JP2000231209A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrophotographic photoreceptor excellent in sensitivity and electrification ability by incorporating a mixture of specified plural tetraazaporaphyrin derivatives into a photosensitive layer on an electrically conductive substrate. SOLUTION: The electrophotographic photoreceptor has a photosensitive layer containing a mixture of two or more tetraazaporphyrin derivatives of at least formula I on an electrically conductive substrate. In the formula I, A-D are each a benzene ring which may have a substituent or a ring of formula II and may be mutually the same or different, M is a metal, a metal oxide, a metal hydroxide or a metal halide, r1-r4 are each H, halogen, optionally substituted alkoxy, optionally substituted aryl, optionally substituted cycloalkyl or nitro.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoreceptor for electrophotography, and more particularly to a novel tetraazaporphyrin derivative as a substance which generates charge carriers when irradiated with light (hereinafter referred to as "charge generating substance"). The present invention relates to an electrophotographic photosensitive member provided with a photosensitive layer containing a mixture.

[0002]

2. Description of the Related Art Conventionally, various inorganic and organic photoconductors are known as photoconductive materials for photoconductors used in electrophotography. The term "electrophotographic method" as used herein generally means that a photoconductive photoreceptor is first charged in a dark place, for example, by corona discharge, and then subjected to image exposure to selectively dissipate the charges in only the exposed portions, and then statically. An image called a Carlson process in which an electrostatic latent image is obtained, and the latent image portion is developed with a toner composed of a colorant such as a dye or a pigment and a polymer material to visualize the image to form an image. This is one of the formation processes. Photoreceptors using organic photoconductors have advantages over inorganic photoconductors in the degree of freedom of the photosensitive wavelength range, film formability, flexibility, film transparency, mass productivity, toxicity and cost. Therefore, organic photoconductors are currently used for most photoconductors. The photoreceptor repeatedly used in the electrophotographic method and similar processes has excellent electrostatic characteristics such as sensitivity, receptive potential, potential holding property, potential stability, residual potential, and spectral sensitivity characteristics. Is required.

In recent years, the development of information processing systems using the electrophotographic system has been remarkable. In particular,
2. Description of the Related Art A printer using a digital recording system in which information is converted into a digital signal and information is recorded by light has been significantly improved in print quality and reliability. This digital recording method is applied not only to printers but also to ordinary copying machines, and so-called digital copying machines have been developed. Further, since the digital copier is added with various information processing functions, its demand is expected to increase in the future.

[0004] A photoconductor compatible with such a digital recording system is required to have characteristics different from those of a conventional analog system. For example, a small, inexpensive and highly reliable semiconductor laser (LD) is currently used as a light source.
And light emitting diodes (LEDs) are often used. The emission wavelength range of the LD that is currently widely used is in the near infrared light range, and the emission wavelength of the LED is longer than 650 nm.
For this reason, in addition to the requirements for the photoreceptor in the digital recording method, it is desired that the photoreceptor has high sensitivity from a visible light region to a near infrared light region.

From this viewpoint, squarylium dyes (JP-A-49-105536 and JP-A-58-21416), triphenylamine-based trisazo pigments (JP-A-61-151659), and phthalocyanine pigments (JP-A-61-151659) Nos. 48-34189 and 57-14874
Have been proposed as photoconductors for digital recording. In particular, the phthalocyanine pigment, which is a tetraazaporphyrin derivative, has a photosensitive wavelength range up to a long wavelength range, has high photosensitivity, and has various characteristics variations depending on the type of central metal and crystal form. Research has been actively conducted as a photoconductor for recording. Known phthalocyanine pigments exhibiting good sensitivity include ε-type copper phthalocyanine, X
Type metal-free phthalocyanine, τ type metal-free phthalocyanine,
Vanadyl phthalocyanine, titanyl phthalocyanine and the like can be mentioned.

Among them, Japanese Patent Application Laid-Open No. Sho 64-17066,
JP-A-3-128973, JP-A-5-98182
Discloses a highly sensitive titanyl phthalocyanine pigment. The spectral wavelength range of these titanyl phthalocyanine pigments shows a maximum absorption in the range of 700 to 860 nm, and shows extremely high sensitivity to semiconductor laser light. However, when the titanyl phthalocyanine pigment shown in the above-mentioned patent publication is used for an electrophotographic photoreceptor,
Although sufficient in sensitivity, there remain many practical problems such as a reduction in chargeability due to repeated fatigue and a large temperature and humidity dependence in sensitivity characteristics [Y, Fujim
aki, Proc. IS &T's 7th International1Congress on Adv
ances in Non-Impact Printing Technologies, 1 , 269
(1991); Daimon, et al. : J. Imaging Sci. Tech
nol., 40 , 249 (1996)].

For asymmetric or mixed pigments, see JP-A-2-39160 and JP-A-3-27111.
JP-A-4-283581, JP-A-4-11336
No. 1 discloses that a mixture of a phthalocyanine, a phthalocyanine nitrogen isostructural pigment, and a phthalocyanine sulfur isostructural pigment is useful as a photoconductor. However, electrophotographic photoreceptors using these do not sufficiently satisfy the requirements of the photoreceptors in terms of sensitivity in the visible region and near infrared region, charging characteristics, durability against repeated use, and the like.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an electrophotographic photoreceptor which eliminates the above-mentioned disadvantages of the photoconductor of the conventional electrophotographic photoreceptor and has excellent sensitivity, chargeability and the like. Is to do.

[0009]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found a novel tetraazaporphyrin derivative mixture which is useful as a charge generating material for an electrophotographic photoreceptor. The invention has been completed.

That is, according to the present invention, first, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, at least two or more types represented by the following general formula (1) are contained in the photosensitive layer. An electrophotographic photoreceptor characterized in that it contains a tetraazaporphyrin derivative mixture consisting of the above tetraazaporphyrin derivative.

Embedded image (In the above formula, A, B, C and D represent a benzene ring which may have a substituent or a ring represented by the following general formula (2),
They may be the same or different. M represents a metal, a metal oxide, a metal hydroxide or a metal halide.

Embedded image However, in the above formula, r _{1 to} r ₄ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group. Or a nitro group. Second, in an electrophotographic photoreceptor having a photosensitive layer on a conductive support, at least one of the general formula (1)
Wherein at least one of A, B, C and D in the general formula (1) is a benzene ring which may have a substituent, and at least one of the benzene rings is represented by the general formula (2). And a tetraazaporphyrin derivative which is a benzene ring in which all of A, B, C and D in the general formula (1) may have a substituent. An electrophotographic photoreceptor is provided. Third, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the photosensitive layer is represented by at least the general formula (1), and A, B, C and At least one of D is a benzene ring which may have a substituent, and at least one is a tetraazaporphyrin derivative which is a ring represented by the general formula (2); An electrophotographic photoreceptor is provided, wherein all of A, B, C and D contain a tetraazaporphyrin derivative which is a ring represented by the general formula (2). Fourthly, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the photosensitive layer is represented by at least the general formula (1), and furthermore, A, B and C in the general formula (1).
And D is a benzene ring which may have a substituent, and at least one is a tetraazaporphyrin derivative which is a ring represented by the general formula (2); Wherein all of A, B, C, and D are benzene rings which may have a substituent, and a tetraazaporphyrin derivative; and, in the general formula (1), all of A, B, C, and D have the general formula ( An electrophotographic photoreceptor comprising a ring represented by 2) and a tetraazaporphyrin derivative. Fifth, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, a tetraazaporphyrin derivative comprising at least two or more tetraazaporphyrin derivatives represented by the following general formula (3) in the photosensitive layer: An electrophotographic photoreceptor characterized by containing a mixture is provided.

Embedded image (In the above formula, A, B, C and D represent a benzene ring which may have a substituent or a ring represented by the following general formula (2),
They may be the same or different. M represents a metal, a metal oxide, a metal hydroxide or a metal halide.

