JPH1017782A - Chlorogallium tetra-2,3-pyrizinoporphyrazine crystal, photoconductive material and electrophotographic receptor containing the material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new chlorogallium tetra-2,3-pyrizinoporphyrazine crystal, having excellent photosensitivity and durability as a photoconductive material and provide an electrophotographic receptor produced by using the crystal as a photoconductive material of a photosensitive layer. SOLUTION: This chlorogallium tetra-2,3-pyrizinoporphyrazine crystal is free from distinct diffraction peak in the range of 5 deg. to 40 deg. of Bragg angle (2θ±0.2 deg.) or has main diffraction peaks at least at 14.15 deg., 17.51 deg. and 25.81 deg. or has main diffraction peaks at least at 10.77 deg., 17.82 deg. and 26.72 deg. in an X-ray diffraction spectrum taken by using CuK αray (λ=1.54Å). The crystal is useful as a photoconductive material for electrophotographic receptor. An electrophotographic receptor can be produced by including the crystal in a photosensitive layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel crystal of specific chlorogallium tetra-2,3-pyridinoporphyrazine excellent in charge generation ability and chlorogallium tetra-2,3 having a novel crystal form thereof. A photoconductive material comprising a pyridinoporphyrazine crystal and an electrophotographic photoreceptor using the same.

[0002]

2. Description of the Related Art Conventionally, various inorganic and organic photoconductive materials have been proposed as a photosensitive material for an electrophotographic photoreceptor, and a laminated type in which a charge generation layer and a charge transport layer are functionally separated. Numerous organic compounds are known for charge generation materials used in electrophotographic photoreceptors composed of a photosensitive layer and electrophotographic photoreceptors composed of a single-layer type photosensitive layer having a single layer having charge generation ability and charge transport ability. I have.

In recent years, there has been an increasing demand for using electrophotographic photoreceptors for digital recording of laser printers and the like, and from this viewpoint, squarylium compounds (JP-A-49-105536 and JP-A-58-105536) have been developed. 2141
No. 6), triphenylamine-based trisazo compounds (JP-A-61-151659), phthalocyanine compounds (JP-A-48-34189, JP-A-57-1979).
No. 148745) has been proposed as a photoconductive material for a semiconductor laser.

When an organic photoconductive material is used as a photoconductive material for a semiconductor laser, first, the photosensitive wavelength has been extended to a long wavelength, and then, the electrophotographic photosensitive member to be formed has high photosensitivity and durability. It is required to have excellent properties. However, many of the organic photoconductive materials described above,
The electron transport ability is not always sufficient, and a problem such as an increase in residual potential and a decrease in photosensitivity upon repeated use occurs, and the above-mentioned conditions are not sufficiently satisfied. In order to overcome these drawbacks, among the above-mentioned organic photoconductive materials, phthalocyanine compounds have been extensively studied in recent years as electrophotographic photoreceptor materials, optical recording materials and photoconductive conversion materials. The relationship between crystal type and electrophotographic properties has been studied.

[0005] In general, it is known that phthalocyanine compounds are divided into several crystal forms due to differences in the production method or treatment method, and that different crystal forms greatly affect the photoelectric conversion characteristics of the phthalocyanine compound. ing. Regarding the crystal form of the phthalocyanine compound, for example, when looking at copper phthalocyanine, besides the stable β form, crystal forms such as α, ε, π, χ, ρ, γ, and δ are known. It is known that the molds can be mutually transformed by mechanical strain, sulfuric acid treatment, organic solvent treatment, heat treatment, and the like (for example, U.S. Pat. Nos. 2,770,629 and 3). , 160,635
No. 3,708,292 and 3,357,989). Also, Japanese Patent Laid-Open No. 50-3
No. 8543 describes a relationship between a difference in crystal form of copper phthalocyanine and electrophotographic properties, and describes α, β, and γ.
In comparison with ε-type, it is described that ε-type shows the highest sensitivity.

