JPH11166129A - Tetrapyrazinoporphyrazine compound and electrophotographic photoreceptor using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrophotographic photoreceptor having excellent chargeability and high sensitivity by incorporating a tetrapyrazinoporphyrazine compound having a specified crystal form in the photoreceptive layer. SOLUTION: This tetrapyrazinoporphyrazine compound is represented by the formula and has a novel crystal form which gives an X-ray (Cu Kα line) diffraction spectrum having an intense diffraction peak at a Brag angle (2θ±0.2 deg.) of 26.8 deg.. In the formula, M is a hydrogen atom or an atom or compound which can covalently bond to the tetrapyrazinoporphyrazine compound to form a covalent or coordination bond; r1 , r2 , r3 , and r4 , which are independent of each other, are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl, alkenyl or aryl, or hydroxyl. In an electrophotographic photoreceptor having a photoreceptive layer on a support, the tetrapyrazinoporphyrazine represented by the formula is incorporated in the photoreceptive layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a tetrapyrazinoporphyrazine compound having a novel crystal form and an electrophotographic photoreceptor using the same, and more particularly, to a tetrapyrazinoporphyrazine compound having a novel crystal form. And an electrophotographic photoreceptor provided with a photosensitive layer containing as a charge generating substance.

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as selenium, cadmium sulfide, and zinc oxide have been used as a photoconductive material of a photoreceptor used in an electrophotographic system.
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 formed, and this 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. By the way, at present, each of the above-mentioned inorganic substances has many advantages and various disadvantages. 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 On the other hand, electrophotographic photoreceptors using organic materials as photoreceptor materials have advantages such as low cost, low toxicity, and suitability for mass production.
It has come to practical use.

Most of the electrophotographic photoreceptors put to practical use have a function-separated type electrophotographic photoreceptor in which a charge generation layer having a charge generation function and a charge transport layer having a charge transport function are laminated on a conductive substrate. As a result, the sensitivity and photoreceptor life, which were inferior to electrophotographic photoreceptors using inorganic substances, have been improved, and the advantages of organic photoconductive substances are low cost, safety and versatility. Electrophotographic photoreceptors are being actively designed by taking advantage of their properties. This type of function-separated electrophotographic photoreceptor generally has a structure in which a charge generation layer composed of a charge generation substance such as a pigment and a dye and a charge transport layer composed of a charge transport substance are sequentially laminated on a conductive support. It has. Such a function-separated type electrophotographic photoreceptor has the advantage that the selection range of each material of the charge generating substance and the charge transporting substance is wide, and an electrophotographic photoreceptor having arbitrary characteristics can be relatively easily prepared. doing. On the other hand, in the copying industry, etc., in recent years, editing functions and complex processing functions have been demanded, and with this, non-impact printer technology has been developed, and digital printers such as laser printers, laser facsimile machines, and digital copiers have been developed. -Type recording devices 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, titanyloxy phthalocyanine and the like. In particular, titanyloxyphthalocyanine is produced under the production conditions, that is, heating conditions, the type of solvent to be treated,
Alternatively, various crystal types can be obtained due to mechanical strain or the like, as disclosed in, for example, JP-A-8-231869, JP-A-5-66595, and JP-B-8-13942. It is generally known, for example, from Japanese Patent Application Laid-Open No. 3-128973 that the difference between these crystal types greatly affects electrophotographic characteristics (sensitivity, potential stability, etc.). However, none of them are still sufficient in sensitivity, chargeability, repetition durability and the like, and further improvement is desired.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve such a problem and to provide a tetrapyrazinoporphy useful as an organic photoconductor used in an electrophotographic photosensitive member for a high-speed copying machine or a laser printer. It is to provide a azine compound. Another object of the present invention is to provide an electrophotographic photoreceptor having particularly excellent chargeability and high sensitivity.

[0006]

According to the present invention, first, a novel crystal showing a strong diffraction peak at a Bragg angle (2θ ± 0.2 °) of 26.8 ° in an X-ray diffraction spectrum by CuKα ray. The present invention provides a tetrapyrazinoporphyrazine compound represented by the following general formula (1), characterized by having a type:

[0007]

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(Wherein, M represents a hydrogen atom or an atom or compound capable of covalently bonding or coordinating with a tetrapyrazinoporphyrazine compound, and r ₁ , r ₂ , r ₃ or r ₄ are each independently Represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an allyl group or a hydroxyl group. K, l, m, and n represent 1 or 2.)