Embedded image However, in the above formula, r _{1 to} r ₄ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group. Or a nitro group. Sixth, in an electrophotographic photoreceptor having a photosensitive layer on a conductive support, at least one of the formula (3)
Wherein at least one of A, B, C and D in the general formula (3) is a benzene ring which may have a substituent, and at least one of the benzene rings is represented by the general formula (2). And a tetraazaporphyrin derivative which is a benzene ring in which all of A, B, C and D in the general formula (3) may have a substituent. An electrophotographic photoreceptor is provided. Seventh, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the photosensitive layer is represented by at least the above-mentioned general formula (3), and A, B, C and At least one of D is a benzene ring which may have a substituent, and at least one is a tetraazaporphyrin derivative which is a ring represented by the general formula (2); An electrophotographic photoreceptor is provided, wherein all of A, B, C and D contain a tetraazaporphyrin derivative which is a ring represented by the general formula (2). Eighth, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the photosensitive layer is represented by at least the general formula (3), and A, B, C in the general formula (3).
And D is a benzene ring which may have a substituent, and at least one is a tetraazaporphyrin derivative which is a ring represented by the general formula (2); Wherein all of A, B, C and D are a benzene ring which may have a substituent, and a tetraazaporphyrin derivative; and in the general formula (3), all of A, B, C and D have the general formula ( An electrophotographic photoreceptor comprising a ring represented by 2) and a tetraazaporphyrin derivative. Ninth, the photosensitive layer according to any one of the above first to eighth aspects comprises a charge generation layer containing a charge generation substance and a charge transport layer containing a charge transport substance, and the charge generation layer Comprising a mixture of various tetraazaporphyrin derivatives represented by the general formula (1) or (3) described in any one of the above first to eighth. A body is provided. Tenth, in the electrophotographic photoreceptor described in the ninth aspect, the photosensitive layer comprises a charge generation layer containing a charge generation substance, and a charge transport layer containing a hole transport substance. A negatively charged electrophotographic photoreceptor characterized by being provided on a body is provided. Eleventhly, there is provided an electrophotographic photoreceptor wherein the hole transporting material is a stilbene compound represented by the following general formula (4) in the photoreceptor described in the tenth aspect.

Embedded image (Wherein, R ₁ and R ₂ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and R ₃ and R ₄ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted Represents an aryl group or a heterocyclic group.
₁ and R ₂ may form a ring with each other. Ar ₁ represents a substituted or unsubstituted arylene group or a heterocyclic group. Twelfth, in the electrophotographic photoreceptor according to the ninth aspect, the photosensitive layer includes a charge generation layer containing a charge generation substance;
A positive charge type electrophotographic photoreceptor is provided, wherein a charge transport layer containing an electron transport material is provided on a conductive support in this order. Thirteenth, in the photoconductor described in the twelfth aspect, the electron transporting material is (2,3-diphenyl-1-indenylidene) malononitrile represented by the following formula (5). A photographic photoreceptor is provided.

Embedded image Fourteenthly, the photosensitive layer according to any one of the first to eighth aspects may be a charge generation substance, wherein the photosensitive layer is represented by the general formula (1) or (3) according to any one of the first to eighth aspects. A single layer containing a tetraazaporphyrin derivative mixture composed of the following tetraazaporphyrin derivative.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the tetraazaporphyrin derivative mixture comprising the tetraazaporphyrin derivative represented by the general formula (1) of the present invention, M in the general formula (1) is, for example, Cu, TiO, Mg, Co, Pb, VO , F
e, Zn, Ge, Sn, Ni, Al, Ga, Mo, In
And the like, metal oxides, metal hydroxides, and metal halides.

The substituents of the rings A, B, C and D in the general formulas (1) and (3) [substituents of the benzene ring and r ₁ to r _{4 in} the general formula (2)} 6) to (8), including r ₅ to r ₆ ｝] are a hydrogen atom, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group Or a substituted or unsubstituted cycloalkyl group. Specifically, as the halogen atom, an iodine atom,
Examples thereof include a bromine atom, a chlorine atom, and a fluorine atom. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, and a
-Butyl group, n-butyl group, iso-butyl group, trifluoromethyl group, 2-cyanoethyl group, benzyl group,
-Chlorobenzyl group, 4-methylbenzyl group, and the like, and examples of the substituent include the above-described halogen atom, nitro group, and cyano group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-
Butoxy group, sec-butoxy group, tert-butoxy group, 2-hydroxyethoxy group, 2-cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group,
Examples of the substituent include a trifluoromethoxy group and the like, and examples of the substituent include the above-described halogen atom, nitro group, and cyano group. Further, as the aryl group, a phenyl group,
Naphthyl group, biphenylyl group, terphenylyl group, pyrenyl group, fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, thienyl group, benzothienyl group, furyl group,
Examples include a benzofuranyl group, a carbazolyl group, a pyridyl group, a pyridinyl group, a pyrrolidyl group, an oxazolyl group, and the like, and examples of the substituent include the above-described halogen atoms, alkyl groups, alkoxy groups, nitro groups, and cyano groups. Examples of the cycloalkyl group include a cyclohexyl group, and examples of the substituent include the above-described halogen atom, alkyl group, alkoxy group, nitro group, and cyano group.

The tetraasaporphyrin derivative mixture represented by the general formula (1) of the present invention is, for example, phthalonitrile represented by the following general formula (6) or the following general formula (7)
A 1,3-diiminoisoindoline derivative represented by
A mixture of a nitrile derivative represented by the following general formula (8) is mixed with a metal or a compound having a metal together with no solvent or α.
-Halogen solvents such as chloronaphthalene, dichlorobenzene and trichlorobenzene, alcohol solvents such as pentanol and octanol, amine solvents such as N, N-dimethylformamide and N-methylpyrrolidone, and aromatics such as benzene, toluene and nitrobenzene. It can be obtained by reacting in the presence of a group-based solvent. The phthalonitrile derivative represented by the following general formula (6) and the 1,3-diiminoisoindoline derivative represented by the following general formula (7) are described in phthalocyanine-chemistry and function-by Shirai and Kobayashi. Although it can be obtained by a known method, some compounds are commercially available.

[0014]

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The above reaction may be carried out, if necessary, with urea, formamide, 1,8-diazabicyclo [5.4.0] -7.
The reaction may be performed in the presence of an amine catalyst such as undecene (DBU). Here, the mixing ratio (molar ratio) of the compound of the general formula (8) and the compound of the general formula (6) or the compound of the general formula (8) and the compound of the general formula (7) is 0.001:
The ratio is preferably 99.999 to 99.999: 0.001, more preferably 0.1: 99.9 to 99.9: 0.1 (molar ratio). When the mixing ratio of the compound of the general formula (8) is smaller than the above-mentioned mixing ratio, and the mixing ratio of the compound of the general formula (6) or the compound of the general formula (7) is larger than the above-mentioned mixing ratio, the residual in the electrophotographic characteristics. There is a possibility that the potential may increase and the chargeability may decrease. Conversely, when the mixing ratio of the compound of the general formula (8) is higher than the above-mentioned mixing ratio and the mixing ratio of the compound of the general formula (6) or the compound of the general formula (7) is lower than the above-mentioned mixing ratio, There is a possibility that the chargeability may decrease in the characteristics. In addition, as the metal described above,
Specifically, for example, Mg, Li, and Na and the compound having a metal include, for example, TiCl ₄ , CoCl ₂ , Cu
Cl ₂ , CuCl, InCl ₃ , InBr ₃ , AlCl ₃ ,
Metal halides such as GaCl ₂ and VCl ₃ and Ti (O
Alkoxy metals such as Bu) ₄ and Mg (OEt) ₂ . The reaction temperature is usually between room temperature and 300 ° C.
It is preferable to perform the reaction at 0 ° C to 250 ° C from the viewpoint of the reaction yield.

Further, the tetraazaporphyrin derivative mixture represented by the general formula (3) is obtained by the above-mentioned general formula (8)
And a compound represented by the general formula (6) or a compound represented by the general formula (8) and a compound represented by the general formula (7) in the absence of a solvent or α-chloronaphthalene. ,
Halogen solvents such as dichlorobenzene and trichlorobenzene; alcohol solvents such as pentanol and octanol; amine solvents such as N, N-dimethylformamide and N-methylpyrrolidone; and aromatic solvents such as benzene, toluene and nitrobenzene. It can be obtained by reacting in the presence. The reaction may be carried out, if necessary, with urea, formamide, 1,8-diazabicyclo [5.4.
0] -7-undecene (DBU), the reaction may be carried out in the presence of an amine catalyst such as ammonia gas. Here, the mixing ratio of the compound of the general formula (8) and the compound of the general formula (6) or the compound of the general formula (8) and the compound of the general formula (7) is as follows:
0.001: 99.999 to 99.999: 0.001
(Molar ratio), preferably 0.1: 99.9-99.9:
It is preferably 0.1 (molar ratio). General formula (8)
When the mixing ratio of the compound of the formula (1) is lower than the above mixing ratio and the mixing ratio of the compound of the general formula (6) or the compound of the general formula (7) is higher than the above mixing ratio, the increase in the residual potential and the charging in the electrophotographic characteristics. There is a danger that sex will decline. Conversely, when the mixing ratio of the compound of the general formula (8) is higher than the above-mentioned mixing ratio and the mixing ratio of the compound of the general formula (6) or the compound of the general formula (7) is lower than the above-mentioned mixing ratio, There is a possibility that the chargeability may decrease in the characteristics. The reaction temperature is usually from room temperature to 300 ° C., especially from 100 ° C. to 25 ° C.
It is preferable to perform the reaction at 0 ° C. from the viewpoint of the reaction yield.

