JP2000122317A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high sensitivity electrophotographic photoreceptor which can be applied to a laser printer as well as to a high-speed copying machine. SOLUTION: A photosensitive layer containing a compound having a tetrazaporphyrin skeleton of formula I is disposed on an electrically conductive substrate as an electric charge generating material. The compound has a new crystal structure having a diffraction peak at a Bragg angle (2θ±0.2 deg.) of 24.8 deg.±0.2 deg. in its X-ray diffraction spectrum using the Cu-Kαcharacteristic X-ray radiation (λ=1.54Å). In the formula, M is H or an atom or compound capable of forming a covalent or coordinate bond with tetrazaporphyrin and R1-R4 are each H, a lower alkyl or aryl.

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 compound 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

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as selenium, cadmium sulfide, and zinc oxide have been used 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 forming method in which an electrostatic latent image is obtained, and the latent image portion is developed with a detection fine particle (toner) composed of a colorant such as a dye or a pigment and a polymer substance to form a visible image. One. The basic characteristics required of the photoreceptor in such an electrophotographic system include (1) being able to be charged to an appropriate potential in a dark place, (2) having little charge dissipation in a dark place, and (3). Charge can be quickly dissipated by light irradiation, and the like.

At present, the above-mentioned inorganic substances have various advantages as well as various advantages. For example, the selenium photoreceptor is difficult to manufacture, its production cost is high, it is difficult to process it into a belt because it is not flexible, and it is sensitive to heat and mechanical shock, so care must be taken when handling it. Disadvantages such as the need for Cadmium sulfide and zinc oxide are used as a photoreceptor by being dispersed in a resin as a binder.
Due to mechanical defects such as smoothness, hardness, tensile strength and friction resistance, it cannot be used repeatedly as it is.

In recent years, electrophotographic photoreceptors using various organic substances have been proposed to eliminate the disadvantages of these inorganic substances, and some of them have been put to practical use. For example, poly
A photoreceptor comprising N-vinylcarbazole and 2,4,7-trinitrofluoren-9-one (US Pat. No. 348)
4237), a photoconductor obtained by sensitizing poly-N-vinylcarbazole with a pyrylium salt-based dye (described in JP-B-48-25658), and a photoconductor containing an organic pigment as a main component (described in JP-B-48-25658). Representative examples thereof include a photoreceptor having a eutectic complex consisting of a dye and a resin (described in JP-A-47-10735). In particular, a laminated photoreceptor in which a thin film of an organic pigment is formed on a conductive support (a charge generation layer) and a layer mainly composed of a charge transport substance (a charge transport layer) is formed thereon, is a conventional organic photoreceptor. Exhibiting higher sensitivity than the photoreceptor
Active research is being conducted on the basis of the variety of materials and the variety of materials, and it is becoming a mainstay as a photoconductor for copying machines and printers. However, in consideration of the demands on the photoreceptor such as the speeding up of a copying machine or the enhancement of the sensitivity in the wavelength range of a semiconductor laser, it is the present situation that none of these requirements has been sufficiently satisfied.

On the other hand, in the copying industry, etc., in recent years, there has been a demand for an editing function and a complex processing function, and with this, non-impact printer technology has been developed, and it has been applied to laser printers, laser facsimile machines, digital copiers and the like. Digital recording devices that can be seen are becoming widespread. Semiconductor lasers are often used as light sources in digital recording devices because of their small size, low cost, and simplicity, but the oscillation wavelength of semiconductors currently used is limited to a wavelength range of 600 nm or more. Have been. Therefore, the electrophotographic photosensitive member used in these recording apparatuses is required to have photosensitivity in a wavelength region of at least 600 to 850 nm.

As organic photoconductive materials satisfying this requirement, phthalocyanine pigments, azo pigments, cyanine pigments, azulene pigments, squarium pigments and the like are known.
In particular, phthalocyanine pigments have spectral absorption up to a relatively long wavelength region, have photosensitivity, and have various variations depending on the type of central metal and crystal type. Research is being actively carried out. Known phthalocyanine pigments include ε-type copper phthalocyanine, X-type metal-free phthalocyanine, τ-type metal-free phthalocyanine, vanadyl phthalocyanine, and titanyloxyphthalocyanine (JP-A-8-231869, JP-A-5-6659).
No. 5, JP-B-8-13942, etc.), but none of these are still sufficient in terms of sensitivity, charging ability, repetition durability and the like, and further improvements have been desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member which can be practically used not only for high-speed copying machines but also for laser printers.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a compound having a tetraazaporphyrin skeleton in a novel crystalline form useful as a charge generating material for an electrophotographic photoreceptor. And completed the present invention. That is, according to the present invention, first, in an electrophotographic photosensitive member having at least a photosensitive layer provided on a conductive support, Cu-Kα characteristic X-rays (λ = 1.
A novel crystal form having a Bragg angle 2θ ± 0.2 ° having a diffraction peak at 24.8 ° ± 0.2 ° in an X-ray diffraction spectrum using the compound represented by the following general formula (I): An electrophotographic photoreceptor characterized by containing a compound having an azaporphyrin skeleton is provided.