[0006] The tetraazaporphyrin derivatives known as phthalocyanine analogs are disclosed in JP-A-2-29660, JP-A-2-33156 and JP-A-2-35463. It describes that the material can be applied to electrophotography. In particular, JP-A-2-33156 describes an electrophotographic photosensitive member containing a compound of a general formula including chlorogallium tetra-2,3-pyridinoporphyrazine in a photosensitive layer.

[0007]

As described above, many studies have been made on phthalocyanine compounds and their analogous compounds for use as photoconductive materials. However, electrophotographic photoreceptors using conventional phthalocyanines and their analogous compounds have high residual potentials, and have potential stability and sensitivity upon repeated use.
It was not always satisfactory.

The present invention has been made to solve the above-mentioned problems in the prior art. That is, an object of the present invention is to provide a novel chlorogallium tetra-2,3-pyridinoporphyrazine crystal having excellent photosensitivity and durability as a photoconductive material. Another object of the present invention is to provide a photoconductive material for an electrophotographic photoreceptor which can be put to practical use in any of a layered type and a single-layer type, and an electrophotographic photoreceptor using the same.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventor has conducted a simple treatment on the chlorogallium tetra-2,3-pyridinoporphyrazine obtained by the synthesis to obtain a photoconductive material. It has been found that a novel crystal excellent in not only hole transport but also electron transport and having high photosensitivity as a photoconductive material for an electrophotographic photosensitive member and excellent in repetition stability can be obtained. It was completed.

The chlorogallium tetra-2,3- of the present invention
Pyridinoporphyrazine crystals have a CuKα ray (λ = 1.
In the X-ray diffraction spectrum for 54 Å, the Bragg angle (2θ ± 0.2 °) of 5 ° to 40 °
Crystal without a clear peak at the Bragg angle (2θ ±
0.2 °) at least 14.15 °, 17.51 ° and 25.81 °, or at least 10. ° Bragg angle (2θ ± 0.2 °).
It is a crystal having main diffraction peaks at 77 °, 17.82 °, and 26.72 °.

The photoconductive material for an electrophotographic photoreceptor of the present invention comprises:
It is characterized by being composed of the chlorogallium tetra-2,3-pyridinoporphyrazine crystal. Further, the electrophotographic photoreceptor of the present invention comprises the above chlorogallium tetra-
A photosensitive support containing at least one kind of 2,3-pyridinoporphyrazine crystals is coated on a conductive support.

[0012]

Embodiments of the present invention will be described below in detail. The chlorogallium tetra- of the present invention
The chlorogallium tetra-2,3-pyridinoporphyrazine for obtaining 2,3-pyridinoporphyrazine crystals has the following formula:

Embedded image It can be produced by a generally known method for synthesizing porphyrazine compounds (in the structural formula, not all N positions of the pyridine nucleus are arranged counterclockwise as described above, and some of them are in the opposite direction. May also include an isomer present at the α-position, for example, in Koka Magazine, Vol. 61, p. 994 (1958)). That is, a method of heating and melting 2,3-dicyanopyridine and a metal chloride or heating in the presence of an organic solvent, obtaining an anhydride thereof from pyridino-2,3-dicarboxylic acid, and adding urea and metal It can be produced by a method such as adding a chloride and heating and melting, or heating in the presence of an organic solvent, a method of reacting pyridino-2,3-benzamide with a metal salt at a high temperature, or the like.

As the organic solvent used in the above synthesis method, α-chloronaphthalene, β-chloronaphthalene, α-chloronaphthalene,
-Methylnaphthalene, methoxynaphthalene, diphenylethane, ethylene glycol, dialkyl ether, quinoline, sulfolane, dichlorobenzene, dichlorotoluene, dimethylformamide, dimethylsulfoxide,
A reaction-inactive, high-boiling solvent such as dimethylsulfamide is preferred.