Secondly, there is provided an electrophotographic photosensitive member having a photosensitive layer on a conductive substrate, wherein the photosensitive layer contains the above-mentioned tetrapyrazinoporphyrazine compound. .

Third, in the electrophotographic photoreceptor described in the second aspect, the photosensitive layer comprises a charge generation layer containing a charge generation substance and a charge transport layer containing a charge transport substance. An electrophotographic photoreceptor comprising the above tetrapyrazinoporphyrazine compound as a charge generating substance therein is provided.

Fourthly, in the electrophotographic photoreceptor described in the third aspect, the photosensitive layer is provided with a charge generation layer containing a charge generation substance and a charge transport layer containing a hole transport substance on a conductive substrate sequentially. The present invention provides a negatively charged electrophotographic photoreceptor characterized by having a photosensitive layer.

Fifth, in the electrophotographic photoreceptor according to the third or fourth aspect, the charge transport material is a stilbene compound represented by the following general formula (2). Is provided.

[0013]

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

Sixth, in the electrophotographic photoreceptor described in the third aspect, the photosensitive layer is provided with a charge generation layer containing a charge generation material and a charge transport layer containing an electron transport material on a conductive substrate in order. A positively chargeable electrophotographic photoreceptor, which is a photosensitive layer, is provided.

Seventh, in the electrophotographic photoreceptor according to the third or sixth aspect, the charge transport material is (2,3-diphenyl-1-indenylidene) malononitrile represented by the following structural formula (3). An electrophotographic photosensitive member is provided.

[0017]

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Eighth, in the electrophotographic photosensitive member according to the second aspect, the photosensitive layer is a single layer containing at least the tetrapyrazinoporphyrazine compound as a charge generating substance. Is provided.

Hereinafter, the present invention will be described in more detail. Examples of atoms or compounds capable of forming a covalent bond or a coordinate bond with the tetrapyrazinoporphyrazine compound in M of the general formula (1) include, for example, Cu, TiO, Mg, Co, P
b, VO, Fe, Zn, Ge, Sn, Ni, Al, G
a, Mo, In, and other metal atoms, metal oxides, metal hydroxides, metal halides, and hydrogen.

The halogen atom in r ₁ , r ₂ , r ₃ or r ₄ is chlorine, bromine or the like, and the alkyl is methyl, ethyl, propyl or the like.
and a t-butyl group. Examples of the substituent in the alkyl group include a halogen atom such as a chlorine atom and a bromine atom.

Specific examples of the tetrapyrazinoporphyrazine compound represented by the general formula (1) include, but are not limited to, those shown in Table 1.

[0022]

[Table 1-1]

[0023]

[Table 1-2]

The Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum by CuKα ray of the present invention is 26.8.
The tetrapyrazinoporphyrazine compound represented by the general formula (1) having a crystal form showing a strong diffraction peak at ° is obtained by combining a dinitrile compound represented by the following general formula (01) with a metal chloride or an alkoxy metal. It can be obtained by heating and stirring without solvent or in the presence of a reaction solvent.

[0025]

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(In the formula, rx independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an allyl group or a hydroxyl group, and y represents 1 or 2.) As the metal chloride, Examples thereof include copper monochloride, cupric chloride, and titanium tetrachloride, and examples of the alkoxy metal include tetrabutoxytitanium and tetrapropyloxytitanium.

Examples of the reaction solvent include halogen solvents such as dichlorobenzene and trichlorobenzene, pentanol,
Alcohol solvents such as octanol, amine solvents such as N, N-dimethylformamide and N-methylpyrrolidone, and aromatic solvents such as benzene, toluene, α-chloronaphthalene and nitrobenzene can be used.
Above all, by using an aromatic solvent, CuKα
Angle (2θ) in X-ray diffraction spectrum by X-ray
(± 0.2 °) A tetrapyrazinoporphyrazine compound having a novel crystal form showing a strong diffraction peak at 26.8 ° can be obtained in high yield. The reaction is usually performed at room temperature to
The reaction is preferably performed at 300 ° C., particularly preferably at 100 ° C. to 250 ° C., from the viewpoint of the reaction yield.