Embedded image (In the above formula, M represents a hydrogen atom or an atom or a compound capable of forming a covalent bond or a coordinate bond with tetraazaporphyrin, and R ¹ , R ² , R ³ , and R ⁴ are the same or different hydrogen atoms, Represents a substituted or unsubstituted lower alkyl group or a substituted or unsubstituted aryl group.) Secondly, in an electrophotographic photosensitive member having at least a photosensitive layer provided on a conductive support, Cu-Kα characteristic X-rays (λ) obtained by subjecting a compound having a tetraazaporphyrin skeleton described in
= 1.54 °), a novel crystal form having a broad diffraction peak at 24.8 ° ± 0.2 ° in the Bragg angle 2θ ± 0.2 ° in the X-ray diffraction spectrum of the above general formula (I) An electrophotographic photoreceptor comprising a compound having a tetraazaporphyrin skeleton represented by the formula: Third, in an electrophotographic photoreceptor having at least a photosensitive layer provided on a conductive support, the compound having a tetraazaporphyrin skeleton described in the above-mentioned first in the photosensitive layer is subjected to an acid treatment, and then an alcohol-based compound. Bragg in X-ray diffraction spectrum using Cu-Kα characteristic X-ray (λ = 1.54 °) obtained by treating with a solvent selected from the group consisting of a solvent, an ether-based solvent, a ketone-based solvent and water. Angle 2θ ± 0.2 ° is 24.8 ° ± 0.2 °
Formula (I) of a novel crystal form having a diffraction peak at
An electrophotographic photoreceptor comprising a compound having a tetraazaporphyrin skeleton represented by the formula: Fourth, in an electrophotographic photosensitive member having at least a photosensitive layer provided on a conductive support, after the compound having a tetraazaporphyrin skeleton described in the above-mentioned first in the photosensitive layer is subjected to an acid treatment, the amine-based compound is further treated. Bragg angle 2θ ± in an X-ray diffraction spectrum using Cu-Kα characteristic X-rays (λ = 1.54 °) obtained by treating with a solvent selected from the group consisting of a solvent and an aromatic hydrocarbon solvent.
0.2 ° contains a compound having a tetraazaporphyrin skeleton represented by the general formula (I) in a novel crystal form having a diffraction peak at 24.8 ° ± 0.2 °. An electrophotographic photoreceptor is provided. Fifth, in an electrophotographic photosensitive member having at least a photosensitive layer provided on a conductive support, the compound having a tetraazaporphyrin skeleton described in the above-described first in the photosensitive layer is mixed with a trihaloacetic acid and an alkylene halide mixed solvent. After adding or dissolving or slurrying, the resulting solution is added to a mixed solvent of cyclic ether / water to precipitate crystals, and the obtained crystals are washed with water and an aliphatic alcohol as necessary. Using Cu-Kα characteristic X-ray (λ = 1.54 °) obtained by
Angle 2θ ± 0.2 ° in X-ray diffraction spectrum
Contains a compound having a tetraazaporphyrin skeleton represented by the above general formula (I) in a novel crystal form having a diffraction peak at 24.8 ° ± 0.2 °. Is provided. Sixth, in an electrophotographic photosensitive member having at least a photosensitive layer provided on a conductive support, the photosensitive layer is obtained after acid-treating the compound having a tetraazaporphyrin skeleton described in the first above. Cu-Kα characteristic X-rays obtained by treating a tetraazaporphyrin compound with a solvent selected from the group consisting of alcohol solvents, ether solvents and ketone solvents without drying in the presence of water without drying. λ = 1.54
Bragg angle 2 in X-ray diffraction spectrum using ス ペ ク ト ル)
θ ± 0.2 ° contains a compound having a tetraazaporphyrin skeleton represented by the general formula (I) in a novel crystal form having a diffraction peak at 24.8 ° ± 0.2 °. Is provided. Seventh, in an electrophotographic photosensitive member having at least a photosensitive layer provided on a conductive support, the photosensitive layer is obtained after acid-treating the compound having a tetraazaporphyrin skeleton described in the first above. A Cu-Kα characteristic X-ray (λ) obtained by treating the tetraazaporphyrin compound with a solvent selected from the group consisting of an amine solvent and an aromatic hydrocarbon solvent in the presence of water without drying. = 1.54Å)
Angle 2θ ± in X-ray diffraction spectrum using
0.2 ° contains a compound having a tetraazaporphyrin skeleton represented by the general formula (I) in a novel crystal form having a diffraction peak at 24.8 ° ± 0.2 °. An electrophotographic photoreceptor is provided. Eighth, the photosensitive layer according to any one of the first to seventh aspects includes a charge generation layer containing a charge generation substance and a charge transport layer containing a charge transport substance, and the charge generation layer And an electrophotographic photoreceptor comprising the compound having a tetraazaporphyrin skeleton according to any one of the first to seventh aspects. Ninth, in the electrophotographic photoreceptor described in the eighth 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. Tenth,
In the photoconductor described in the ninth aspect, the hole transporting substance is
An electrophotographic photoreceptor is provided, which is a stilbene compound represented by the following general formula (II).

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. Eleventh, in the electrophotographic photoreceptor according to the eighth aspect, wherein 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. Twelfth, in the photoconductor according to the eleventh, the electron transporting substance is (2,3-diphenyl-1-indenylidene) malononitrile represented by the following formula (III). A photographic photoreceptor is provided.

Embedded image Thirteenth, the photosensitive layer according to any one of the first to seventh aspects is a single layer containing the compound having a tetraazaporphyrin skeleton according to any one of the first to seventh aspects as a charge generating substance. An electrophotographic photosensitive member is provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the compound having a tetraazaporphyrin skeleton represented by the general formula (I) used in the present invention, M in the general formula (I) is, for example, a hydrogen atom or Ti, Co, Ni, Cu, Al , Mg, Pb, V, F
e, Zn, Ge, Sn, Ga, Mo, In and other metal atoms, oxides of these metals, hydroxides of these metals, and halides of these metals (for example, fluoride, chloride, bromide, iodide) And the like). Also, R
¹ , R ² , R ³ and R ⁴ represent a hydrogen atom which may be the same or different, a substituted or unsubstituted lower alkyl group or a substituted or unsubstituted aryl group. Specific examples of the lower alkyl group include a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, and the substituent includes a fluorine atom and a halogen atom such as a chlorine atom. No. Specific examples of the substituted or unsubstituted aryl group include a phenyl group, a naphthyl group, a pyrenyl group, and the like.
Examples include a halogen atom such as a chlorine atom and an alkyl group such as a methyl group and an ethyl group.

M, R ¹ , R ² , R ³ in the general formula (I)
And although specific examples of R ⁴ include those shown in Table 1 and Table 2, but is not limited thereto.

[0011]

[Table 1]

[0012]

[Table 2]

The tetraazaporphyrin compound represented by the general formula (I) of the present invention can be prepared by, for example, converting a corresponding dinitrile compound and a metal salt compound or an alkoxy metal without solvent, α-chloronaphthalene, dichlorobenzene, In the presence of halogen solvents such as 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. Obtained by heating. The reaction temperature is usually from room temperature to 300 ° C., particularly preferably from 100 ° C. to 250 ° C., from the viewpoint of the reaction yield.

Further, the tetraazaporphyrin compound represented by the general formula (I) of the present invention comprises a corresponding acid anhydride;
It is also possible to synthesize in the presence of a metal salt compound and an amine such as urea or ammonium molybdate as a catalyst. The reaction is usually in the absence of a solvent or a halogenated solvent such as α-chloronaphthalene, dichlorobenzene, trichlorobenzene,
Alcoholic solvents such as pentanol and octanol,
Heating is performed in the presence of an amine solvent such as N, N-dimethylformamide and N-methylpyrrolidone, and an aromatic solvent such as benzene, toluene and nitrobenzene. 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.

The tetraazaporphyrin reaction product used in the present invention is a Cu-Kα characteristic X-ray (λ = 1.54 °)
Angle 2θ ± in X-ray diffraction spectrum using
Preferably, 0.2 ° is in a crystalline state having a main peak at 24.8 ° ± 0.2 °. The electrophotographic photoreceptor of the present invention has a photosensitive layer using a charge generation material containing the above crystal of the tetraazaporphyrin reaction product used in the present invention. The photosensitive layer has a Cu-Kα characteristic X-ray. (Λ = 1.54 °) in an X-ray diffraction spectrum using a Bragg angle 2θ ± 0.2 ° of 24.8 ° ± 0.2 °.
A photosensitive layer having a main peak at 2 ° is preferred.