The raw material chlorogallium tetra-2,3-pyridinoporphyrazine used in the present invention is, for example,
It can be produced by heating and stirring 2,3-dicyanopyridine and gallium trichloride in the above organic solvent in a temperature range of 170 to 250 ° C. The obtained chlorogallium tetra-2,3-pyridinoporphyrazine contains an isomer generated depending on the position of the nitrogen atom in the pyridine nucleus.

Next, a crystal of chlorogallium tetra-2,3-pyridinoporphyrazine having a novel crystal form of the present invention and a method for producing the same will be described. The novel crystal form of the present invention is: (1) a Bragg angle (2θ ± 0.2 °) of 5 ° measured by a powder X-ray diffractometer using CuKα ray (λ = 1.54 Å) as an X-ray source; ~ 40 °
(2) at least 14.1 of the above Bragg angle (2θ ± 0.2 °).
Those having main diffraction peaks at 5 °, 17.51 °, 25.81 ° (see FIG. 7), or (3) 10.77 °, 17.82 ° of the Bragg angle (2θ ± 0.2 °) ,
It has a main diffraction peak at 26.72 ° (see FIG. 8).

These crystal types are produced as follows. That is, a chlorogallium tetra-2,3-pyridinoporphyrazine crystal having no clear peak at a Bragg angle (2θ ± 0.2 °) of 5 ° to 40 ° is obtained from an automatic mortar, a planetary mill, and a vibrating ball mill. And the like, by dry milling using a known mechanical treatment method. The dry grinding time is preferably 5 hours or more, and grinding aids such as salt and sodium sulfate can be used as necessary. Bragg angle (2θ
± 0.2 °) at least 14.15 °, 17.51
°, a chlorogallium tetra-2,3-pyridinoporphyrazine crystal having a main diffraction peak at 25.81 ° is obtained by dry-grinding a crude crystal immediately after synthesis by a known method.
Along with the grinding media, dimethylformamide (DM
It is obtained by wet grinding with an aprotic solvent such as F), dimethyl sulfoxide, dimethoxyethane, acetonitrile and the like. The wet grinding time is preferably 12 to 72 hours, particularly preferably 24 hours. In addition, the Bragg angle (2θ ±
0.2 °) 10.77 °, 17.82 °, 26.72
Chlorogallium tetra-
The 2,3-pyridinoporphyrazine crystals are obtained by dry-grinding crude crystals immediately after synthesis by a known method, and then, together with grinding media, methanol, ethanol, n-butanol, n-butanol.
Aliphatic alcohols such as propanol, benzyl alcohol, aromatic alcohols such as phenethyl alcohol,
It is obtained by wet grinding with any of polyhydric alcohol solvents such as glycerin and polyethylene glycol, or a mixed solvent thereof. Wet grinding time is 12
７２72 hours, especially 24 hours are preferred.

Chlorogallium tetra-
In 2,3-pyridinoporphyrazine crystals, the longest primary particle diameter is 3 μm or less on the major axis, 1 μm or less on the minor axis, 1.5 μm or less on the major axis, and 0.5 μm or less on the minor axis. Is preferred.

Next, an electrophotographic photosensitive member using a chlorogallium tetra-2,3-pyridinoporphyrazine crystal obtained by the above-mentioned processing method as a photoconductive material of a photosensitive layer will be described. The electrophotographic photoreceptor of the invention may have a single-layered photosensitive layer or a laminated structure in which the photosensitive layer is functionally separated into a charge generation layer and a charge transport layer. When the photosensitive layer has a laminated structure, the charge generation layer is composed of the chlorogallium tetra-2,3-pyridinoporphyrazine crystal and a binder resin.

FIGS. 1 to 4 are cross-sectional views schematically showing an electrophotographic photosensitive member having a photosensitive layer having a laminated structure according to the present invention. FIG. 1 shows that a photosensitive layer comprising a charge generation layer 1 and a charge transport layer 2 laminated thereon is electrically conductive support 3
Is coated on the surface. FIG. 2 shows that the undercoat layer 4 is interposed between the charge generation layer 1 and the conductive support 3 of the laminated structure of FIG. FIG. 3 is similar to FIG.
In the above laminated structure, a protective layer 5 is further coated on the surface of the photosensitive layer. FIG. 4 shows the laminated structure of FIG. 2 further provided with a protective layer 5.