In the tetraazaporphyrin derivative mixture represented by the general formula (1), M = Mg, Li, Na
The tetraazaporphyrin derivative mixture represented by the general formula (3) can be obtained in a high yield by treating the tetraazaporphyrin derivative mixture in an acidic solvent.

According to the required characteristics of the photoreceptor, in addition to obtaining the tetraazaporphyrin derivative mixture by the above-mentioned reaction, the phthalocyanine pigment and the tetraazaporphyrin derivative mixture may be simply mixed together to obtain the general formula (I). The tetraazaporphyrin derivative mixture represented by 1) or 3) can be obtained. In the present invention, the mixing method is not particularly limited,
Various methods can be adopted.

The tetraazaporphyrin derivative mixture according to the present invention can be produced, for example, by the following method. 1) A method of synthesizing or preparing a phthalocyanine pigment and a tetraazaporphyrin derivative mixture in advance and mixing them by the method described below, 2) A method of synthesizing a tetraasaporphyrin derivative mixture in advance and synthesizing a phthalocyanine pigment in the presence thereof, and the like. However, the present invention is not limited to this.

Next, the mixing method is as follows: 1-a) In the above production method 1), a mixture of a phthalocyanine pigment and a tetraasavolphyrin derivative is uniformly mixed by mechanical milling by a known method. a) mixing a phthalocyanine pigment and a tetraazaporphyrin derivative mixture with a usual mixing device, for example, a tumbler for mixing powder; 3-a) mixing a phthalocyanine pigment and a tetraazaporphyrin derivative mixture with a suitable organic solvent such as xylene; 4-a) adding a phthalocyanine pigment and a tetraazaporphyrin derivative mixture to a binder resin and dispersing with a device such as a ball mill or a sand mill; and 5-a) binding a phthalocyanine pigment or a tetraazaporphyrin derivative mixture. Phthalo is dispersed in the binder resin. 6-a) An inorganic acid such as sulfuric acid or phosphoric acid, or an organic acid such as acetic acid or trifluoroacetic acid, which dissolves both the phthalocyanine pigment and the tetraazaporphyrin derivative mixture, is simply added with an anine pigment or a tetraazaporphyrin derivative mixture. After mixing, a mixing method such as precipitation with water or a basic substance may be mentioned, but the present invention is not limited thereto. The production method of the above 2) can be obtained by a generally known method of synthesizing phthalocyanine in the presence of a mixture of tetraazaporphyrin derivatives.

The mixing ratio of the phthalocyanine pigment of the present invention and the tetraazaporphyrin derivative mixture is 0.001:
99.999-99.999: 0.001 (molar ratio),
Preferably, the ratio is 0.1: 99.9 to 99.9: 0.1 (molar ratio). When the mixing ratio of the tetraazaporphyrin derivative mixture is lower than the above mixing ratio, and the mixing ratio of the phthalocyanine pigment is higher than the above mixing ratio, the residual potential may increase in the electrophotographic characteristics and the chargeability may decrease. Conversely, if the mixing ratio of the tetraazaporphyrin derivative mixture is higher than the above-mentioned mixing ratio and the mixing ratio of the phthalocyanine pigment is lower than the above-mentioned mixing ratio, there is a possibility that the electrification property may decrease in electrophotographic waiting time.

The phthalocyanine pigment according to the present invention includes metal-free phthalocyanine, metal phthalocyanine, or a mixture thereof. As metal phthalocyanines, copper phthalocyanine, aluminum phthalocyanine, magnesium phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, vanadyl phthalocyanine, titanyl phthalocyanine, chloroindium phthalocyanine, hydroxyindium phthalocyanine, zinc phthalocyanine, iron phthalocyanine,
Examples include, but are not limited to, cobalt phthalocyanine.

The crystal conversion treatment of the tetraazaporphyrin derivative mixture includes, for example, acid treatment, solvent treatment, mechanical treatment, heat treatment and the like. Acid treatment refers to the treatment of acid in sulfuric acid, trichloroacetic acid,
This shows that after dissolving the pigment at a temperature of from 0 ° C. to room temperature, the pigment is dropped into ice, water, or a sparingly soluble organic solvent to precipitate the crystal of the pigment, and the crystal is obtained by means such as filtration. What is solvent treatment?
At room temperature or under heating, it indicates a suspension and stirring treatment of the pigment in a solvent, and the milling treatment is performed by using a milling device such as a sand mill or a ball mill using, for example, glass beads, steel beads, or alumina balls at room temperature. Alternatively, a treatment performed under heating is shown. In the milling process,
It may be performed in a system in which a solvent is added together with the above-mentioned milling media. Solvents used for these treatments include, for example, benzene, toluene, dichlorobenzene, nitrobenzene, methanol, ethanol, benzyl alcohol, acetone, cyclohexanone, methyl ethyl ketone, n-butyl ether, ethylene glycol, tetrahydrofuran, N, N-dimethylformamide, N -Methylpyrrolidone, quinoline, pyridine, dimethylsulfoxide, water and the like, and these solvents may be used in combination.

The tetraazaporphyrin derivative mixture represented by the general formula (1) or (3) of the present invention may be used alone or in combination with a charge transport material to form a single-layer or laminated (separated-function) electrophotographic photosensitive material. Body can be created. In the case of a single layer structure, a photosensitive layer in which a tetraazaporphyrin derivative mixture alone or a charge transport material is combined and dispersed in a binder is provided on a conductive substrate.
In the case of the function separation type, a charge generation layer composed of a tetraazaporphyrin derivative mixture is formed on a substrate, and a charge transport layer composed of a charge transport substance is formed thereon, but the charge generation layer and the charge transport layer are reversed. They may be stacked.

In the electrophotographic photoreceptor of the present invention,
An intermediate layer (for example, an undercoat layer) may be provided between the photosensitive layer and the conductive support in order to improve adhesion and charge blocking properties. A protective layer may be provided on the photosensitive layer to improve the quality.

The tetraazaporphyrin derivative mixture comprises:
It can be provided by dissolving or dispersing it in an appropriate solvent together with a binder resin as required, coating and drying. Examples of the method for dispersing the tetraazaporphyrin derivative mixture include a ball mill, an ultrasonic wave, and a homomixer, and examples of the application method include a dipping coating method, a blade coating method, and a spray coating method.

When the charge generation layer is formed by dispersing the tetraazaporphyrin derivative mixture, the tetraazaporphyrin derivative mixture has an average particle size of 2 μm or less, preferably 1 μm or less, in order to improve the dispersibility in the layer. Are preferred. However, if the particle size is too small, it tends to agglomerate, the resistance of the charge generation layer increases, and crystal defects increase, and the sensitivity and the repetition characteristics decrease.
Alternatively, the lower limit of the average particle size is preferably 0.01 μm because there is a limit in miniaturization.

As the solvent used for preparing the dispersion or solution of the photosensitive layer, for example, N, N-dimethylformamide, toluene, xylene, monochlorobenzene, 1,2-dichloroethane, 1,1,1-trichlor Examples thereof include ethane, dichloromethane, 1,1,2-trichloroethane, trichloroethylene, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, and butyl acetate.

As the binder used in forming the photosensitive layer, any binder can be used as long as it has good insulating properties, and there is no particular limitation. Specific examples of the binder include, for example, polyethylene, polyvinyl butyral, polyvinyl formal, polystyrene resin, phenoxy resin, polypropylene, acrylic resin, methacrylic acid resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin , Polyester resin, alkyd resin, polycarbonate resin, polyamide resin, silicone resin, melamine resin, etc., addition polymerization type resin, polyaddition type resin, polycondensation type resin, and those containing two or more of repeating units of these resins. Polymer resins, such as vinyl chloride-vinyl acetate copolymer, styrene-acrylic copolymer,
In addition to insulating resins such as a vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, polymer organic semiconductors such as poly-N-vinyl carbazole may be mentioned. These binders can be used alone or as a mixture of two or more.