Examples of the method for treating the obtained tetraazaporphyrin compound include an acid treatment, a solvent treatment, and a milling treatment. The acid treatment is a treatment in which a pigment is dissolved in an acid such as sulfuric acid at 5 ° C. or lower, and then dropped on ice water to precipitate a crystal of the pigment, and a crystal is obtained by a means such as filtration. In this case, it is preferable to perform acid treatment using sulfuric acid also from the viewpoint of cost. The solvent treatment is a suspension and stirring treatment of the pigment in a solvent at room temperature or under heating, and the milling treatment is, for example, a milling apparatus such as a sand mill or a ball mill using glass beads, steel beads, alumina balls, or the like. This is a process performed using. Examples of the solvent used for the solvent treatment include, for example, aromatic solvents such as benzene, toluene, dichlorobenzene, and nitrobenzene; alcohol solvents such as methanol and ethanol;
Cyclohexanone, ketone solvents such as methyl ethyl ketone, n-butyl ether, ethylene glycol n-butyl ether, ether solvents such as tetrahydrofuran,
Examples include amine solvents such as N, N-dimethylformamide, N-methylpyrrolidone, and quinoline, and water. Alternatively, a mixed system of these solvents can be used. Examples of the solvent used for the milling treatment include alcohol solvents such as methanol and ethanol, ketone solvents such as cyclohexanone and methyl ethyl ketone, ether solvents such as n-butyl ether, ethylene glycol n-butyl ether and tetrahydrofuran, and N, N-dimethyl. Formamide,
There are amine solvents such as N-methylpyrrolidone, basic solvents such as quinoline and pyridine, and water.

Further, according to the present invention, the tetraazaporphyrin pigment represented by the general formula (I) is added to a mixed solvent of trihaloacetic acid and alkylene halide and dissolved or slurried. A Cu-Kα characteristic X-ray (λ = 1.54 °) characterized by adding a crystal to a mixed solvent of water to precipitate a crystal and optionally washing the obtained crystal with water and an aliphatic alcohol. A tetraazaporphyrin pigment having a main peak at a Bragg angle of 2θ ± 0.2 ° at least at 24.8 ° ± 0.2 ° in the X-ray diffraction spectrum used can be provided. The trihaloacetic acid used here includes trichloroacetic acid, trifluoroacetic acid and the like. As the alkylene halide, dichloromethane, dichloroethane, chloroform, trichloroethylene and the like can be used. The mixing ratio of trihaloacetic acid and alkylene halide is preferably trihaloacetic acid / alkylene halide = 4/1 to 1/20 (volume ratio), particularly trihaloacetic acid / alkylene halide =
1/1 to 1/8 is preferred. When dissolving the tetraazaporphyrin pigment, the tetraazaporphyrin pigment is added at room temperature under stirring for an appropriate time, for example, over 2 to 10 minutes, and stirring is preferably continued for about 30 minutes to completely dissolve the tetraazaporphyrin pigment. . As the cyclic ether to be used, tetrahydrofuran, 1,4-dioxane, tetrahydropyran, tetrafurfuryl alcohol and the like can be used. The mixing ratio of cyclic ether and water is preferably cyclic ether / water = 3/1 to 1/3 (volume ratio). When dropping the tetraazaporphyrin pigment, it is preferable to cool the mixed solvent of cyclic ether / water to -5 to 10 ° C and to drop the mixture over a suitable period of time, for example, 5 minutes to 1 hour with stirring. After the completion of the dropwise addition, the mixture is stirred for about 30 minutes and filtered to obtain a precipitated tetraazaporphyrin pigment. Further, if necessary, washing is performed with water and an aliphatic alcohol. As the aliphatic alcohol used here, methanol, ethanol, n-propanol, isopropanol, and n-butanol can be used.

Further, according to the present invention, the tetraazaporphyrin pigment represented by the general formula (I) is specified by the acid treatment shown as the above-mentioned treatment method, and then mixed with an organic solvent in the presence of water. A crystalline tetraazaporphyrin pigment is obtained. As the organic solvent used at this time, for example, benzene, toluene, dichlorobenzene,
Aromatic solvents such as nitrobenzene, alcohol solvents such as methanol, ethanol, n-propanol, n-butanol and n-pentanol; ketone solvents such as cyclohexanone and methyl ethyl ketone; n-butyl ether; ethylene glycol n-butyl ether; tetrahydrofuran Ether solvents such as N, N-dimethylformamide, N-methylpyrrolidone and quinoline; and water. The amount of the organic solvent is preferably 5 times or more, and more preferably 5 to 100 times, the volume of the solid content of the tetraazaporphyrin pigment. If the amount is small, stirring is not sufficiently performed, and it is difficult to obtain uniform crystals. The organic solvent, water and the tetraazaporphyrin pigment may be added in any order. In order to further ensure the presence of water, there is a method in which water is added to a reaction vessel together with a solvent, and a tetraazaporphyrin pigment is added to an organic solvent saturated with water from an early stage.
The temperature at which the crystal conversion is performed may be in a range in which water exists as a liquid, and may be 0 to 100 ° C, preferably 15 to 80 ° C. The time is not particularly limited, but it is preferable that stirring can be performed in a sufficiently uniform state.

The tetraazaporphyrin compound represented by the general formula (I) used in the present invention may be used, for example, by mixing and dispersing with the following pigments. Examples of such organic pigments include C.I. Pigment Blue 25 (Color Index CI21180), C.I. Pigment Red 41 (CI2200), C.I. Acid Red 52 (CI.45100), C.I. (Described in JP-A-53-95033), azo pigments having a distyrylbenzene skeleton (JP-A-53-133445), and azo pigments having a triphenylamine skeleton (described in JP-A-53-132347).
Azo pigments having a dibenzothiophene skeleton (described in JP-A-54-21728), and azo pigments having an oxadiazole skeleton (described in JP-A-54-127).
No. 42), an azo pigment having a fluorenone skeleton (described in JP-A-54-22834), an azo pigment having a bisstilbene skeleton (described in JP-A-54-17733)
Azo pigments having a distyryloxadiazole skeleton (described in JP-A-54-2129),
Azo pigments such as azo pigments having a distyrylcarbazole skeleton (described in JP-A-54-14967), and, for example, CI Pigment Blue 16 (CI74
100), phthalocyanine pigments such as titanyl phthalocyanine, and further, for example, C-Ivat Brown 5 (C
I73410), sea butt die (CI7303)
0) and the like, furthermore, Argoscarlet B (manufactured by Bayer AG), Insence Scarlet R
(Manufactured by Bayer AG) and the like. These organic pigments may be used alone or in combination of two or more.