Hereinafter, each layer of the electrophotographic photosensitive member of the present invention will be described for the case where the photosensitive layer of the electrophotographic photosensitive member has a laminated structure. The charge generation layer of the photosensitive layer is composed of the chlorogallium tetra-2,3-pyridinoporphyrazine crystal and a binder resin. This charge generation layer is prepared by dispersing the chlorogallium tetra-2,3-pyridinoporphyrazine crystal in a solution obtained by dissolving a binder resin in an organic solvent to prepare a coating solution, and forming the coating solution on a conductive support. It is formed by coating on the surface.

The binder resin to be used can be selected from a wide range of resins. For example, polyvinyl formal resin, polyvinyl acetal such as partially acetalized polyvinyl butyral resin in which a part of butyral is modified with formal or acetoacetal, etc. Acetal resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.),
Polycarbonate resin, polyester resin, modified polyether type polyester resin, phenoxy resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polystyrene resin, acrylic resin, methacrylic resin, polyacrylamide resin, polyamide resin, polyvinylpyridine resin , Cellulose resin, polyurethane resin, epoxy resin, silicone resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, casein, vinyl chloride-vinyl acetate copolymer, hydroxyl-modified vinyl chloride-vinyl acetate copolymer, carboxyl-modified vinyl chloride-acetic acid Vinyl copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, styrene-alkyd resin Silicone - alkyd resin,
An insulating resin such as a phenol-formaldehyde resin may be used. Further, it can be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, and polyvinylpyrene. However,
It is not limited to these insulating resins or organic photoconductive polymers. These binder resins can be used alone or in combination of two or more.

As a dispersion medium for dissolving the binder resin, methanol, ethanol, n-propanol, is
o-propanol, n-butanol, alcohols such as benzyl alcohol, acetone, methyl ethyl ketone,
Ketones such as cyclohexanone, amides such as dimethylformamide and dimethylacetamide, sulfoxides such as dimethylsulfoxide, cyclic or linear ethers such as tetrahydrofuran, dioxane, diethyl ether, methyl cellosolve and ethyl cellosolve, methyl acetate, and acetic acid Esters such as ethyl and n-butyl acetate;
Aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, dichloroethylene and trichloroethylene; mineral oils such as ligroin; aromatic hydrocarbons such as benzene, toluene and xylene; aromatic hydrocarbons such as chlorobenzene and dichlorobenzene And these can be used alone or in combination of two or more.

The compounding ratio (weight) of the chlorogallium tetra-2,3-pyridinoporphyrazine crystal and the binder resin
Is 40: 1 to 1:20, preferably 10: 1 to 1: 1
It is set in the range of 0. Chlorogallium tetra-2,3
If the ratio of the -pyridinoporphyrazine crystals is too high, the stability of the coating solution is reduced, while if it is too low, the sensitivity of the electrophotographic photoreceptor is reduced. . As a method of dispersing the chlorogallium tetra-2,3-pyridinoporphyrazine crystal, a known method, for example, a ball mill, a sand grind mill, a planetary mill, a coball mill, a roll mill, or the like can be used.

Binder resin and chlorogallium tetra-2,3
-As a method of mixing the pyridinoporphyrazine crystals, for example, the binder resin as powder during the dispersion treatment of the crystals,
Alternatively, any method such as a method of adding and dispersing simultaneously as a polymer solution, a method of mixing a dispersion in a polymer solution of a binder resin, and a method of conversely mixing a polymer solution in a dispersion can be used. In addition, a condition is required in which the crystal form of the chlorogallium tetra-2,3-pyridinoporphyrazine crystal does not change due to dispersion. However, even if any of the above dispersion methods is adopted, the crystal form remains unchanged before dispersion. And what has not changed is obtained.