The obtained tetrapyrazinoporphyrazine compound can be used, for example, to reduce the particle size as a pigment, dispersibility,
In order to improve the purity, a treatment such as an acid treatment, a solvent treatment, and a milling treatment may be performed before use. The acid treatment is, for example, a treatment in which a tetrapyrazinoporphyrazine compound is dissolved in sulfuric acid, and the resulting solution is dropped on ice water to precipitate crystals, and crystals are obtained by means such as filtration. Under room temperature or under heating, a treatment in which a tetrapyrazinoporphyrazine compound is suspended and stirred in a solvent, and milling treatment is, for example, a glass bead, a steel bead, a sand mill using alumina balls, etc. This is a process performed using a milling device.

In the milling treatment, an inorganic compound such as NaCl, sodium sulfate and magnesium chloride may be used as a grinding aid. Examples of the solvent used for the solvent treatment and milling treatment include alcohol solvents such as methanol and ethanol, ketone solvents such as cyclohexanone and methyl ethyl ketone, and ether solvents such as n-butyl ether, ethylene glycol, n-butyl ether and tetrahydrofuran. , N, N-dimethylformamide, N-methylpyrrolidone, quinoline, pyridine and the like; amine solvents such as α-chloronaphthalene, toluene and xylene; and water. The milling treatment may be performed without a solvent.

Next, the electrophotographic photosensitive member of the present invention will be described. According to the present invention, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the Bragg angle (2θ ±
0.2 °) By incorporating the tetrapyrazinoporphyrazine compound represented by the above general formula (1) having a novel crystal form showing a strong diffraction peak at 26.8 °, it is particularly excellent in chargeability and high in chargeability. An electrophotographic photosensitive member having sensitivity can be obtained.

In the electrophotographic photoreceptor of the present invention, the above-mentioned tetrapyrazinoporphyrazine compound may be used after being mixed and dispersed with, for example, the following pigments. That is, as the organic pigment, for example, CI Pigment Blue 25 (color index CI 21180),
CI Pigment Red 41 (CI 21200),
C.I. Acid Red 52 (CI 45100), C.I. Basic Red 3 (CI 45210), azo pigments having a carbazole skeleton (JP-A-53-9503)
No. 3), azo pigments having a distyrylbenzene skeleton (JP-A-53-133445), and azo pigments having a triphenylamine skeleton (JP-A-53-132347).
JP-A-54-21728), an azo pigment having an oxadiazole skeleton (JP-A-54-12742), and an azo pigment having a fluorenone skeleton (JP-A-54-12742). Showa 54
No. 22834), an azo pigment having a bisstilbene skeleton (Japanese Patent Application Laid-Open No. 54-17733), and an azo pigment having a distyryloxadiazole skeleton (Japanese Patent Application Laid-Open No.
Azo pigments having a distyrylcarbazole skeleton (Japanese Patent Application Laid-Open No. 54-14967), and C.I. Pigment Blue 16 (CI 741).
00), phthalocyanine-based pigments such as titanyl phthalocyanine, C-Ivat Brown 5 (CI 7341)
0), indigo-based pigments such as sea bat die (CI73030), Argo Scarlet B (manufactured by Bayer), Indance Scarlet R (manufactured by Bayer)
And the like. These organic pigments may be used alone or in combination of two or more.

The electrophotographic photoreceptor of the present invention uses the above-mentioned tetrapyrazinoporphyrazine compound as a charge-generating substance and uses it in combination with a charge-transporting substance to form a laminated or single-layer type electrophotographic photoreceptor. can do. The electrophotographic photoreceptor of the laminated type comprises, on a conductive substrate, a charge generation layer containing a binder used as necessary and the tetrapyrazinoporphyrazine compound as a charge generation material, and a charge transport material. It has a photosensitive layer in which a charge transport layer containing a binder is sequentially provided. However, in the case of a positively charged electrophotographic photosensitive member, the charge generation layer and the charge transport layer may be reversed. The single-layer type electrophotographic photoreceptor has a single-layer photosensitive layer in which a charge generating substance and a charge transporting substance are dispersed in a binder on a conductive substrate.

As the charge transport material, any of a hole transport material and an electron transport material can be used. Examples of the hole transport material include poly-N-vinylcarbazole and its derivatives, poly-γ-carbazolylethylglutamate and its derivatives, pyrene-formaldehyde condensate and its derivatives, polyvinylpyrene, polyvinylphenanthrene, and oxazole derivatives. Examples thereof include an imidazole derivative and a triphenylamine derivative. Among them, a stilbene compound represented by the following general formula (2) is suitably used because of its high charge transport ability.