The tetraazaporphyrin compounds represented by the general formulas (1) and (3) used in the present invention are:
For example, they may be mixed and dispersed with the following pigments. Examples of such organic pigments include C.I. Pigment Blue 25 (Color Index CI)
21180), C.I. Pigment Red 41 (CI2
1200), CI Acid Red 52 (CI451)
00), CI Basic Red 3 (CI4521)
0), an azo pigment having a carbazole skeleton (JP-A-53
95033), an azo pigment having a distyrylbenzene skeleton (Japanese Patent Application Laid-Open No. 53-133445), an azo pigment having a triphenylamine skeleton (described in Japanese Patent Application Laid-Open No. 53-132347), dibenzothiophene Azo pigments having a skeleton (described in JP-A-54-21728), azo pigments having an oxadiazole skeleton (described in JP-A-54-12742), and azo pigments having a fluorenone skeleton (described in JP-A-54-12742) No. 22834), azo pigments having a bisstilbene skeleton (described in JP-A-54-17733), and azo pigments having a distyryloxadiazole skeleton (described in JP-A-54-21)
No. 29), an azo pigment having a distyrylcarbazole skeleton (described in JP-A-54-14967)
Azo pigments such as, for example, C.I. Pigment Blue 16 (CI74100), phthalocyanine-based pigments such as titanyl phthalocyanine, and further, for example, indigo-based pigments such as C.I. Examples include perylene pigments such as Argoscarlet B (manufactured by Bayer), and Insence Scarlet R (manufactured by Bayer). These organic pigments may be used alone or in combination of two or more.

In the case where a photoreceptor is manufactured using the above-described layer constitution and substance, there are preferable ranges of the film thickness and the ratio of the substance. For example, in the case of a function-separated type (lamination of a substrate / charge generation layer / charge transport layer), a binder is used as needed in the charge generation layer, in which case the ratio of the tetraazaporphyrin derivative mixture to the binder is used. Is preferably 20% by weight, and the film thickness is preferably 0.01 to 5 μm. In the charge transport layer, the ratio of the charge transport material to the binder is 20 to 200.
It is preferable that the weight% and the film thickness be 5 to 100 μm. In the case of the positive charge type, in the charge transport layer, the ratio of the charge transport material to the binder is 20 to 200% by weight or more,
The film thickness is preferably 5 to 100 μm. When a high molecular charge transport material is used, the charge transport layer may be formed alone. Further, the charge generation layer preferably contains a charge transporting substance, which has an effect on suppressing residual potential and improving sensitivity. In this case, the charge transporting material is 20 to 200% by weight based on the binder.
It is preferable to include them.

In the case of a single-layer type photosensitive member, the ratio of the tetraazaporphyrin derivative mixture to the binder resin in the photosensitive layer is 5 to 95% by weight, and the film thickness is 10 to 100%.
It is preferably set to μm. When combined with a charge transport material, the ratio of the charge transport material to the binder resin is preferably 30 to 200% by weight. Also,
The photosensitive layer may be formed of a mixture of a polymer-type charge transport material and a tetraazaporphyrin derivative. In this case, the ratio of the tetraazaporphyrin derivative mixture to the polymer-type charge transport material is 5 to 95% by weight, and the film thickness is 10%. ~ 100 μm
It is preferred that

Further, in these photosensitive layers, phenol compounds, hydroquinone compounds, hindered phenol compounds, hindered amine compounds, compounds in which hindered amine and hindered phenol are present in the same molecule, etc. are used for the purpose of improving the chargeability. Can be added.

In the present invention, as the conductive support,
Metal plate of aluminum, nickel, copper, titanium, gold, stainless steel, etc., metal drum or metal foil, plastic film on which aluminum, nickel, copper, titanium, tin oxide, indium oxide, etc. are deposited, or paper coated with conductive material And films or drums of plastics and the like.

In the electrophotographic photoreceptor of the present invention, an intermediate layer can be provided on a conductive substrate, if necessary. The intermediate layer generally contains a resin as a main component. However, considering that these resins are coated on the photosensitive layer with a solvent, it is desirable that the resin be a resin having high solvent resistance to a general organic solvent. . Such resins include polyvinyl alcohol,
Water-soluble resins such as casein and sodium polyacrylate,
Curable resins that form a three-dimensional network structure, such as alcohol-soluble resins such as copolymerized nylon and methoxymethylated nylon, polyurethanes, melamine resins, phenol resins, alkyd-melamine resins, and epoxy resins. In order to prevent moiré and reduce residual potential, a fine powder pigment of a metal oxide exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the intermediate layer.

These intermediate layers can be formed by using an appropriate solvent and a coating method as in the case of the above-mentioned photosensitive layer. Further, as the intermediate layer of the present invention, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used. In addition, an organic material such as polyparaxylylene (parylene), SiO ₂ , Sn
An inorganic material such as O ₂ , TiO ₂ , ITO, or CeO ₂ provided by a vacuum thin film forming method can also be used favorably. In addition, known materials can be used. The thickness of the intermediate layer is 0
５5 μm is appropriate.

In the electrophotographic photosensitive member of the present invention, a protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer. Materials used for the protective layer include ABS resin and A
CS resin, olefin-vinyl monomer copolymer, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallyl sulfone, polybutylene, polybutylene terephthalate, polycarbonate, polyether sulfone, polyethylene, Polyethylene terephthalate, polyimide, acrylic resin, polymethylpentene,
Resins such as polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resin, butadiene-styrene copolymer, polyurethane, polyvinyl chloride, polyvinylidene chloride, and epoxy resin. For the purpose of improving abrasion resistance, the protective layer is made of a fluororesin such as polytetrafluoroethylene, a silicone resin, or an inorganic material such as titanium oxide, tin oxide or potassium titanate dispersed in these resins. Etc. can be added.

As a method for forming the protective layer, a usual coating method is employed. The thickness of the protective layer is suitably about 0.1 to 10 μm. In addition to the above, known materials such as aC and a-SiC formed by a vacuum thin film forming method can be used as the protective layer.

The charge transport material includes a hole transport material and an electron transport material. As the hole transport material, for example, poly-N
Carbazole and its derivatives, poly-γ-carbazolylethyl glutamate and its derivatives, pyrene-formaldehyde condensate and its derivatives, polyvinylpyrene,
There are polyvinyl phenanthrene, oxazole derivative, imidazole derivative, triphenylamine derivative and the like,
Among them, a stilbene compound represented by the following general formula (4) is preferably used because of its high charge transport ability.

[0040]

Embedded image (Wherein, R ₁ and R ₂ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and R ₃ and R ₄ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted Represents an aryl group or a heterocyclic group.
₁ and R ₂ may form a ring with each other. Ar ₁ represents a substituted or unsubstituted arylene group or a heterocyclic group. )

Specific examples of the stilbene compound represented by the general formula (4) are shown in Tables 1 to 10, but are not limited to these in the present invention.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

[0047]

[Table 6]

[0048]

[Table 7]

[0049]

[Table 8]

[0050]

[Table 9]

[0051]

[Table 10]

Examples of the hole transport material include compounds represented by the following general formulas (11) to (28).

(1) Compounds represented by the following general formula (11) (JP-A-55-154955, JP-A-55-1569)
No. 54)

Embedded image (Wherein, R ¹ represents a methyl group, an ethyl group, 2-hydroxyethyl group or a 2-chloroethyl group, R ² represents a methyl group, an ethyl group, a benzyl group or a phenyl group, R ³
Represents a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a dialkylamino group or a nitro group. )

The compound represented by the general formula (11) includes, for example, 9-ethylcarbazole-3-aldehyde-1-aldehyde.
Methyl-1-phenylhydrazone, 9-ethylcarbazole-3-aldehyde-1-benzyl-1-phenylhydrazone, 9-ethylcarbazole-3-aldehyde-
Examples include 1,1-diphenylhydrazone.

(2) Compound represented by the following formula (12) (described in JP-A-55-52063)

Embedded image (In the formula, Ar represents a naphthalene ring, an anthracene ring, a styryl ring, a substituted product thereof, a pyridine ring, a furan ring, or a thiophene ring, and R represents an alkyl group or a benzyl group.)