As a coating method for applying a coating solution to form a charge generation layer, a dip coating method,
Spray coating, spinner coating, bead coating, wire bar coating, blade coating, roller coating, air knife coating or curtain coating can be employed. The coating solution is dried at a temperature of 30 to 200 ° C. for 5 minutes after touch drying at room temperature.
It is preferable to heat and dry for 2 hours at rest or under blowing. The thickness of the charge generation layer is usually 0.05 to 5 μm.
, Preferably in the range of 0.15 to 2.0 μm.

The charge transport layer in the electrophotographic photoreceptor of the present invention is formed by including a charge transport material in a suitable binder resin. Examples of the charge transport material include oxadiazole derivatives such as 2,5-bis- (p-diethylaminophenyl) -1,3,4-oxadiazole,
5-triphenylpyrazoline, 1- [pyridyl-
(2)]-3- (p-Diethylaminostyryl) -5-
Pyrazoline derivatives such as (p-diethylaminophenyl) pyrazoline; aromatic tertiary monoamine compounds such as triphenylamine and benzylaniline; N, N'-diphenyl-N, N'-bis- (m-tolyl) benzidine; Aromatic tertiary diamine compound, 3- (p-diethylaminophenyl) -5,6-di (p-methoxyphenyl)-
1,2,4-triazine derivatives such as 1,2,4-triazine, 4-diethylaminobenzaldehyde-2,2-
Hydrazone derivatives such as diphenylhydrazone, quinazoline derivatives such as 2-phenyl-4-styrylquinazoline,
6-hydroxy-2,3-di (p-methoxyphenyl)
Benzofuran derivatives such as benzofuran, p- (2,2-
Electron donor substances such as α-stilbene derivatives such as diphenylvinyl) -N, N-diphenylaniline, triphenylmethane derivatives, and polymers having a group consisting of these compounds in the main chain or side chain. It is not limited. These charge transporting materials may be used alone or as a mixture of two or more kinds. When the charge transporting material is a polymer, a layer may be formed by itself.

As the binder resin used for the charge transport layer, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin,
Styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, Resins similar to those used for the charge generation layer, such as styrene-alkyd resin and poly-N-vinylcarbazole resin, may be mentioned.

The charge transporting layer is prepared by using the same charge transporting material and binder resin and the same organic solvent as used in forming the charge generating layer 1 to prepare a coating solution. The coating solution can be formed by applying the coating solution on the charge generation layer by the above-mentioned means. At that time, the charge transport material and the binder resin are mixed in a proportion of 5 to 500 parts by weight of the charge transport material with respect to 100 parts by weight of the binder resin. The thickness of the charge transport layer is generally 5
About 50 μm, preferably about 10 to 30 μm.

When the photosensitive layer of the present invention has a single-layer structure, the photosensitive layer is a photoconductive layer in which chlorogallium tetra-2,3-pyridinoporphyrazine crystal and a charge transport material are dispersed in a binder resin. Consisting of The charge transport material and the binder resin are the same as those described above, and the photoconductive layer is formed by the same method as described above. In this case, the binder resin is preferably selected from at least one selected from a polyvinyl acetal resin, a vinyl chloride-vinyl acetate copolymer, a phenoxy resin and a modified ether type polyester resin. Also, in the photosensitive layer,
If necessary, various additives such as an antioxidant and a sensitizer may be contained. The compounding ratio (weight) of the charge transport material to the binder resin is 1:20 to 5: 1, and the compounding ratio (weight) of the chlorogallium tetra-2,3-pyridinoporphyrazine crystal to the charge transport material is: Is preferably set to about 1:10 to 10: 1.

In the present invention, as the conductive support,
Any material can be used as long as it can be used as an electrophotographic photosensitive member. Specifically, metals such as aluminum, nickel, chromium, stainless steel, aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, IT
Examples include a plastic film or the like coated with a thin film such as O, paper or a plastic film coated or impregnated with a conductivity imparting agent. Further, if necessary, the surface of the conductive support may be subjected to various treatments within a range that does not affect the image quality. For example, the surface may be subjected to an oxidizing treatment, a chemical treatment, a coloring treatment, or a irregular reflection treatment such as graining. Etc. may be applied.