[0034]

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(Wherein R ₁ and R ₂ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group;
R ₃ and R _{4 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted aryl group or heterocyclic group.
R 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 (2) are shown in Table 2, but are not limited thereto.

[0037]

[Table 2-1]

[0038]

[Table 2-2]

[0039]

[Table 2-3]

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 and the like. The structural formulas (a) and (b) ) And (c) can be suitably used.

[0041]

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As described above, the charge transport substances are used alone or in combination of two or more. As the binder used for forming the charge generation layer, the charge transport layer and the single-layer photosensitive layer, any binder can be used as long as it has good insulating properties, and there is no particular limitation.

Examples of the binder include polyethylene,
Polyvinyl butyral, polyvinyl formal, polystyrene resin, phenoxy resin, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol 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 copolymer resins containing two or more of the repeating units of these resins, such as vinyl chloride-vinyl acetate copolymer, styrene-acryl copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, and the like. In addition to the insulating resin described above, a polymer organic semiconductor such as poly-N-vinyl carbazole may be used. These binders can be used alone or as a mixture of two or more.

In the case of a negatively charged electrophotographic photosensitive member having a photosensitive layer in which a charge generation layer and a charge transport layer are sequentially laminated on a conductive substrate, the ratio of the charge generation substance to the binder in the charge generation layer is 20. % By weight or more, and the thickness of the charge generation layer is preferably 0.01 to 5 μm. In the charge transport layer, the ratio of the charge transport material to the binder is preferably 20 to 200% by weight or more, and the film thickness is 5 to 10%.
0 μm is preferred.

In the case of the positive charge type, the ratio of the charge transport material to the binder in the charge transport layer is 20 to 2
It is preferably at least 00% by weight, and the film thickness is preferably 5 to 100 μm. In the charge generation layer, the charge generation substance is preferably contained in an amount of 20% by weight or more based on the binder. Further, it is preferable that a charge transporting material is contained in the charge generating layer, whereby a rise in residual potential can be suppressed and sensitivity can be improved. 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 an electrophotographic photosensitive member having a single photosensitive layer in which a charge generating substance and a charge transporting substance are dispersed in a binder resin, the ratio of the charge generating substance in the photosensitive layer is small. 5 to 95% by weight with respect to the adhesive resin is preferable,
The ratio of the charge transport material is 30 to 200 with respect to the binder resin.
% By weight is preferred. The thickness of the photosensitive layer is 10 to 100.
μm is preferred.

Further, in these photosensitive layers, a phenol compound, a hydroquinone compound, a hindered phenol compound, a hindered amine compound, a hindered amine are used in both the single-layer type and the laminated type, particularly for the purpose of improving the chargeability upon repeated use. Compounds in which hindered phenol is present in the same molecule can be added.

The electrophotographic photosensitive member of the present invention can be manufactured, for example, as follows. That is, by using the tetrapyrazinoporphyrazine compound as a charge generating substance, and dissolving or dispersing the binder and other additives in a solvent as necessary, and applying and drying it on a conductive substrate. A charge generation layer is provided, and then a solution in which a charge transport material and a binder and other additives are dissolved in a solvent is applied on the charge generation layer and dried to form a charge transport layer, as described below. An electrophotographic photoreceptor can be manufactured.

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 agglomerate, 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. Examples of the method for dispersing the charge generating substance include a ball mill, ultrasonic waves, and a homomixer. In addition, examples of a coating means for forming the charge generation layer and the charge transport layer include a dipping coating method, a blade coating method, and a spray coating method.

The solvent used for 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. Examples of the conductive substrate in the electrophotographic photoreceptor of the present invention include metal plates such as aluminum, nickel, copper, titanium, gold, and stainless steel, metal drums or metal foils, aluminum, nickel, copper, titanium, gold, tin oxide, and oxides. Examples of the material include a plastic film on which indium or the like is vapor-deposited, a paper or a film of plastic or the like coated with a conductive substance, a drum, and the like.

