 and Comparative Example 17 were -6 KV, and the photoconductors of Example 27 and Comparative Example 18 were +6.
Corona discharge at KV for 20 seconds to charge, then 2
It was dark-decayed for 0 second, and thereafter, a tungsten light was irradiated for 30 seconds so that the illuminance on the surface of the photoreceptor was 20 lux.
The measurement was performed 100 times continuously under the above conditions, and the surface potential Vs (V) after charging for 20 seconds, the surface potential Vo (V) after dark decay for 20 seconds, and the exposure amount E required for Vo to become 1/2
Surface potential V3 after exposure for 1/2 (lux seconds) and 30 seconds
0 (V) was measured. The results are shown in Table 19.

[Table 19]

[0194]

As described above, according to the present invention, since the hole transport material and the electron transport material are contained in the charge generation layer as essential components, the charge generation property is improved with a relatively small content of the charge generation material. It is possible to obtain a function-separated type electrophotographic photosensitive member which is excellent and has excellent stability of electrostatic properties and mechanical durability against repeated copying processes.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of an electrophotographic photoreceptor according to the present invention.

[Explanation of Codes] 1 charge transport layer 2 charge generation layer 3 conductive substrate

 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Akio Kojima 1-3-6 Nakamagome, Ota-ku, Tokyo Stock company Ricoh (72) Inventor Yumi Ichikawa 1-3-6 Nakamagome, Ota-ku, Tokyo Shares In Ricoh Company (72) Inventor Masayuki Oyano 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company Ricoh (72) Inventor Emi Kawahara 1-3-6 Nakamagome, Tokyo-shi Ricoh Company ( 72) Inventor Hisao Kurosu 1-3-6 Nakamagome, Ota-ku, Tokyo Within Ricoh Co., Ltd.

Claims (13)

[Claims] 1. A charge generating layer capable of generating conductive carriers at least by absorbing light on a conductive support,
In an electrophotographic photoreceptor having a photosensitive layer comprising a charge transport layer capable of transporting the conductive carriers generated in the charge generation layer, the charge generation layer, as an essential component, a charge generation substance, a hole transport substance, An electrophotographic photoreceptor comprising an electron transporting material and a binder resin. 2. The electrophotographic photosensitive member according to claim 1, wherein the electron transporting material contained in the charge generating layer is a fluorene compound represented by the following general formula 1. [Chemical 1] (In the formula, R ₁ represents a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, or an alkoxycarbonyl group, and x and y represent integers of 0, 1, 2, 3 or 4. However, 1 ≦ x + y ≦ 4.) 3. The electrophotographic photosensitive member according to claim 1, wherein the electron transporting material contained in the charge generating layer is a fluorene compound represented by the following general formula 2. [Chemical 2] (In the formula, R ₁ , R ₂ and R ₃ are a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted sulfonyl group. Represents a group, a substituted or unsubstituted sulfonamide group, a substituted or unsubstituted carbamoyl group, a halogen atom, a cyano group, a nitro group, may form a R ₁ ring, and X represents O or S, l, m, and n represent the integers of 1 to 4.) 4. The electrophotographic photosensitive member according to claim 1, wherein the electron transporting substance contained in the charge generating layer is a fluorene compound represented by the following general formula 3. [Chemical 3] (In the formula, R ₁ represents an alkyl group. However, R ₁ may combine with each other to form a ring. Further, n represents an integer of 1, 2, 3 or 4.) 5. The electrophotographic photoreceptor according to claim 1, wherein the electron transporting material contained in the charge generating layer is a homophthalic acid derivative represented by the following general formula 4. [Chemical 4] (In the formula, R ₁ is a hydrogen atom, an alkyl group, a halogen atom,
Represents a cyano group or a nitro group, R ₂ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkane group, a substituted or unsubstituted phenyl group, and Ar represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenyl group It represents an unsubstituted polycyclic aromatic group or a substituted or unsubstituted heterocyclic group. ) 6. The photoconductor for electrophotography according to claim 1, wherein the electron transporting material contained in the charge generating layer is an oxazole or thiazole compound represented by the following general formula 5. [Chemical 5] (In the formula, X represents O or S, R is a substituent, n is an integer, and represents the number of substituents R. Also, R may be the same or different.) 7. The photoconductor for electrophotography according to claim 1, wherein the electron transporting substance contained in the charge generating layer is a pyrazine compound represented by the following general formula (6). [Chemical 6] (In the formula, X is = C (Y) (Z), = N (CN),
Further, Y and Z each represent a substituent selected from hydrogen, a cyano group, COOR, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group. R represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group. W represents a substituent selected from an alkyl group, a halogen atom, an alkoxycarbonyl group, a phenyl group, a cyano group and a nitro group. n represents an integer of 0 to 4. ) 8. The electrophotographic photosensitive member according to claim 1, wherein the electron transporting material contained in the charge generating layer is a pyrazine compound represented by the following general formula 7. [Chemical 7] (In the formula, R represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.) 9. The electrophotographic photoreceptor according to claim 1, wherein the electron transporting material contained in the charge generating layer is an anthraquinone derivative represented by the following general formula (8). [Chemical 8] 10. The electrophotographic photosensitive member according to claim 1, wherein the electron transporting substance contained in the charge generating layer is an anthraquinone derivative represented by the following general formula 9. [Chemical 9] 11. The electrophotographic photosensitive member according to claim 1, wherein the electron transporting material contained in the charge generating layer is a phthalimide compound represented by the following general formula 10. [Chemical 10] (In the formula, R ₁ and R ₂ are substituted or unsubstituted alkyl groups,
A substituted or unsubstituted cycloalkane group, a substituted or unsubstituted phenyl group, X is = O, = (Y) (Z), = N (C
N) and Y and Z each represent a hydrogen atom, a substituted or unsubstituted phenyl group, a cyano group, or a substituted or unsubstituted alkoxycarbonyl group. ) 12. The electron according to claim 1, wherein the charge generating substance in the charge generating layer is contained in a proportion of 0.1 to 40% by weight with respect to the binder resin which is the essential component. Photoreceptor for photography. 13. The electron according to claim 1, wherein the charge generating substance in the charge generating layer is contained in a proportion of 0.3 to 25% by weight with respect to the binder resin which is the essential component. Photoreceptor for photography.