An undercoat layer 4 may be further provided between the conductive support and the photosensitive layer. As the undercoat layer, for example, aluminum anodic oxide film, aluminum oxide,
Inorganic layer such as aluminum hydroxide, etc., organic layer such as polyvinyl alcohol, casein, polyvinylpyrrolidone, polyacrylic acid, celluloses, gelatin, starch, polyglutamic acid, amino starch, polyurethane, polyimide, polyamide, zirconium chelate compound, zirconium alkoxide compound , A titanyl chelate compound,
Organic metals such as titanyl alkoxide compounds and known binder resins such as silane coupling agents can be used. The thickness of the undercoat layer is preferably in the range of 0.01 to 20 μm, and more preferably in the range of 0.05 to 10 μm.

Further, a protective layer may be provided on the surface of the photosensitive layer, if necessary. The protective layer is formed by including a conductive material in a suitable binder resin. As the conductive material, metallocene compounds such as dimethylferrocene,
Aromatic amino compounds such as N, N'-diphenyl-N, N'-bis- (m-tolyl) benzidine; metal oxides such as antimony oxide, tin oxide, titanium oxide, indium oxide, tin oxide-antimony oxide; Although it can be used, it is not limited to these. Further, as the binder resin used for the protective layer, for example, those exemplified as the binder resin can be used. Further, it is preferable that the protective layer is configured so that its electric resistance is 10 ⁹ to 10 ¹⁴ Ω · cm. Electric resistance is 10 ¹⁴ Ω · c
If it is higher than m, the residual potential rises to produce a copy with a lot of fog, while if it is lower than 10 ⁹ Ω · cm, image blur, reduction in resolution and the like occur. Further, the protective layer must be configured so as not to substantially impede the transmission of the light irradiated with the resolution light. The thickness of the protective layer is 0.5
An appropriate range is from 20 to 20 μm, preferably from 1 to 10 μm.

[0033]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In Examples and Comparative Examples, “parts” means “parts by weight”. Synthesis Example (Synthesis of chlorogallium tetra-2,3-pyridinoporphyrazine) Under a nitrogen atmosphere, 8.3 parts of gallium trichloride was added to 230 parts of quinoline at room temperature, and then 30 parts of 1,3-dicyanopyridine was added. In addition, the reaction was performed at 200 ° C. for 4 hours.
The reaction product was filtered while hot, washed hot with dimethylformamide and methanol, and then washed with acetone and distilled water. Next, the obtained wet cake was dried under reduced pressure to obtain 27.3 parts of chlorogallium tetra-2,3-pyridinoporphyrazine crystals. The powder X-ray diffraction pattern of the obtained chlorogallium tetra-2,3-pyridinoporphyrazine crystal is shown in FIG. 5, and the infrared absorption spectrum is shown in FIG. In the present invention, the powder X-ray diffraction pattern of each crystal was obtained from Rigaku R manufactured by Rigaku Denshi.
Using an otaflex X-ray diffractometer, a cathode voltage of 40
It was measured at kV and a cathode current of 30 mA.

Example 1 3.0 parts of the chlorogallium tetra-2,3-pyridinoporphyrazine crystal obtained in the synthesis example was placed in an automatic mortar (Labo-MILL MODELUT 21 manufactured by Yamato Scientific Co., Ltd.).
Chlorogallium tetra-2,3-pyridinoporphyrazine crystals were obtained by dry milling for 12 hours using a mold (type). FIG. 6 shows a powder X-ray diffraction diagram of the obtained chlorogallium tetra-2,3-pyridinoporphyrazine crystal. The infrared absorption spectrum was almost the same as in the case of the synthesis example.