Further, in the electrophotographic photoreceptor of the present invention,
An intermediate layer may be provided between the photosensitive layer and the conductive substrate to improve adhesion and charge blocking properties, and further, on the photosensitive layer to improve mechanical durability such as friction resistance. A protective layer may be provided. As the material of the intermediate layer, in addition to the resins mentioned as the binder, a polyamide resin, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride polymer ,
Resins such as casein and N-alkoxymethyl nylon;
Aluminum oxide, titanium oxide, silicon oxide, indium oxide, or the like can be dispersed and used. Alternatively, a deposited film of aluminum oxide, zinc oxide, titanium oxide, silicon oxide, or the like can be used.

As the material of the protective layer, it is appropriate to use the above-mentioned resin as it is, or to use a material in which a low-resistance substance such as tin oxide or indium oxide is dispersed. Also, an organic plasma polymerized film can be used, and the organic plasma polymerized film may contain oxygen, halogen, and atoms of Group III and Group V of the periodic table, if necessary.

[0053]

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

Example 1 52 g (0.4 mol) of o-dicyanopyrazine, 10 g (0.1 mol) of cuprous chloride, α-chloronaphthalene 6
The resulting mixture was stirred and mixed for 5 hours while maintaining the reaction temperature between 190 ° C. and 210 ° C., and reacted. After the reaction, allow to cool,
When the temperature reached 130 ° C., the mixture was filtered while hot, then washed with α-chloronaphthalene and methanol until the powder turned blue, and further washed several times with hot water at 80 ° C., and dried.
g (73% yield) of Cu tetrapyrazinoporphyrazine pigment was obtained. FIG. 1 shows the IR spectrum of the obtained Cu tetrapyrazinoporphyrazine pigment. The elemental analysis values are as shown in Table 3 below.

[0055]

[Table 3]

An X-ray diffraction spectrum of the obtained Cu tetrapyrazinoporphyrazine pigment was measured under the following conditions. The X-ray diffraction spectrum is shown in FIG. X-ray tube Cu (wavelength 1.54 °) Voltage 40 kV Current 20 mA Scanning speed 1 deg / min Scanning range 3 to 40 deg Time constant 2 sec As is clear from FIG. 2, the Bragg angle (2θ ± 0.2)
°) shows a strong diffraction peak at 26.8 °.

Example 2 4 g of the Cu tetrapyrazinoporphyrazine pigment obtained in Example 1 was placed in a 500 ml Erlenmeyer flask, and heated under stirring with 200 ml of methyl ethyl ketone and 10 ml of water.
Refluxed for hours. Thereafter, the mixture was cooled to room temperature, filtered and dried to obtain 3.95 g of Cu tetrapyrazinoporphyrazine pigment.

Example 3 2 g of the Cu tetrapyrazinoporphyrazine pigment obtained in Example 2 was put in a 500 ml Erlenmeyer flask, and heated and stirred at 60 ° C. for 6 hours together with 200 ml of α-chloronaphthalene. After cooling to room temperature, filtration and drying, 1.97 g of Cu tetrapyrazinoporphyrazine pigment was obtained.

Example 4 2 g of the Cu tetrapyrazinoporphyrazine pigment obtained in Example 1 and 100 g of glass beads having a diameter of 2 mm were added to 50 m of the pigment.
The resulting mixture was charged in a wide-mouthed bottle and subjected to dry milling in a sand mill for 2 hours to obtain a Cu tetrapyrazinoporphyrazine pigment.

Example 5 2 g of the Cu tetrapyrazinoporphyrazine pigment obtained in Example 1, 10 g of NaCl, and 100 g of glass beads having a diameter of 2 mm were charged into a 50 ml wide-mouthed bottle, and dry milling was carried out for 2 hours by a sand mill to obtain Cu tetrapyrazine. A dinoporphyrazine pigment was obtained.

Example 6 2 g of the Cu tetrapyrazinoporphyrazine pigment obtained in Example 1, 5 g of NaCl, 20 ml of water and 100 g of glass beads having a diameter of 2 mm were charged into a 50 ml wide-mouth bottle, and wet milling was performed for 2 hours by a sand mill. A Cu tetrapyrazinoporphyrazine pigment was obtained.

The X-ray diffraction spectrum of the Cu tetrapyrazinoporphyrazine pigment obtained in Examples 2 to 6 was measured in the same manner as in Example 1. It was confirmed that each of the Cu tetrapyrazinoporphyrazine pigments obtained in Examples 2 to 6 had a strong diffraction peak at a Bragg angle (2θ ± 02 °) of 26.8 °.