In the present invention, a dispersion-type or function-separation-type electrophotographic photoreceptor can be prepared by using the organic pigment represented by the general formula (I) as a charge generating substance and combining it with a charge transporting substance. In the case of a dispersion type layer structure, a photosensitive layer in which a charge generating substance and a charge transporting substance are dispersed in a binder is provided on a conductive support. In the case of the function separation type, a charge generation layer containing a charge generation substance and a binder is formed on a support, and a charge transport layer containing a charge transport substance and a binder is formed thereon. In this case, the charge generation layer and the charge transport layer may be stacked in reverse order.

Further, in the electrophotographic photosensitive member 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 charge generating substance can be provided by dissolving or dispersing it in a suitable solvent together with a binder resin, if necessary, coating and drying. Examples of the method for dispersing the charge generating substance 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 material is dispersed to form the charge generation layer, the charge generation material is 2 μm or less, preferably 1 μm, in order to improve the dispersibility in the charge generation layer.
Those having the following average particle size are preferred. However, if the particle size is too small, it tends to aggregate rather than increase, the resistance of the charge generation layer increases, the number of crystal defects increases, the sensitivity and repetition characteristics decrease, or there is a limit in miniaturization. Is preferably 0.01 μm.

The solvent used in preparing the dispersion or solution for the charge generation layer or the charge transport layer includes:
For example, N, N-dimethylformamide, toluene, xylene, monochlorobenzene, 1,2-dichloroethane, 1,1,1-trichloroethane, dichloromethane,
1,1,2-trichloroethane, trichloroethylene,
Examples thereof include tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, and butyl acetate.

As the binder used for forming the charge generating layer, the charge transport layer and the dispersion type photosensitive layer, any known binder having good insulating properties for an electrophotographic photosensitive member can be used. Yes, 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 resin, vinyl chloride resin, vinyl acetate resin, epoxy resin,
Polyurethane resin, phenolic resin, polyester resin, alkyd resin, polycarbonate resin, polyamide resin, silicone resin, addition polymerization type resin such as melamine resin, polyaddition type resin, polycondensation type resin, and 2 of repeating units of these resins Insulating resins such as vinyl chloride-vinyl acetate copolymer, styrene-acryl copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, and poly-N Polymer organic semiconductors such as vinyl carbazole. These binders can be used alone or as a mixture of two or more.

In the case where a photoreceptor is manufactured using the above-described layer constitution and substance, there are preferable ranges for the film thickness and the ratio of the substance. For example, in the case of the negative charge type (lamination of the substrate / charge generation layer / charge transport layer), the charge generation layer has a charge generation substance ratio of 20% by weight and a film thickness of 0.01 in the charge generation layer.
５5 μm is preferred. In the charge transport layer, the ratio of the charge transport material to the binder is preferably 20 to 200% by weight, and the film thickness is preferably 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, and the film thickness is 5 to 1%.
It is preferably set to 00 μm. The charge generation layer preferably contains a charge generation substance in an amount of 20% by weight or more based on the binder. 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 preferably contained in an amount of 20 to 200% by weight based on the binder. In the case of a so-called dispersion type photoconductor in which a charge generating material and a charge transporting material are dispersed in a binder resin, the ratio of the pigment as the charge generating material to the binder resin in the photosensitive layer is as follows. 5 to 95% by weight, film thickness 1
It is preferably from 0 to 100 μm. In this case, the ratio of the charge transporting substance to the binder resin is preferably 30 to 200% by weight.

Further, in these photosensitive layers, a phenol compound, a hydroquinone compound, a hindered phenol compound, a hindered amine compound, a hindered amine, A compound in which dophenol is present in the same molecule 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.

As the material of the intermediate layer, in addition to the above-mentioned binder resins, polyamide resin, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride Acid copolymer, casein, resin such as N-alkoxymethyl nylon as it is, or tin oxide, aluminum oxide, titanium oxide, silicon oxide, or a dispersion of indium oxide or the like, aluminum oxide, zinc oxide, titanium oxide, Alternatively, a deposition film of silicon oxide or the like can be given.

Further, as the material used for the protective layer, it is appropriate to use the above-mentioned resin as it is, or to disperse a low-resistance substance such as tin oxide or indium oxide. Also, organic plasma polymerized membranes can be used,
The organic plasma polymerized film may optionally contain oxygen, halogen, and atoms of Group III and Group V of the periodic table.

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 (II) is suitably used because of its high charge transport ability.

[0032]

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 (II) are shown in Tables 3 to 12, but the present invention is not limited thereto.

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

[Table 5]

[0037]

[Table 6]

[0038]

[Table 7]

[0039]

[Table 8]

[0040]

[Table 9]

[0041]

[Table 10]

[0042]

[Table 11]

[0043]

[Table 12]

Further, examples of the hole transport material include compounds represented by the following general formulas (1) to (18).

(1) Compounds represented by the following general formula (1) (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. )

Compounds represented by the general formula (1) include, for example, 9-ethylcarbazole-3-aldehyde-1-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 general formula (2) (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 (2) includes, for example, 4-diethylaminostyryl-3-aldehyde-1
-Methyl-1-phenylhydrazone, 4-methoxynaphthalene-1-aldehyde-1-benzyl-1-phenylhydrazone and the like.

(3) Compound represented by the following formula (3) (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.)

The compound represented by the general formula (3) includes, for example, 4-methoxybenzaldehyde-1-methyl-1-
Phenylhydrazone, 2,4-dimethoxybenzaldide-1-benzyl-1-phenylhydrazone, 4-diethylaminobenzaldehyde-1,1-diphenylhydrazone, 4-methoxybenzaldehyde-1-benzyl-1- (4-methoxy) Phenylhydrazone, 4-diphenylaminobenzaldehyde-1-benzyl-1-
Examples include phenylhydrazone and 4-dibenzylaminobenzaldehyde-1,1-diphenylhydrazone.

(4) Compound represented by the following formula (4) (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. )

Compounds represented by the general formula (4) include, for example, 1,1-bis (4-dibenzylaminophenyl) 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 general formula (5) (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 (5) includes, for example, 9- (4-diethylaminostyryl) anthracene, 9-bromo-10- (4-diethylaminostyryl) anthracene and the like.

(6) Compound represented by the following general formula (6) (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. ]

As the compound represented by the general formula (6),
For example, 9- (4-dimethylaminobenzylidene) fluorene, 3- (9-fluorenylidene) -9-ethylcarbazole, and the like can be given.