The compound represented by the general formula (12) includes, for example, 4-diethylaminostyryl-3-aldehyde-
There are 1-methyl-1-phenylhydrazone, 4-methoxynaphthalene-1-aldehyde-1-benzyl-1-phenylhydrazone and the like.

(3) Compound represented by the following formula (13) (described in JP-A-56-81850)

Embedded image (Wherein, R ¹ represents an alkyl group, a benzyl group, a phenyl group or a naphthyl group; R ² represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group, Represents an aralkylamino group or a diarylamino group, n represents an integer of 1 to 4, and when n is 2 or more, R ² may be the same or different. R ³ represents a hydrogen atom or a methoxy group.)

Compounds represented by the general formula (13) include, for example, 4-methoxybenzaldehyde-1-methyl-1
-Phenylhydrazone, 2,4-dimethoxybenzaldavido-1-benzyl-1-phenylhydrazone, 4-
Diethylaminobenzaldehyde-1,1-diphenylhydrazone, 4-methoxybenzaldehyde-1-benzyl-1- (4-methoxy) phenylhydrazone, 4-
Diphenylaminobenzaldehyde-1-benzyl-1
-Phenylhydrazone, 4-dibenzylaminobenzaldehyde-1,1-diphenylhydrazone and the like.

(4) Compound represented by the following formula (14) (described in JP-A-51-10983)

Embedded image (Wherein, R ¹ represents an alkyl group having 1 to 11 carbon atoms, a substituted or unsubstituted phenyl group or a heterocyclic group, and R ² , R ³
May be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, a chloroalkyl group or a substituted or unsubstituted aralkyl group, and R ² and R ³ are bonded to each other And may form a heterocycle containing nitrogen. R ⁴ may be the same or different and represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a halogen atom. )

The compound represented by the general formula (14) includes, for example, 1,1-bis (4-dibenzylaminophenyl)
Examples include propane, tris (4-diethylaminophenyl) methane, 1,1-bis (4-dibenzylaminophenyl) propane, and 2,2′-dimethyl-4,4′-bis (diethylamino) -triphenylmethane.

(5) Compound represented by the following formula (15) (described in JP-A-51-94829)

Embedded image (In the formula, R represents a hydrogen atom or a halogen atom, and Ar represents a substituted or unsubstituted phenyl group, naphthyl group, anthryl group, or carbazolyl group.)

The compound represented by the general formula (15) includes, for example, 9- (4-diethylaminostyryl) anthracene and 9-bromo-10- (4-diethylaminostyryl) anthracene.

(6) Compound represented by the following formula (16) (described in JP-A-52-128373)

Embedded image [In the formula, R ¹ represents a hydrogen atom, a halogen atom, a cyano group, an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and Ar represents

Embedded image R ² represents an alkyl group having 1 to 4 carbon atoms, R ³ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms,
Represents an alkoxy group or a dialkylamino group having 1 to 4 carbon atoms, n is 1 or 2, when n is 2, R ³ may be the same or different, and R ⁴ and R ⁵ are a hydrogen atom, a carbon atom Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted benzyl group represented by Formulas 1 to 4. ]

The compound represented by the general formula (16) includes, for example, 9- (4-dimethylaminobenzylidene)
Fluorene, 3- (9-fluorenylidene) -9-ethylcarbazole and the like.

(7) Compound represented by the following formula (17) (described in JP-A-56-29245)

Embedded image (Wherein R is a carbazolyl group, a pyridine group, a thienyl group, an indolyl group, a furyl group or a substituted or unsubstituted phenyl group, a styryl group, a naphthyl group or an anthryl group, and these substituents are a dialkylamino group,
Alkyl group, alkoxy group, carboxy group or ester thereof, halogen atom, cyano group, aralkylamino group,
Represents a group selected from the group consisting of N-alkyl-N-aralkylamino, amino, nitro and acetylamino. )

Compounds represented by the general formula (17) include, for example, 1,2-bis (4-diethylaminostyryl) benzene, 1,2-bis (2,4-dimethoxystyryl)
There is benzene.

(8) Compound represented by the following formula (18) (described in JP-A-58-58552)

Embedded image (Wherein, R ¹ represents a lower alkyl group, a substituted or unsubstituted phenyl group or a benzyl group, and R ² and R ³ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a nitro group, an amino group or Represents an amino group substituted by a lower alkyl group or a benzyl group, and n represents an integer of 1 or 2.)

Compounds represented by the general formula (18) include, for example, 3-styryl-9-ethylcarbazole,
(4-methoxystyryl) -9-ethylcarbazole and the like.

(9) Compound represented by the following formula (19) (described in JP-A-57-73075)

Embedded image (Wherein, R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, R ² and R ³ represents an alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, R ⁴ Represents a hydrogen atom or a substituted or unsubstituted phenyl group, and Ar represents a substituted or unsubstituted phenyl group or a naphthyl group.)

Compounds represented by the general formula (19) include, for example, 4-diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene,
1- (4-diphenylaminostyryl) naphthalene, 1
-(4-diethylaminostyryl) naphthalene and the like.

(10) Compound represented by the following general formula (20) (described in JP-A-58-198043)

Embedded image [Wherein, n is an integer of 0 or 1, R ¹ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted phenyl group;
¹ represents a substituted or unsubstituted aryl group, R ⁵ represents an alkyl group containing a substituted alkyl group or a substituted or unsubstituted aryl group, A represents a 9-anthryl group, a substituted or unsubstituted carbazolyl group or

Embedded image Wherein R ² is a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or

Embedded image (However, R ³ and R ⁴ represent an alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, and R ³ and R ⁴ may be the same or different, and form a ring. M is an integer of 0, 1, 2 or 3, and when m is 2 or more, R ² may be the same or different. When n is 0, A and R ¹ may form a ring together. ]

The compound represented by the general formula (20) includes, for example, 4'-diphenylamino-α-phenylstilbene, 4'-bis (methylphenyl) amino-α-phenylstilbene and the like.

(11) Compound represented by the following formula (21) (described in JP-A-49-105537)

Embedded image (In the formula, R ¹ , R ² and R ³ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a dialkylamino group or a halogen atom, and n represents 0 or 1.)

Compounds represented by the general formula (21) include, for example, 1-phenyl-3- (4-diethylaminostyryl) -5- (4-diethylaminophenyl) pyrazolin, 1-phenyl-3- (4- Dimethylaminostyryl) -5- (4-dimethylaminophenyl) pyrazolin.

(12) Compound represented by the following formula (22) (described in JP-A-52-139066)

Embedded image (In the formula, R ¹ and R ² represent an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and A represents a substituted amino group, a substituted or unsubstituted aryl group, or an allyl group.)

The compound represented by the general formula (22) includes, for example, 2,5-bis (4-diethylaminophenyl)-
1,3,4-oxadiazole, 2-N, N-diphenylamino-5- (4-diethylaminophenyl) -1,
3,4-oxadiazole, 2- (4-dimethylaminophenyl) -5- (4-diethylaminophenyl)-
1,3,4-oxadiazole and the like.

(13) Compound represented by the following general formula (23) (described in JP-A-52-139065)

Embedded image (Wherein, X represents a hydrogen atom, a lower alkyl group or a halogen atom, R represents an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and A represents a substituted amino group or a substituted or unsubstituted group. Represents an aryl group.)

As the compound represented by the general formula (23), for example, 2-N, N-diphenylamino-5- (N
-Ethylcarbazol-3-yl) -1,3,4-oxadiazole, 2- (4-diethylaminophenyl)-
5- (N-ethylcarbazol-3-yl) -1,3,3
4-oxadiazole and the like.

(14) Compound represented by the following formula (24) (described in JP-A-58-32372)

Embedded image (Wherein, R ¹ represents a lower alkyl group, a lower alkoxy group or a halogen atom, n represents an integer of 0 to 4, R ² ,
R ³ may be the same or different and represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom. )

The benzidine compound represented by the general formula (24) includes, for example, N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl]
-4,4'-diamine, 3,3'-dimethyl-N, N,
N ', N'-tetrakis (4-methylphenyl)-
[1,1′-biphenyl] -4,4′-diamine and the like.