Example 2 0.3 part of the chlorogallium tetra-2,3-pyridinoporphyrazine crystal obtained in Example 1 was mixed with 40 parts of 1 mmφ glass beads in 40 parts of dimethylformamide at room temperature for 24 hours. After ball milling, the glass beads and the dispersion were separated, and the dispersion was centrifuged (K
CENTRIKON, manufactured by ONTRON / HERMLE
H-401). The resulting wet cake was washed with 10 parts of ethyl acetate and then dried under reduced pressure,
0.25 parts of chlorogallium tetra-2,3-pyridinoporphyrazine crystals were obtained. The powder X-ray diffraction pattern of the obtained chlorogallium tetra-2,3-pyridinoporphyrazine crystal is shown in FIG. 7, and the infrared absorption spectrum is shown in FIG.
0 is shown.

Example 3 0.3 parts of the chlorogallium tetra-2,3-pyridinoporphyrazine crystal obtained in Example 1 was mixed with 40 parts of 1 mmφ alumina beads in 40 parts of methanol at room temperature for 24 hours. After milling, the alumina beads and the dispersion were separated, and the dispersion was centrifuged (KONTT).
CENTRIKON H-, manufactured by RON / HERMLE
401). The obtained wet cake was dried under reduced pressure to obtain 0.27 parts of chlorogallium tetra-2,3-pyridinoporphyrazine crystals. The powder X-ray diffraction pattern of the obtained chlorogallium tetra-2,3-pyridinoporphyrazine crystal is shown in FIG. 8, and the infrared absorption spectrum is shown in FIG.

Example 4 1.0 part of the chlorogallium tetra-2,3-pyridinoporphyrazine crystal obtained in Example 1 was combined with 1 part of a polyvinyl butyral resin (Eslec BM-1 manufactured by Sekisui Chemical Co., Ltd.) and acetic acid. After mixing with 100 parts of butyl and dispersing for 2 hours using a paint shaker with 250 parts of 1/8 inch steel balls, the obtained coating solution was applied on an aluminum substrate by a dip coating method,
Heat and dry at 0 ° C for 10 minutes to form a film
Was formed.

Next, the following structural formula (1)

Embedded image N, N'-diphenyl-N, N'-bis (m
-Tolyl) benzidine (2 parts) and the following structural formula (2)

Embedded image A viscosity average molecular weight of 390 consisting of a repeating unit represented by
3 parts of poly [1,1'-di- (p-phenylene) cyclohexane carbonate] of No. 00 are dissolved in 20 parts of chlorobenzene, and the obtained coating solution is applied on the charge generating layer formed above by dip coating. And at 115 ° C
After heating for an hour to form a charge transport layer having a thickness of 20 μm, an electrophotographic photoreceptor was produced.

Example 5 The chlorogallium tetra-2,3-pyridinoporphyrazine crystal obtained in Example 2 was replaced with the chlorogallium tetra-2,3-pyridinoporphyrazine crystal used in Example 4 An electrophotographic photoreceptor was prepared in the same manner as in Example 4, except that 0.0 parts was used. Example 6 Instead of the chlorogallium tetra-2,3-pyridinoporphyrazine crystal used in Example 4, 1.0 part of the chlorogallium tetra-2,3-pyridinoporphyrazine crystal obtained in Example 3 An electrophotographic photoreceptor was prepared in the same manner as in Example 4 except for using.

Comparative Example In place of the chlorogallium tetra-2,3-pyridinoporphyrazine crystal used in Example 4, the chlorogallium tetra-2,3-pyridinoporphyrazine crystal 1.0 obtained in the synthesis example was used. An electrophotographic photoreceptor was produced in the same manner as in Example 4, except for using parts.