(7) Compound represented by the following formula (7) (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. )

The compound represented by the general formula (7) includes, for example, 1,2-bis (4-diethylaminostyryl) benzene, 1,2-bis (2,4-dimethoxystyryl) benzene and the like.

(8) Compound represented by the following formula (8) (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 (8) include, for example, 3-styryl-9-ethylcarbazole, 3- (4
-Methoxystyryl) -9-ethylcarbazole and the like.

(9) Compound represented by the following formula (9) (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.)

The compound represented by the general formula (9) includes, for example, 4-diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene,
-(4-diphenylaminostyryl) naphthalene, 1-
(4-Diethylaminostyryl) naphthalene and the like.

(10) A compound represented by the following formula (10) (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 (10) includes, for example, 4'-diphenylamino-α-phenylstilbene, 4'-bis (methylphenyl) amino-α-phenylstilbene and the like.

(11) Compound represented by the following general formula (11) (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 (11) include, for example, 1-phenyl-3- (4-diethylaminostyryl) -5- (4-diethylaminophenyl) pyrazoline, 1-phenyl-3- (4- Dimethylaminostyryl) -5- (4-dimethylaminophenyl) pyrazolin.

(12) Compound represented by the following formula (12) (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 (12) 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) A compound represented by the following general formula (13) (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 (13), 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 (14) (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 (14) 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 (15) (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 (15) 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) A compound represented by the following formula (16) (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 (16) includes, for example, 1-laminopyrene, 1-di (p-tolylamino) pyrene and the like.

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

A-CH = CH-Ar-CH = CH-A (17) [wherein, Ar represents a substituted or unsubstituted aromatic hydrocarbon group;

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 compounds represented by the general formula (17) include, for example, 1,4-bis (4-diphenylaminostyryl) benzene, 1,4-bis [4-di (p-tolyl) [Aminostyryl] benzene.

(18) A compound represented by the following formula (18) (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 (18) 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] thiophen-4-one, 1,3,7-trinitrodibenzothiophene-5,5-dioxide, etc., and the following (II)
The electron transporting substances listed in the formulas (I), (19) and (20) can be suitably used. These charge transport materials are used alone or in combination of two or more.

[0082]

Embedded image

Embedded image

Embedded image

[0083]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Production Example 1 6.3 g (0.04 mol) of 5,6-dihydro-1,4-dithiin-2,3-dicarbonitrile, 0.99 g (0.01 mol) of cuprous chloride, 1. 2 g (0.0
2 mol) and 60 ml of 1-octanol were stirred and mixed,
The temperature was gradually raised to 160 ° C. in a nitrogen stream,
The mixture was stirred and reacted for 5 hours while maintaining the temperature between 50 and 160 ° C. After completion of the reaction, the reaction solution was allowed to cool, and when it reached 130 ° C., it was filtered while hot, then washed with dimethylformamide and methanol, further washed several times with hot water and ethanol at 80 ° C., and then dried and dried to obtain 4.2 g (yield). (58%) of crude copper tetraazaporphyrin pigment. FIG. 1 shows the IR spectrum.
The results of elemental analysis are shown below. CH N actual value (%) 39.38 2.12 15.28 calculated value (%) 39.14 2.19 15.21 The X-ray diffraction spectrum of the pigment obtained in Production Example 1 is shown in FIG.

Production Example 2 5.1 g (0.03 mol) of 5,6-dihydro-1,4-dithiin-2,3-dicarbonitrile, 2.6 g (7.6 mol) of titanium tetrabutoxide, 0.9 g of urea
g (0.015 mol) and 50 ml of 1-octanol were stirred and mixed, and gradually heated to 160 ° C. under a nitrogen stream.
The mixture was stirred and reacted for 5 hours while maintaining the reaction temperature between 150 and 160 ° C. After completion of the reaction, the reaction solution was allowed to cool, and when heated to 130 ° C., filtered by heating, and then dimethylformamide,
After washing with methanol, further washing with hot water and ethanol at 80 ° C. several times, and drying, 4.2 g (yield 76%) of crude T
An i = O tetraazaporphyrin pigment was obtained. Fig. 3 shows IR
The spectrum is shown. The results of elemental analysis are shown below. CHN actual value (%) 39.32 2.29 15.35 calculated value (%) 39.12 2.19 15.21 The X-ray diffraction spectrum of the pigment obtained in Production Example 2 is shown in FIG.

Production Example 3 3 g of the crude Ti ＝ O tetraazaporphyrin pigment obtained in Production Example 2 was gradually dissolved in 60 g of 98% sulfuric acid at 5 ° C., and the mixture was heated at a temperature of 5 ° C. or less for about 1 hour. Stir while keeping. Subsequently, the sulfuric acid solution was stirred at a high speed of 800 m.
The mixture was slowly poured into 1 l of ice water, and the precipitated crystals were filtered. After washing the crystals with distilled water until the filtrate is neutral,
After drying, 2.9 g of TiＴｉO tetraazaporphyrin pigment was obtained. The X-ray diffraction spectrum of the pigment obtained in Production Example 3 is shown in FIG.

Production Example 4 1 g of the Ti ＝ O tetraazaporphyrin pigment obtained in Production Example 3 was placed in a 200 ml Erlenmeyer flask, and MeOH 5
The mixture is refluxed for 8 hours with heating and stirring with 0 ml. After cooling to room temperature, filtration and drying, 0.97 g of crystalline Ti = O tetraazaporphyrin pigment was obtained. Production Example 4
FIG. 6 shows an X-ray diffraction spectrum of the pigment obtained in the above step.

Production Example 5 1 g of the Ti ＝ O tetraazaporphyrin pigment obtained in Production Example 3 is placed in a 200 ml Erlenmeyer flask, and refluxed with 50 ml of cyclohexanone under heating and stirring for 8 hours. After cooling to room temperature, filtration and drying, 0.97 g
A crystalline Ti = O tetraazaporphyrin pigment was obtained.
FIG. 7 shows an X-ray diffraction spectrum of the pigment obtained in Production Example 5.

Production Example 6 1 g of the Ti ＝ O tetraazaporphyrin pigment obtained in Production Example 3 is placed in a 200 ml Erlenmeyer flask, and refluxed for 8 hours with heating and stirring with 50 ml of tetrahydrofuran. After cooling to room temperature, filtration and drying,
g of crystalline Ti = O tetraazaporphyrin pigment was obtained. FIG. 8 shows an X-ray diffraction spectrum of the pigment obtained in Production Example 6.

Production Example 7 1 g of the Ti ＝ O tetraazaporphyrin pigment obtained in Production Example 3 is placed in a 200 ml Erlenmeyer flask, and refluxed with heating and stirring for 8 hours together with 36 ml of methyl ethyl ketone and 4 ml of water. After cooling to room temperature, filtration and drying, 0.93 g of crystalline Ti = O tetraazaporphyrin pigment was obtained. FIG. 9 shows an X-ray diffraction spectrum of the pigment obtained in Production Example 7.