(15) Compound represented by the following formula (25) (described in JP-A-2-178669)

Embedded image (Wherein R ¹ , R ³ and R ⁴ are a hydrogen atom, an amino group, an alkoxy group, a thioalkoxy group, an aryloxy group, a methylenedioxy group, a substituted or unsubstituted alkyl group, a halogen atom, or a substituted or unsubstituted Is an aryl group of R
² represents a hydrogen atom, an alkoxy group, a substituted or unsubstituted alkyl group, or a halogen atom. Where R ¹ , R ² ,
R ³ and R ⁴ exclude the case where all are hydrogen atoms. Also,
k, l, m and n are integers of ¹ , ² , 3 or 4, and when each is an integer of 2, 3 or 4, R ¹ , R ² , R ³ and R ⁴ may be the same or different. Is also good. )

The biphenylamine compound represented by the general formula (25) includes, for example, 4′-methoxy-N, N-diphenyl- [1,1′-biphenyl] -4-amine, 4 ′
-Methyl-N, N'-bis (4-methylphenyl)-
[1,1′-biphenyl] -4-amine, 4′-methoxy-N, N′-bis (4-methylphenyl)-[1,
1'-biphenyl] -4-amine and the like.

(16) Compound represented by the following formula (26) (described in JP-A-3-285960)

Embedded image (Wherein, Ar represents a condensed polycyclic hydrocarbon group having 18 or less carbon atoms, and R ¹ and R ² represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group,
Represents a substituted or unsubstituted phenyl group, which may be the same or different. )

The triarylamine compound represented by the general formula (26) includes, for example, 1-laminopyrene, 1-di (p-tolylamino) pyrene and the like.

(17) Compound represented by the following formula (27) (described in JP-A-62-98394)

A-CH = CH-Ar-CH = CH-A (27) wherein Ar represents a substituted or unsubstituted aromatic hydrocarbon group, and A represents

Embedded image (However, Ar ′ represents a substituted or unsubstituted aromatic hydrocarbon group, and R ¹ and R ² are a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group). ]

The diolefin aromatic compound represented by the general formula (27) includes, for example, 1,4-bis (4-diphenylaminostyryl) benzene, 1,4-bis [4-di (p-tolyl) [Aminostyryl] benzene.

(18) Compound represented by the following formula (28) (described in JP-A-4-230766)

Embedded image (In the formula, Ar represents an aromatic hydrocarbon group, R represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, n is 0 or 1, and m is 1
Or 2, when n = 0 and m = 1, Ar and R may form a ring together. )

Examples of the styrylpyrene compound represented by the general formula (28) include 1- (4-diphenylaminostyryl) pyrene and 1- [4-di (p-tolyl) aminostyryl] pyrene.

Examples of the electron transporting substance include chloranil, bromanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9
-Fluorenone, 2,4,5,7-tetranitro-9-
Fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6
8-trinitro-indeno 4H-indeno [1,2-
b] Thiophene-4-one, 1,3,7-trinitrodibenzothiophene-5,5-dioxide and the like, and the following (5), (29) and The electron transporting substances listed in the formula (30) can be suitably used. These charge transport materials are used alone or in combination of two or more.

[0090]

Embedded image

Embedded image

Embedded image

The mixture of the tetraazaporphyrin derivatives represented by the general formulas (1) and (3) of the present invention is not only useful as a photoconductor of an electrophotographic photoreceptor, but also
It can be suitably used as an electronic device in the field of electronics such as solar cells and optical disks.

[0092]

EXAMPLES The present invention will be described below with reference to production examples and examples, but the present invention is not limited to these. In the following, all parts shown are on a weight basis.

Production Example 1 0.2 mol of a nitrile derivative having a group represented by the general formula (8) (provided that r ₁ , r ₂ , r ₃ , and r ₄ = H), 0.2 mol of phthalonitrile, Copper chloride 0.1 mol, α-
1000 ml of chloronaphthalene was stirred and mixed, and the temperature was gradually raised to 200 ° C. under a nitrogen stream to raise the reaction temperature to 190 to 200 ° C.
While maintaining the temperature at 10 ° C, the mixture was heated and stirred for 5 hours. After the completion of the reaction, the mixture was allowed to cool and was filtered at 130 ° C., and then α
-Wash thoroughly with chloronaphthalene, then add methanol,
After washing several times with toluene and water, it was dried to obtain a copper tetraazaporphyrin derivative mixture with a yield of 76%.

Induction of copper tetraazaporphyrin obtained here
As a result of mass analysis of the body mixture, in the general formula (1), A = B = C = D = unsubstituted benzene ring A = B = C = unsubstituted benzene ring, D = general formula (2)
(However, r₁, R_Two, R _Three, R_Four= H) A = B = unsubstituted benzene ring, C = D = general formula (2)
(However, r₁, R_Two, R _Three, R_Four= H) or A = C = unsubstituted
Benzene ring, B = D = general formula (2) (provided that r₁,
r_Two, R_Three, R_Four= H) A = B = C = D = general formula (2) (where r₁, R_Two,
r_Three, R_Four= H) A peak corresponding to the molecular weight of the compound where M = Cu was observed.
The presence of these compounds was confirmed and tetraazaporphyri
It was shown to be a mixture of derivatives.

Production Example 2 0.2 mol of a nitrile derivative having a group represented by the general formula (8) (provided that r ₁ , r ₂ , r ₃ , and r ₄ = H), 0.2 mol of phthalonitrile, and titanium tetrabutoxide 0.
11mol, urea 0.2mol and octanol 1000
Then, the mixture was heated and stirred for 6 hours while maintaining the reaction temperature at 150 to 160 ° C under a nitrogen stream. After the completion of the reaction, the reaction solution was allowed to cool, filtered, washed sufficiently with octanol, further washed several times with methanol, toluene and water, and dried to obtain a 84% yield of a titanyltetraazaporphyrin derivative mixture.

The titanyltetraazaporphyrie obtained here
As a result of mass spectrometry of the mixture of derivatives of
A = B = C = D = unsubstituted benzene ring A = B = C = unsubstituted benzene ring, D = general formula (2)
(However, r₁, R_Two, R _Three, R_Four= H) A = B = unsubstituted benzene ring, C = D = general formula (2)
(However, r₁, R_Two, R _Three, R_Four= H) or A = C = unsubstituted
Benzene ring, B = D = general formula (2) (provided that r₁,
r_Two, R_Three, R_Four= H) A = B = C = D = general formula (2) (where r₁, R_Two,
r_Three, R_Four= H) A peak corresponding to the molecular weight of the compound where M = TiO 2 is observed.
The presence of these compounds was confirmed and tetraazaporphyri
It was shown to be a mixture of derivatives.

Production Example 3 0.4 mol of metallic magnesium, a catalytic amount of iodine and 500 ml of pentanol were stirred and mixed, and the temperature was gradually raised to 120 ° C. under a nitrogen stream while maintaining the reaction temperature at 110 to 120 ° C. The mixture was stirred for 1 hour to activate Mg. After the completion of the reaction, the reaction mixture was allowed to cool to room temperature, and then subjected to the general formula (8)
(Provided that r ₁ , r ₂ , r ₃ , r ₄ ＨH) 0.2 mol of a nitrile derivative having a group represented by the formula: 0.2 mol of phthalonitrile
mol, and mixed with stirring.
C., and the mixture was heated and stirred for 3 hours while maintaining the reaction temperature at 110 to 120.degree. After completion of the reaction, the reaction solution was allowed to cool to 80 ° C., filtered while hot, washed sufficiently with pentanol, further washed several times with methanol, toluene, and water, dried, and dried at a yield of 89% of magnesium tetraaza. A porphyrin derivative mixture was obtained.

The magnesium tetraazaporph obtained here
As a result of mass spectrometry of the mixture of pilin derivatives,
A = B = C = D = unsubstituted benzene ring A = B = C = unsubstituted benzene ring, D = general formula (2)
(However, r₁, R_Two, R _Three, R_Four= H) A = B = unsubstituted benzene ring, C = D = general formula (2)
(However, r₁, R_Two, R _Three, R_Four= H) or A = C = unsubstituted
Benzene ring, B = D = general formula (2) (provided that r₁,
r_Two, R_Three, R_Four= H) A = B = C = D = general formula (2) (where r₁, R_Two,
r_Three, R_Four= H) A peak corresponding to the molecular weight of the compound where M = Mg was observed.
The presence of these compounds was confirmed and tetraazaporphyri
It was shown to be a mixture of derivatives.

Production Example 4 40 g of the magnesium tetraazaporphyrin derivative mixture obtained in Production Example 3 was treated at 5 ° C. with trifluoroacetic acid 3
Then, the mixture was added little by little into 000 ml, stirred for about 1 hour while maintaining the temperature at 5 ° C. or lower, then slowly poured into 10,000 ml of ice water, and the precipitated crystals were filtered. The crystals are washed with distilled water until no acid remains and dried, yielding 90%
Thus, a metal-free tetraazaborphyrin derivative mixture was obtained.