Example 7 One part by weight of the Cu tetrapyrazinoporphyrazine pigment obtained in Example 1 was added to a polyvinyl butyral resin (BM-
S, Sekisui Chemical Co., Ltd.) 2% by weight butyl acetate solution 50
Parts by weight 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 dried at 80 ° C. for 5 minutes to form a 0.2 μm-thick charge generation layer. 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), and 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 dried at 80 ° C. for 5 minutes and at 110 ° C. for 10 minutes to form a charge transport layer having a thickness of 20 μm to obtain an electrophotographic photosensitive member.

[0064]

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Example 8 The procedure of Example 7 was repeated, except that the Cu tetrapyrazinoporphyrazine pigment obtained in Example 2 was used instead of the Cu tetrapyrazinoporphyrazine pigment obtained in Example 1. An electrophotographic photosensitive member was obtained in the same manner as in Example 7.

Example 9 The procedure of Example 7 was repeated, except that the Cu tetrapyrazinoporphyrazine pigment obtained in Example 3 was used instead of the Cu tetrapyrazinoporphyrazine pigment obtained in Example 1. An electrophotographic photosensitive member was obtained in the same manner as in Example 7.

Example 10 In the same manner as in Example 7, except that the hole transporting material represented by the following structural formula (D-2) was used instead of the hole transporting material (D-1). Thus, an electrophotographic photosensitive member was obtained.

[0068]

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Example 11 Example 11 was the same as Example 7 except that the hole transport material represented by the following structural formula (D-3) was used instead of the hole transport material (D-1). Thus, an electrophotographic photosensitive member was obtained.

[0070]

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Example 12 Example 7 was the same as Example 7 except that the hole transport material represented by the following structural formula (D-4) was used instead of the hole transport material (D-1). Thus, an electrophotographic photosensitive member was obtained.

[0072]

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The electrophotographic photosensitive members obtained in Examples 7 to 12 were charged by performing a corona discharge at −6 KV for 20 seconds at −6 KV using an electrostatic characteristic measuring device (EPA-8200, manufactured by Kawaguchi Electric Co., Ltd.). Surface potential Vo (V) after dark decay for 20 seconds, and Vo after light irradiation of 20 lux is ２
Exposure amount E1 / 2 (lux · sec) required to obtain was measured. The results are shown in Table 3 below.

[0074]

[Table 3]

As is clear from Table 3, the electrophotographic photosensitive members of the examples are excellent in chargeability and sensitivity.

Example 13 In the same manner as in Example 7, a charge generation layer was formed on an aluminum-deposited PET base. Next, 8 parts by weight of an electron transport material having the following structural formula (A-1), 11 parts by weight of polycarbonate Z (manufactured by Teijin Chemicals Limited), and 0.02 parts by weight of silicone oil (KF50, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to 91 parts by weight of tetrahydrofuran. The solution was cast on a charge generating layer by a doctor blade, and dried to form a charge transport layer having a thickness of 20 μm to obtain an electrophotographic photosensitive member.

[0077]

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Example 14 Example 13 was carried out in the same manner as in Example 13, except that the electron transporting material represented by the following structural formula (A-2) was used instead of the electron transporting material (A-1). An electrophotographic photosensitive member was obtained.

[0079]

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The electrophotographic photosensitive members obtained in Examples 13 and 14 were subjected to an electrostatic property measuring device (EPA-820).
0, manufactured by Kawaguchi Electric Co., Ltd.) and charged by performing a corona discharge at +5.3 kV for 20 seconds, followed by a surface potential Vo (V) after dark decay for 20 seconds and a Vo after light irradiation of 20 lux of 1 / 2 required exposure amount E1 / 2 (lux
・ Sec) was measured. Table 4 shows the results.

[0081]

[Table 4]

As is clear from Table 4, the electrophotographic photosensitive members of the examples are excellent in chargeability and sensitivity.

Example 15 0.5 g of the Cu tetrapyrazinoporphyrazine pigment obtained in Example 1 was dissolved in 10 g of a polycarbonate Z (manufactured by Teijin Chemicals Ltd.) solution (to a concentration of 10% by weight in tetrahydrofuran). ) And 9 g of tetrahydrofuran, and after ball milling, the pigment composition was 2% by weight, the polycarbonate Z composition was 50% by weight, and the charge transport material (D
10% by weight of a polycarbonate Z solution was added so that -1) became 28% by weight, and the mixture was sufficiently stirred to prepare a photosensitive layer coating solution. The photosensitive layer coating solution prepared in this manner is applied by casting with a doctor blade onto a polyester film on which aluminum is deposited, and dried to form a photosensitive layer having a thickness of 15 μm. I got The electrophotographic photoreceptor was charged by performing a corona discharge at +6 kV for 20 seconds using the above-described electrostatic property measuring device, and then a surface potential Vo after dark attenuation for 20 seconds.
(V) The exposure amount E1 / 2 (lux · sec) necessary for reducing Vo to 1/2 after light irradiation of 20 lux was measured. Table 5 shows the results.