Production Example 8 1 g of the Ti ＝ O tetraazaporphyrin pigment obtained in Production Example 3 is placed in a 200 ml Erlenmeyer flask and refluxed with heating and stirring with 50 ml of N, N-dimethylformamide for 8 hours. After cooling to room temperature, filtration and drying, 0.93 g of crystalline Ti = O tetraazaporphyrin pigment was obtained. The X-ray diffraction spectrum of the pigment obtained in Production Example 8 is shown in FIG.

Production Example 9 1 g of the Ti ＝ O tetraazaporphyrin pigment obtained in Production Example 3 is placed in a 200 ml Erlenmeyer flask, and refluxed with 50 ml of nitrobenzene under heating and stirring for 8 hours. After cooling to room temperature, filtration and drying, 0.97 g of crystalline Ti = O tetraazaporphyrin pigment was obtained. FIG. 11 shows an X-ray diffraction spectrum of the pigment obtained in Production Example 9.

Production Example 10 1 g of the crude Ti ＝ O tetraazaporphyrin pigment obtained in Production Example 2 was mixed with 2 ml of trifluoroacetic acid / dichloromethane.
This was dissolved in a mixed solvent of / 8 ml, and this was dropped into a mixed solvent of tetrahydrofuran / water = 25 ml / 25 ml cooled with ice at 5 ° C. while stirring to precipitate crystals, which were allowed to stand for 30 minutes after stirring. After the crystals precipitated, the supernatant was removed, 50 ml of methanol was added, the mixture was stirred for 30 minutes, and filtered. The obtained solid is dispersed in 100 ml of hot water, washed repeatedly,
A wet cake of Ti = O tetraazaporphyrin pigment was obtained. Wash the obtained wet cake with methanol,
Dry to obtain Ti = O tetraazaporphyrin pigment 0.95
g was obtained. FIG. 12 shows an X-ray diffraction spectrum of the pigment obtained in Production Example 10.

Production Example 11 Without drying the Ti ＝ O tetraazaporphyrin pigment obtained in the same manner as in Production Example 3, 4.89 g (21% solid content) of this wet cake was mixed with 6.1 parts of ion-exchanged water.
g was added thereto, and 40.1 g of tetrahydrofuran was added thereto, followed by stirring at room temperature for 6 hours, followed by filtration. The obtained crystals were washed with methanol and dried to obtain 0.93 g of the desired Ti = O tetraazaporphyrin pigment. FIG. 13 shows an X-ray diffraction spectrum of the pigment obtained in Production Example 11.

Production Example 12 Without drying the Ti ＝ O tetraazaporphyrin pigment obtained in the same manner as in Production Example 3, 4.89 g (21% solid content) of this wet cake was mixed with 6.1 parts of ion-exchanged water.
g was added thereto, and 40.1 g of dimethylformamide was added thereto. The mixture was stirred at room temperature for 6 hours and filtered. The obtained crystals were washed with methanol and dried to obtain 0.98 g of a target Ti ＝ O tetraazaporphyrin pigment. FIG. 14 shows an X-ray diffraction spectrum of the pigment obtained in Production Example 12.

The conditions for measuring the X-ray diffraction spectrum of the tetraazaporphyrin pigments obtained in the above Production Examples 1 to 12 are as follows. X-ray tube Cu (wavelength 1.54Å) Voltage 40 kV Current 20 mA Scanning speed 1 deg / min Scanning range 3 to 40 deg

Example 1 1 part by weight of the Ti ＝ O tetraazaporphyrin pigment obtained in Production Example 2, a polyvinyl butyral resin (BM-S,
50 parts by weight of a 2% by weight butyl acetate solution (manufactured by Sekisui Chemical Co., Ltd.) and 49 parts by weight of n-butyl acetate were dispersed in a sand mill using glass beads having a diameter of 2 mm for 2 hours. This was applied on a 75 μm aluminum deposited PET base and
After drying at 0 ° C. for 5 minutes, a charge generation layer having a thickness of 0.2 μm was formed. Next, 42 parts by weight of a hole transporting substance represented by the following structural formula (D-1), 60 parts by weight of a polycarbonate resin (Iupilon Z200, manufactured by Mitsubishi Gas Chemical Company), silicone oil (KF50, manufactured by Shin-Etsu Chemical Co., Ltd.) 001 parts by weight were dissolved in 638 parts by weight of dichloromethane to prepare a charge transport layer coating solution. This was applied on the charge generation layer, and 8
After drying at 0 ° C. for 2 minutes and at 110 ° C. for 10 minutes, a film thickness of 20
A μm charge transport layer was formed to obtain an electrophotographic photosensitive member of Example 1.

[0098]

Embedded image

Example 2 Example 1 was repeated except that the Ti ＝ O tetraazaporphyrin pigment obtained in Preparation Example 3 was used instead of the Ti ＝ O tetraazaporphyrin pigment obtained in Preparation Example 2. In the same manner as in the above, an electrophotographic photosensitive member of Example 2 was obtained.

Example 3 The procedure of Example 1 was repeated, except that the Ti ポ O tetraazaporphyrin pigment obtained in Preparation Example 4 was used instead of the Ti ＝ O tetraazaporphyrin pigment obtained in Preparation Example 2. In the same manner as in the above, an electrophotographic photosensitive member of Example 3 was obtained.

Example 4 Example 1 was repeated except that the Ti を O tetraazaporphyrin pigment obtained in Preparation Example 5 was used instead of the Ti ＝ O tetraazaporphyrin pigment obtained in Preparation Example 2. In the same manner as in the above, an electrophotographic photosensitive member of Example 4 was obtained.

Example 5 Example 1 was repeated except that the Ti 代 わ り O tetraazaporphyrin pigment obtained in Preparation Example 6 was used instead of the Ti 代 わ り O tetraazaporphyrin pigment obtained in Preparation Example 2. In the same manner as in the above, an electrophotographic photosensitive member of Example 5 was obtained.

Example 6 The procedure of Example 1 was repeated except that the Ti ＝ O tetraazaporphyrin pigment obtained in Preparation Example 7 was used instead of the TiＴｉO tetraazaporphyrin pigment obtained in Preparation Example 2. In the same manner as in the above, an electrophotographic photosensitive member of Example 6 was obtained.

Example 7 Example 1 was repeated except that the Ti 代 わ り O tetraazaporphyrin pigment obtained in Preparation Example 8 was used instead of the Ti ＝ O tetraazaporphyrin pigment obtained in Preparation Example 2. In the same manner as in the above, an electrophotographic photosensitive member of Example 7 was obtained.