The metal-free tetraazaporphyrin obtained here
As a result of mass spectrometry of the derivative mixture, in the general formula (3), A = B = C = D = unsubstituted benzene ring A = B = C = unsubstituted benzene ring, D = general formula (2)
(However, r₁, R_Two, R _Three, R_Four= H) A = B = unsubstituted benzene ring, C = D = general formula (2)
(However, r₁, R_Two, R _Three, R_Four= H) or A = C = unsubstituted
Benzene ring, B = D = general formula (2) (provided that r₁,
r_Two, R_Three, R_Four= H) A = B = C = D = general formula (2) (where r₁, R_Two,
r_Three, R_Four= H), a peak corresponding to the molecular weight of the compound was observed.
The presence of these compounds was confirmed and tetraazaporphyri
It was shown to be a mixture of derivatives.

Production Example 5 In Production Example 2, the general formula (8) (provided that r ₁ , r ₂ , r
₃ , r ₄ = H) A titanyl tetraazaporphyrin derivative mixture was synthesized in the same manner as in Production Example 2 except that the nitrile derivative having a group represented by r ₄ = H) was changed to 0.02 mol, and phthalonitrile was changed to 0.38 mol. .

Production Example 6 In Production Example 2, the general formula (8) (provided that r ₁ , r ₂ , r
₃ , r ₄ = H) A titanyl tetraazaporphyrin derivative mixture was synthesized in the same manner as in Production Example 2, except that the nitrile derivative having a group represented by r) was changed to 0.01 mol and the phthalonitrile was changed to 0.39 mol. .

Production Example 7 In Production Example 2, the general formula (8) (provided that r ₁ , r ₂ , r
0.001 mol of a nitrile derivative having a group represented by formula ( ₃ , r ₄ = H), and 0.399 mol of phthalonitrile.
A titanyl tetraazaporphyrin derivative mixture was synthesized in the same manner as in Production Example 2 except that the above procedure was replaced with the same procedure.

Comparative Production Example 5.1 g (0.03 mol) of a nitrile derivative having a group represented by the general formula (8) (provided that r ₁ , r ₂ , r ₃ , and r ₄ = H).
1) and 2.6 g of titanium tetrabutoxide (7.6 m
mol), 0.9 g (0.015 mol) of urea and 1-
50 ml of octanol was stirred and mixed, the temperature was gradually raised to 160 ° C. under a nitrogen stream, and the mixture was stirred and reacted for 5 hours while maintaining the reaction temperature at 150 to 160 ° C. After the reaction,
The mixture was allowed to cool, filtered when hot at 130 ° C., washed with dimethylformamide and methanol.
After washing several times with hot water and ethanol at a temperature of 4.degree.
g (yield 76%) of the titanyltetraazaporphyrin derivative was obtained.

Example 1 A mixture having the following composition was placed in a ball mill pot,
Using an alumina ball of m, ball milling was performed for 48 hours to prepare an undercoat layer coating solution. Oil-free alkyd resin (manufactured by Dainippon Ink and Chemicals, Inc .: Beckolite M640)
1) 1.5 parts, melamine resin (manufactured by Dainippon Ink and Chemicals, Inc .:
1 part of Super Beckamine G-821), 5 parts of titanium dioxide (Taipei CR-EL, manufactured by Ishihara Sangyo Co., Ltd.)
22.5 parts of 2-butanone. This coating solution was applied on an aluminum plate support and dried at 130 ° C. for 20 minutes to form an intermediate layer.

Next, a dispersion comprising 3 parts of the copper tetraazaporphyrin derivative mixture obtained in Production Example 1, 1 part of polyvinyl butyral resin (BM-S: manufactured by Sekisui Chemical Co., Ltd.), and 80 parts of tetrahydrofuran was placed in a ball mill pot. Using a 2 mm PSZ ball, ball milling was performed for 3 hours to prepare a charge generating layer coating solution. This coating solution was applied on the undercoat layer and dried at 100 ° C. for 20 minutes to form a charge generating layer having a thickness of about 0.3 μm.

Subsequently, 7 parts of a charge transporting material represented by the following structural formula (D-1) and a polycarbonate resin (PCX-
5: Teijin Chemicals Ltd.) 10 parts, dichloromethane 83 parts, silicone oil (KF-50: Shin-Etsu Chemical Co., Ltd.) 0.00
A coating solution of 02 parts of the charge transport layer was prepared, coated on the charge generation layer, and dried at 110 ° C. for 20 minutes to form a charge transport layer having a thickness of about 28 μm. did.

[0108]

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Example 2 The procedure of Example 1 was repeated, except that the titanyltetraazaporphyrin derivative mixture obtained in Production Example 2 was used instead of the copper tetraazaporphyrin derivative mixture obtained in Production Example 1. Thus, an electrophotographic photosensitive member of Example 2 was obtained.

Example 3 The procedure of Example 1 was repeated, except that the mixture of the magnesium tetraazaporphyrin derivative obtained in Preparation Example 3 was used instead of the mixture of the copper tetraazaporphyrin derivative obtained in Preparation Example 1. Thus, an electrophotographic photosensitive member of Example 3 was obtained.

Example 4 The procedure of Example 1 was repeated except that the mixture of the metal-free tetraazaporphyrin derivative obtained in Preparation Example 4 was used instead of the mixture of the copper tetraazaporphyrin derivative obtained in Preparation Example 1. An electrophotographic photosensitive member of Example 4 was obtained in the same manner.

Example 5 The procedure of Example 1 was repeated, except that the titanyltetraazaporphyrin derivative mixture obtained in Preparation Example 5 was used instead of the copper tetraazaporphyrin derivative mixture obtained in Preparation Example 1. Thus, an electrophotographic photosensitive member of Example 5 was obtained.

Example 6 The procedure of Example 1 was repeated, except that the titanyltetraazaporphyrin derivative mixture obtained in Production Example 6 was used instead of the copper tetraazaporphyrin derivative mixture obtained in Production Example 1. Thus, an electrophotographic photosensitive member of Example 6 was obtained.

Example 7 The procedure of Example 1 was repeated, except that the mixture of titanyltetraazaporphyrin derivatives obtained in Production Example 7 was used instead of the mixture of copper tetraazaporphyrin derivatives obtained in Production Example 1. Thus, an electrophotographic photosensitive member of Example 7 was obtained.

Example 8 The procedure of Example 1 was repeated, except that the hole transport material (D-1) represented by the following structural formula was used instead of the hole transport material (D-1) used in Example 1. In the same manner as in Example 7, an electrophotographic photosensitive member of Example 8 was obtained.

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Example 9 The procedure of Example 1 was repeated, except that the hole transport material (D-1) represented by the following structural formula was used instead of the hole transport material (D-1) used in Example 1. In the same manner as in Example 7, an electrophotographic photosensitive member of Example 9 was obtained.

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Example 10 The procedure of Example 1 was repeated, except that the hole transporting material (D-4) represented by the following structural formula was used instead of the hole transporting material (D-1) used in Example 1. In the same manner as in Example 7, an electrophotographic photosensitive member of Example 10 was obtained.

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Comparative Example The procedure of Example 1 was repeated, except that the titanyltetraazaporphyrin derivative obtained in Comparative Production Example was used instead of the copper tetraazaporphyrin derivative mixture obtained in Production Example 1. An electrophotographic photosensitive member of a comparative example was obtained.

<Evaluation> The electrostatic characteristics of the electrophotographic photosensitive members produced in Examples 1 to 10 and Comparative Example were measured at 25 ° C./55% RH.
EPA-8 manufactured by Kawaguchi Electric Co., Ltd.
The measurement was performed by a dynamic method using 100. First,
After charging for 20 seconds with an applied voltage of −6 KV, the surface potential V ₀ (V) when dark decay for 20 seconds was measured, and then 780
nm monochromatic light so that the illuminance on the surface of the photoreceptor is 1 μW / cm ² , and the half-reduction exposure amount Em1 / 2 (μJ) required when the surface potential of the photoreceptor is -800 V to -400 V
/ Cm ² ) was measured as the sensitivity in the LD light source region (near infrared region). The results are shown in Table 11 below.