(Measurement and Evaluation of Electrophotographic Photoreceptor) The electrical characteristics of the electrophotographic photoreceptors produced in Examples 4 to 6 and Comparative Example were measured as follows. Using an electrostatic copying paper test apparatus (manufactured by Kawaguchi Electric Co., Ltd., Electrostatic Analyzer EPA-8100), room temperature and normal humidity (20
C., 50% RH), the photoreceptor is charged by a corona discharge of -6 kV, and then a tungsten lamp light is applied.
The light was split into monochromatic light of 780 nm using a monochromator, and adjusted to 1 μW / cm ² on the surface of the photoreceptor for irradiation. The half-exposure amount E1 / 2 (μJ / μC) until the initial surface potential V0 (volt) becomes 1/2.
cm ² ), and the surface of the photoreceptor was irradiated with tungsten light of 10 lux for 1 second to measure the residual potential VR (volt). Further, the attenuation rate DDR (%) was also measured. Further, VO, E1 / 2, DDR and VR after repeating the above charging and exposure 2000 times were also measured. Table 1 shows the results.

[0042]

[Table 1]

[0043]

The chlorogallium tetra-2,3 of the present invention
-Pyridinoporphyrazine crystals have a novel crystal form, are highly sensitive, have excellent electric properties such as low residual potential, and have durability such as repetition stability. It is extremely useful as a photoconductive material for an excellent electrophotographic photosensitive member. Further, an electrophotographic photoreceptor manufactured using such a crystal has excellent electric characteristics and durability, and can be used as a photoreceptor for a laser printer or the like.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of an example of an electrophotographic photosensitive member according to the present invention.

FIG. 2 is a schematic sectional view of another example of the electrophotographic photosensitive member according to the present invention.

FIG. 3 is a schematic sectional view of another example of the electrophotographic photosensitive member according to the present invention.

FIG. 4 is a schematic sectional view of another example of the electrophotographic photosensitive member according to the present invention.

FIG. 5 shows chlorogallium tetra- obtained in Synthesis Example.
1 shows a powder X-ray diffraction diagram of 2,3-pyridinoporphyrazine crystals.

FIG. 6 shows chlorogallium tetra- obtained in Example 1.
1 shows a powder X-ray diffraction diagram of 2,3-pyridinoporphyrazine crystals.

FIG. 7 shows chlorogallium tetra- obtained in Example 2.
1 shows a powder X-ray diffraction diagram of 2,3-pyridinoporphyrazine crystals.

FIG. 8 shows chlorogallium tetra- obtained in Example 3.
1 shows a powder X-ray diffraction diagram of 2,3-pyridinoporphyrazine crystals.

FIG. 9 shows chlorogallium tetra- obtained in Synthesis Example.
3 shows an infrared absorption spectrum of a 2,3-pyridinoporphyrazine crystal.

10 shows an infrared absorption spectrum of a chlorogallium tetra-2,3-pyridinoporphyrazine crystal obtained in Example 2. FIG.

11 shows an infrared absorption spectrum of a chlorogallium tetra-2,3-pyridinoporphyrazine crystal obtained in Example 3. FIG.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Charge generation layer, 2 ... Charge transport layer, 3 ... Conductive support,
4: Undercoat layer, 5: Protective layer.

Claims (3)

[Claims] 1. A chlorogallium tetra-2 having no clear peak at a Bragg angle (2θ ± 0.2 °) of 5 ° to 40 ° in an X-ray diffraction spectrum with respect to CuKα ray (λ = 1.54 Å). , 3-pyridinoporphyrazine crystals, at least 14.15 °, 17.51 ° and 25.81 ° with Bragg angles (2θ ± 0.2 °)
Chlorogallium tetra- having a main diffraction peak
2,3-pyridinoporphyrazine crystal and at least 10.77 ° of Bragg angle (2θ ± 0.2 °), 1
A chlorogallium tetra-2,3-pyridinoporphyrazine crystal having main diffraction peaks at 7.82 ° and 26.72 °. 2. A photoconductive material for an electrophotographic photoreceptor, comprising the chlorogallium tetra-2,3-pyridinoporphyrazine crystal according to claim 1. 3. The chlorogallium tetra-2,3-pyridinoporphyrazine crystal according to claim 1,
An electrophotographic photoreceptor characterized in that a photosensitive layer containing a seed is coated on a conductive support.