Example 8 Example 1 was repeated except that the Ti を O tetraazaporphyrin pigment obtained in Preparation Example 9 was used instead of the Ti ＝ O tetraazaporphyrin pigment obtained in Preparation Example 2. In the same manner as in the above, an electrophotographic photosensitive member of Example 8 was obtained.

Example 9 Instead of using the Ti ＝ O tetraazaporphyrin pigment obtained in Production Example 2, the Ti ＝ O obtained in Production Example 10 was used.
An electrophotographic photosensitive member of Example 9 was obtained in the same manner as in Example 1, except that a tetraazaporphyrin pigment was used.

Example 10 Instead of using the Ti ＝ O tetraazaporphyrin pigment obtained in Production Example 2, the Ti ＝ O obtained in Production Example 11 was used.
An electrophotographic photosensitive member of Example 10 was obtained in the same manner as in Example 1, except that a tetraazaporphyrin pigment was used.

Example 11 Instead of using the Ti ＝ O tetraazaporphyrin pigment obtained in Production Example 2, the Ti ＝ O obtained in Production Example 12 was used.
An electrophotographic photosensitive member of Example 11 was obtained in the same manner as in Example 1, except that a tetraazaporphyrin pigment was used.

Example 12 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 1, an electrophotographic photosensitive member of Example 12 was obtained.

Embedded image

Example 13 The procedure of Example 1 was repeated, except that the hole transport material (D-1) represented by the following structural formula was used in place of the hole transport material (D-1) used in Example 1. In the same manner as in Example 1, an electrophotographic photosensitive member of Example 13 was obtained.

Embedded image

Example 14 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 1, an electrophotographic photosensitive member of Example 14 was obtained.

Embedded image

<Evaluation> The electrophotographic photosensitive members produced in Examples 1 to 14 were subjected to an electrostatic property measuring device EPA-8 manufactured by Kawaguchi Electric Co., Ltd.
Using a 200, a corona discharge was performed at -6 kV for 20 seconds to charge the surface, and then the surface potential Vo after dark decay for 20 seconds.
(V) After irradiation with 20 lux of light, the exposure amount E _1/2 (lux · sec) required to reduce Vo to １ ／ was measured. Table 13 shows the results.

[0113]

[Table 13]

Example 15 In the same manner as in Example 1, a charge generation layer was formed on an aluminum-deposited PET base. Next, 8 parts by weight of the electron transport material represented by the structural formula (III), 11 parts by weight of polycarbonate Z (manufactured by Teijin Chemicals Limited), and silicone oil (KF50,
0.02 parts by weight of tetrahydrofuran 9
This was dissolved in 1 part by weight, and the solution was cast-coated on the charge generation layer with a doctor blade and dried to form a charge transport layer having a thickness of 20 μm. Thus, an electrophotographic photoreceptor of Example 15 was obtained.

Example 16 The same procedure as in Example 15 was repeated, except that the electron transporting material used in Example 15 was replaced with the electron transporting material represented by the structural formula (19). I got a body.

The photoreceptors produced in Examples 15 and 16 were subjected to a corona discharge of 20 at +5.3 kV using the above-described measuring apparatus.
After charging for 20 seconds, surface potential Vo (V) after dark decay for 20 seconds, and after irradiation with light of 20 lux, Vo is 1
/ _1/2 Exposure E1 _{/ 2} (lux · sec)
Was measured. Table 14 shows the results.

[0117]

[Table 14]

Example 17 A solution of 0.5 g of the Ti ＝ O tetraazaporphyrin pigment obtained in Production Example 2 in a polycarbonate Z (manufactured by Teijin Chemicals Ltd.) solution 1
After ball milling with 0 g (dissolved in tetrahydrofuran to a concentration of 10% by weight) and 9 g of tetrahydrofuran, 2% by weight of a pigment composition, 50% by weight of a polycarbonate Z composition, and a charge transport material (D-1)
Was adjusted to 28% by weight, and a 10% by weight polycarbonate Z solution was added thereto, followed by sufficient stirring to prepare a photosensitive layer coating solution. The single-layer electrophotographic photoreceptor of Example 17 having the coating liquid prepared in this manner cast and applied on a polyester film on which aluminum is deposited by a doctor blade and having a photosensitive layer having a thickness of 15 μm after drying. I got

The electrophotographic photosensitive member produced in Example 17 was charged by performing a corona discharge at −6 kV for 20 seconds using the above-described measuring apparatus, and then the surface potential Vo (V) after dark attenuation for 20 seconds. , After irradiation with light of 20 lux, Vo
It was measured necessary exposure amount _{E 1/2 (lux · sec} ) to become. Table 15 shows the results.

[0120]

[Table 15]

[0121]

According to the present invention, by using a compound represented by the above general formula (I) having a novel crystalline form of a tetraazaporphyrin skeleton as a charge generating substance of an electrophotographic photoreceptor, chargeability is improved. An excellent and highly sensitive electrophotographic photoreceptor can be provided. For example, by using the above compound as a charge generating substance, a highly sensitive laminated or single-layer type electrophotographic photoreceptor can be provided. Specifically, by using the above compound as a charge generating substance and using a hole transporting substance or an electron transporting substance as a charge transporting substance, a highly sensitive laminated electrophotographic photosensitive member can be provided. Then, in the electrophotographic photoreceptor, using the above compound as a charge generating substance,
By using a specific hole transporting substance or a specific electron transporting substance, it is possible to provide a laminated electrophotographic photoreceptor having higher sensitivity.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of the tetraazaporphyrin pigment obtained in Production Example 1.

FIG. 2 is an X-ray diffraction spectrum of the tetraazaporphyrin pigment obtained in Production Example 1.

FIG. 3 is an IR spectrum of the tetraazaporphyrin pigment obtained in Production Example 2.

FIG. 4 is an X-ray diffraction spectrum of the tetraazaporphyrin pigment obtained in Production Example 2.

FIG. 5 is an X-ray diffraction spectrum of the tetraazaporphyrin pigment obtained in Production Example 3.

FIG. 6 is an X-ray diffraction spectrum of the tetraazaporphyrin pigment obtained in Production Example 4.

FIG. 7 is an X-ray diffraction spectrum of the tetraazaporphyrin pigment obtained in Production Example 5.

8 is an X-ray diffraction spectrum of the tetraazaporphyrin pigment obtained in Production Example 6. FIG.

9 is an X-ray diffraction spectrum of the tetraazaporphyrin pigment obtained in Production Example 7. FIG.

FIG. 10 is an X-ray diffraction spectrum of the tetraazaporphyrin pigment obtained in Production Example 8.