[0120]

[Table 11]

Example 11 In the same manner as in Example 1, a charge generation layer was formed on an aluminum-deposited PET base. Next, 8 parts of an electron transport material represented by the following structural formula (5), 11 parts of polycarbonate Z (manufactured by Teijin Chemicals Ltd.), and 0.02 part of silicone oil (KF50, manufactured by Shin-Etsu Chemical Co., Ltd.) are dissolved in 91 parts of tetrahydrofuran. And
This was applied onto the charge generation layer by casting with a doctor blade and dried to provide a charge transport layer having a thickness of 20 μm. Thus, an electrophotographic photosensitive member of Example 11 was obtained.

[0122]

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Example 12 The procedure of Example 11 was repeated, except that the electron transport material used in Example 11 was replaced by an electron transport material represented by the following structural formula (29). I got a body.

[0124]

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The photosensitive members produced in Examples 11 and 12 were operated in the same manner as in Examples 1 to 10 except that the applied voltage in Examples 1 to 10 was changed to +6 KV using the above-described measuring apparatus. Body characteristics evaluation was performed. Table 12 shows the results.

[0126]

[Table 12]

Example 13 0.5 g of the mixture of titanyltetraazaporphyrin derivatives obtained in Production Example 7 was mixed with polycarbonate Z (manufactured by Teijin Chemicals Ltd.).
10 g of solution (dissolved to a concentration of 10% by weight in tetrahydrofuran), 9 g of tetrahydrofuran
Then, a 10% by weight polycarbonate Z solution is added so that the derivative mixture composition becomes 2% by weight, the polycarbonate Z composition becomes 50% by weight, and the charge transport material (D-1) becomes 28% by weight, and the mixture is sufficiently stirred. Then, a photosensitive layer coating solution was prepared. The single-layer electrophotographic photoreceptor of Example 13 having a photosensitive layer having a thickness of 15 μm after drying by coating the coating solution thus prepared on a polyester film on which aluminum was vapor-deposited with a doctor blade, and having a thickness of 15 μm after drying. I got

The characteristics of the electrophotographic photosensitive member produced in Example 13 were evaluated in the same manner as in Examples 1 to 10 using the above-described measuring apparatus. Table 13 shows the results.

[0129]

[Table 13]

[0130]

According to the present invention, by using a specific tetraazaporphyrin derivative mixture as a charge generating substance for an electrophotographic photoreceptor, an electrophotographic photoreceptor having excellent chargeability and high sensitivity can be provided. For example, a specific tetraazaporphyrin derivative mixture can be used as the charge generating substance to provide a highly sensitive laminated or single-layer electrophotographic photoreceptor. Specifically, using a specific tetraazaporphyrin derivative mixture as a charge generating substance,
By using a hole transporting substance or an electron transporting substance as the charge transporting substance, a highly sensitive laminated electrophotographic photosensitive member can be provided. Further, in the electrophotographic photoreceptor, a specific tetraazaporphyrin derivative mixture is used as a charge generating substance, and a specific hole transporting substance or a specific electron transporting substance is used as a charge transporting substance. Type electrophotographic photoreceptor can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tomoyuki Shimada 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Kaoru Tadokoro 1-3-6 Nakamagome, Ota-ku, Tokyo Share In Ricoh Company (72) Inventor Chiaki Tanaka 1-3-6 Nakamagome, Ota-ku, Tokyo F-term in Ricoh Company (reference) 2H068 AA19 AA20 AA34 AA35 BA13 BA14 BA15 BA38 BA39 BA63 BA64 FA12 FA13 FC02 FC03

Claims (14)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the photosensitive layer comprises at least two or more tetraazaporphyrin derivatives represented by the following general formula (1): An electrophotographic photosensitive member comprising a derivative mixture. Embedded image (In the above formula, A, B, C and D represent a benzene ring which may have a substituent or a ring represented by the following general formula (2),
They may be the same or different. M represents a metal, a metal oxide, a metal hydroxide or a metal halide. Embedded image However, in the above formula, r _{1 to} r ₄ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group. Or a nitro group. ) 2. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer is represented by at least the general formula (1), and A, B, C in the general formula (1). And D is a benzene ring which may have a substituent, and at least one is a tetraazaporphyrin derivative which is a ring represented by the general formula (2); An electrophotographic photoreceptor, wherein all of A, B, C and D contain a tetraazaporphyrin derivative which is a benzene ring which may have a substituent. 3. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer is represented by at least the general formula (1), and A, B, and C in the general formula (1). And D is a benzene ring which may have a substituent, and at least one is a tetraazaporphyrin derivative which is a ring represented by the general formula (2); An electrophotographic photoreceptor, wherein all of A, B, C and D contain a tetraazaporphyrin derivative which is a ring represented by the general formula (2). 4. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer is represented by at least the general formula (1), and further comprises A, B, and C in the general formula (1). And D is a benzene ring which may have a substituent, and at least one is a tetraazaporphyrin derivative which is a ring represented by the general formula (2); Wherein all of A, B, C, and D are benzene rings which may have a substituent, and a tetraazaporphyrin derivative; and, in the general formula (1), all of A, B, C, and D have the general formula ( An electrophotographic photoreceptor comprising a ring represented by 2) and a tetraazaporphyrin derivative. 5. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the photosensitive layer comprises at least two or more tetraazaporphyrin derivatives represented by the following general formula (3): An electrophotographic photosensitive member comprising a derivative mixture. Embedded image (In the above formula, A, B, C and D represent a benzene ring which may have a substituent or a ring represented by the following general formula (2),
They may be the same or different. M represents a metal, a metal oxide, a metal hydroxide or a metal halide. Embedded image However, in the above formula, r _{1 to} r ₄ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group. Or a nitro group. ) 6. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer is represented by at least the general formula (3), and A, B, C in the general formula (3). And D is a benzene ring which may have a substituent, and at least one is a tetraazaporphyrin derivative which is a ring represented by the general formula (2); An electrophotographic photoreceptor, wherein all of A, B, C and D contain a tetraazaporphyrin derivative which is a benzene ring which may have a substituent. 7. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer is represented by at least the general formula (3), and A, B, and C in the general formula (3). And D is a benzene ring which may have a substituent, and at least one is a tetraazaporphyrin derivative which is a ring represented by the general formula (2); An electrophotographic photoreceptor, wherein all of A, B, C and D contain a tetraazaporphyrin derivative which is a ring represented by the general formula (2). 8. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer is represented by at least the general formula (3), and A, B, and C in the general formula (3). And D is a benzene ring which may have a substituent, and at least one is a tetraazaporphyrin derivative which is a ring represented by the general formula (2); Wherein all of A, B, C and D are a benzene ring which may have a substituent, and a tetraazaporphyrin derivative; and in the general formula (3), all of A, B, C and D have the general formula ( An electrophotographic photoreceptor comprising a ring represented by 2) and a tetraazaporphyrin derivative. 9. The charge-generating layer according to claim 1, comprising a charge-generating layer containing a charge-generating substance and a charge-transporting layer containing a charge-transporting substance. An electrophotographic photoreceptor comprising a tetraazaporphyrin derivative mixture comprising various tetraazaporphyrin derivatives represented by the general formula (1) or (3) according to any one of claims 1 to 8. . 10. The electrophotographic photoreceptor according to claim 9, wherein the photosensitive layer comprises: a charge generation layer containing a charge generation substance;
A charge transporting layer containing a hole transporting substance and a charge transporting layer provided on a conductive support in this order. 11. The electrophotographic photoreceptor according to claim 10, wherein the hole transporting substance is a stilbene compound represented by the following general formula (4). Embedded image (Wherein, R ₁ and R ₂ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and R ₃ and R ₄ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted Represents an aryl group or a heterocyclic group.
₁ and R ₂ may form a ring with each other. Ar ₁ represents a substituted or unsubstituted arylene group or a heterocyclic group. ) 12. The electrophotographic photoreceptor according to claim 9, wherein the photosensitive layer comprises: a charge generation layer containing a charge generation substance;
A positive charge type electrophotographic photoreceptor, comprising: a charge transport layer containing an electron transport material; 13. The photoconductor according to claim 12, wherein the electron transporting substance is (2,3-diphenyl-1-indenylidene) malononitrile represented by the following formula (5). body. Embedded image 14. The photosensitive layer according to any one of claims 1 to 8, wherein the photosensitive layer is a charge generation material represented by any one of formulas (1) and (3) according to any one of claims 1 to 8. An electrophotographic photoreceptor comprising a single layer containing a tetraazaporphyrin derivative mixture comprising a tetraazaporphyrin derivative.