[0084]

[Table 5]

As is clear from Table 5, the electrophotographic photosensitive members of the examples are excellent in chargeability and sensitivity.

[0086]

According to the present invention, a tetrapyrazinoporphyrazine compound useful as an organic photoconductor used for an electrophotographic photoreceptor for a high-speed copying machine or a laser printer can be obtained. Further, according to the present invention, it is possible to obtain an electrophotographic photoreceptor having particularly high chargeability and high sensitivity.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of the tetrapyrazinoporphyrazine compound of the present invention.

FIG. 2 is an X-ray diffraction spectrum of the tetrapyrazinoporphyrazine compound of the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03G 5/06 370 G03G 5/06 370 372 372 373 373 373

Claims (8)

[Claims] An X-ray diffraction spectrum by CuKα radiation has a novel crystal form showing a strong diffraction peak at a Bragg angle (2θ ± 0.2 °) of 26.8 °, and is represented by the following general formula (1): A tetrapyrazinoporphyrazine compound represented by the formula: Embedded image (Wherein, M represents a hydrogen atom or an atom or a compound capable of covalently bonding or coordinating with a tetrapyrazinoporphyrazine compound, and r ₁ , r ₂ , r ₃ or r ₄ each independently represent a hydrogen atom , A halogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an allyl group or a hydroxyl group. K, l, m, and n represent 1 or 2.) 2. An electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, wherein the Bragg angle (2θ ± 0.2 °) 2 in the X-ray diffraction spectrum of CuKα ray in the photosensitive layer.
An electrophotographic photoreceptor comprising a tetrapyrazinoporphyrazine compound represented by the following general formula (1) having a novel crystal form showing a strong diffraction peak at 6.8 °. Embedded image (In the formula, M represents a hydrogen atom or an atom or a compound capable of forming a covalent bond or a coordination bond with a tetrapyrazinoporphyrazine compound, and r ₁ , r ₂ , r _3, or r ₄ each independently represent a hydrogen atom , A halogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an allyl group or a hydroxyl group. K, l, m, and n represent 1 or 2.) 3. The photosensitive layer comprises a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance, wherein the charge generating layer has a Bragg angle (2θ ± 0.2) as a charge generating substance. 3) The electrophotographic photoreceptor according to claim 2, which contains a tetrapyrazinoporphyrazine compound represented by the general formula (1) having a novel crystal form showing a strong diffraction peak at 26.8 °. . 4. The photosensitive layer according to claim 3, wherein the photosensitive layer is a photosensitive layer in which a charge generating layer containing a charge generating substance and a charge transporting layer containing a hole transporting substance are sequentially provided on a conductive substrate. Negatively charged electrophotographic photoreceptor. 5. The electrophotographic photosensitive member according to claim 3, wherein the charge transporting substance is a stilbene compound represented by the following general formula (2). 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, and R ₁ and R ₂ may form a ring with each other, and Ar ₁ represents a substituted or unsubstituted arylene group or a heterocyclic group. 6. The photosensitive layer according to claim 3, wherein the photosensitive layer is a photosensitive layer in which a charge generating layer containing a charge generating substance and a charge transporting layer containing an electron transporting substance are sequentially provided on a conductive substrate. Positive charging type electrophotographic photoreceptor. 7. The electrophotographic photoreceptor according to claim 3, wherein the charge transport material is (2,3-diphenyl-1-indenylidene) malononitrile represented by the following structural formula (3). Embedded image 8. A tetrapyrazino represented by the general formula (1) wherein the photosensitive layer has a novel crystal form showing a strong diffraction peak at least at a Bragg angle (2θ ± 0.2 °) of 26.8 ° as a charge generating substance. 3. The electrophotographic photoconductor according to claim 2, wherein the electrophotographic photoconductor is a single layer containing a porphyrazine compound.