FIG. 11 is an X-ray diffraction spectrum of the tetraazaporphyrin pigment obtained in Production Example 9.

FIG. 12 is an X-ray diffraction spectrum of the tetraazaporphyrin pigment obtained in Production Example 10.

FIG. 13 is an X-ray diffraction spectrum of the tetraazaporphyrin pigment obtained in Production Example 11.

14 is an X-ray diffraction spectrum of the tetraazaporphyrin pigment obtained in Production Example 12. FIG.

 ──────────────────────────────────────────────────続 き Continued on front page (72) Inventor Kaoru Tadokoro 1-36 Nakamagome, Ota-ku, Tokyo F-term in Ricoh Co., Ltd. (Reference) 2H068 AA19 AA20 AA21 AA28 AA37 BA13 BA14 BA38 BA39 BA63 EA05 FB07

Claims (13)

[Claims] 1. An electrophotographic photoreceptor comprising at least a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains Cu-
The Bragg angle 2θ ± 0.2 ° in the X-ray diffraction spectrum using the Kα characteristic X-ray (λ = 1.54 °) is 24.8.
An electrophotographic photosensitive member containing a compound having a tetraazaporphyrin skeleton represented by the following general formula (I) in a novel crystal form having a diffraction peak at ° ± 0.2 °. Embedded image (In the above formula, M represents a hydrogen atom or an atom or a compound capable of covalently or coordinating with tetraazaporphyrin, and R ¹ , R ² , R ³ , and R ⁴ are the same or different hydrogen atoms, Represents a substituted or unsubstituted lower alkyl group or a substituted or unsubstituted aryl group.) 2. An electrophotographic photoreceptor comprising at least a photosensitive layer provided on a conductive support, which is obtained by acid-treating the compound having a tetraazaporphyrin skeleton according to claim 1 in the photosensitive layer. , The Bragg angle 2θ ± 0.2 ° in the X-ray diffraction spectrum using Cu-Kα characteristic X-ray (λ = 1.54 °) is 24.8 ° ± 0.2 °
An electrophotographic photoreceptor comprising a compound having a tetraazaporphyrin skeleton represented by the above general formula (I) in a novel crystal form having a broad diffraction peak. 3. An electrophotographic photoreceptor comprising at least a photosensitive layer provided on a conductive support, wherein the compound having a tetraazaporphyrin skeleton according to claim 1 is subjected to an acid treatment in the photosensitive layer, and then an alcohol-based compound. Solvent, ether solvent,
Cu-Kα characteristic X-rays (λ =＝) obtained by treating with a solvent selected from the group consisting of ketone solvents and water.
The Bragg angle 2θ ± 0.2 ° in the X-ray diffraction spectrum using 1.54 °) is represented by the general formula (I) of a novel crystal form having a diffraction peak at 24.8 ° ± 0.2 °. An electrophotographic photoreceptor comprising a compound having a tetraazaporphyrin skeleton. 4. An electrophotographic photoreceptor comprising at least a photosensitive layer provided on a conductive support, after the compound having a tetraazaporphyrin skeleton according to claim 1 in the photosensitive layer is subjected to an acid treatment, and further comprising an amine-based compound. Bragg angle 2θ ± in an X-ray diffraction spectrum using Cu-Kα characteristic X-rays (λ = 1.54 °) obtained by treating with a solvent selected from the group consisting of a solvent and an aromatic hydrocarbon solvent. 0.
An electrophotograph wherein 2 ° contains a compound having a tetraazaporphyrin skeleton represented by the above general formula (I) in a novel crystal form having a diffraction peak at 24.8 ° ± 0.2 °. Photoconductor. 5. An electrophotographic photosensitive member comprising at least a photosensitive layer provided on a conductive support, wherein the compound having a tetraazaporphyrin skeleton according to claim 1 is provided in the photosensitive layer.
Added to the mixed solvent of trihaloacetic acid and alkylene halide,
After dissolving or slurrying, the obtained solution was added to a mixed solvent of cyclic ether / water to precipitate crystals, and the obtained crystals were washed with water and an aliphatic alcohol as necessary. , Cu-Kα characteristic X-ray (λ = 1.
A novel crystal form having a Bragg angle 2θ ± 0.2 ° having a diffraction peak at 24.8 ° ± 0.2 ° in the X-ray diffraction spectrum using (54 °) represented by the general formula (I) An electrophotographic photoreceptor comprising a compound having an azaporphyrin skeleton. 6. An electrophotographic photosensitive member having at least a photosensitive layer provided on a conductive support, obtained by subjecting the compound having a tetraazaporphyrin skeleton according to claim 1 to an acid treatment in the photosensitive layer. Cu-K obtained by treating the tetraazaporphyrin compound with a solvent selected from the group consisting of an alcohol-based solvent, an ether-based solvent and a ketone-based solvent in the presence of water without drying.
The Bragg angle 2θ ± 0.2 ° in the X-ray diffraction spectrum using α characteristic X-rays (λ = 1.54 °) is 24.8 °.
An electrophotographic photosensitive member containing a compound having a tetraazaporphyrin skeleton represented by the above general formula (I) in a novel crystal form having a diffraction peak at ± 0.2 °. 7. An electrophotographic photoreceptor comprising at least a photosensitive layer provided on a conductive support, obtained by subjecting the compound having a tetraazaporphyrin skeleton according to claim 1 to an acid treatment in the photosensitive layer. A Cu-Kα characteristic X-ray (λ) obtained by treating the tetraazaporphyrin compound with a solvent selected from the group consisting of an amine solvent and an aromatic hydrocarbon solvent in the presence of water without drying.
= 1.54 °), a Bragg angle 2θ ± 0.2 ° in the X-ray diffraction spectrum using the above-mentioned general formula (I) of a novel crystal form having a diffraction peak at 24.8 ° ± 0.2 ° An electrophotographic photoreceptor comprising a compound having a tetraazaporphyrin skeleton. 8. 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 photosensitive member comprising the compound having a tetraazaporphyrin skeleton according to any one of claims 1 to 7. 9. The electrophotographic photoreceptor according to claim 8, 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. 10. The electrophotographic photoconductor according to claim 9, wherein the hole transporting material is a stilbene compound represented by the following general formula (II). 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. ) 11. The electrophotographic photoreceptor according to claim 8, 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; 12. The electrophotographic photosensitive member according to claim 11, wherein the electron transporting substance is (2,3-diphenyl-1-indenylidene) malononitrile represented by the following formula (III). body. Embedded image 13. The photosensitive layer according to any one of claims 1 to 7, which is a single layer containing the compound having a tetraazaporphyrin skeleton according to any one of claims 1 to 7 as a charge generating substance. An electrophotographic photosensitive member characterized by the following.