JPH06329943A - Metal phthalocyanine compound and electrophotographic photoreceptor containing the same - Google Patents

Abstract

PURPOSE:To provide a metal phthalocyanine compound having a new crystal form, a high sensitivity and durability as a photoconductive material and to provide an electrophotographic photoreceptor containing the same. CONSTITUTION:The metal phthalocyanine compound is represented by the formula (wherein M is a metal; R is halogen; X1 to X4 are each hydrogen, halogen, alkyl or alkoxyl; and k, l, m and n are each an integer of 1-4), belongs to the space group P(-1), and has lattice constants such that a=12.0+ or -2.0Angstrom , b=12.5+ or -2.0Angstrom , c=8.5+ or -2.0Angstrom , alpha=96.0+ or -10.0 deg., beta=95.0+ or -10.0 deg., and gamma=68.0+ or -10.0 deg., and crystal coordinates such that x=0.22+ or -0.05, y=0.01+ or -0.5 and z=-0.16+ or -0.05 for the central metal, x=0.31+ or -0.06, y=-0.05+ or -0.06 and z=-0.30+ or -0.06 for the halogen bonded to the central metal, and x=0.08+ or -0.06, y=0.14+ or -0.06 and z=-0.25+ or -0.06 for each nitrogen atom bonded to the central metal.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a metal phthalocyanine compound having a specific crystal type in which a halogen atom is bonded to a central metal. Further, the present invention relates to an electrophotographic photoreceptor containing the metal phthalocyanine compound in a photosensitive layer, particularly an electrophotographic photoreceptor which can be effectively used in a printer or a copying machine.

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as zinc oxide, selenium and cadmium sulfide have been used as photoconductive materials for electrophotographic photoreceptors. However, these inorganic materials have insufficient electrophotographic properties, are highly toxic, and have a problem in disposal processing. In order to improve such problems, photoconductive materials have been made to contain various organic materials in the photosensitive layer. Organic materials have advantages such as nontoxicity, easy processability, and light weight, and many studies have been conducted so far, but they were not sufficient in terms of sensitivity and durability. In recent years, there has been an increasing demand for extending the photosensitive wavelength range of conventionally proposed organic photoconductive materials to the wavelength (780 to 830 nm) of a semiconductor laser of near infrared rays and using it as a photoconductor for digital recording such as a laser printer. There is. From this viewpoint, squarylium compounds (JP-A-49-105536 and JP-A-58-105536).
-21216), triphenylamine-based trisazo compounds (JP-A-61-151659), phthalocyanine compounds (JP-A-48-34189 and JP-A-48-18989).
No. 7-148745) has been proposed as a photoconductive material for semiconductor lasers. When using an organic photoconductive material as a photosensitive material for a semiconductor laser, first,
It is required that the photosensitive wavelength range extends to a long wavelength and that the photosensitive member formed next has good sensitivity and durability.
However, the above-mentioned organic photoconductive material does not fully satisfy these conditions. In order to overcome these drawbacks, the relationship between the crystal type and the electrophotographic characteristics of the above-mentioned organic photoconductive material has been studied, and many reports have been made on phthalocyanine compounds.

Generally, phthalocyanine compounds show several crystal types depending on the difference in production method and treatment method, and it is known that this difference in crystal type has a great influence on photoelectric conversion characteristics of phthalocyanine compounds. Regarding the crystal type of the phthalocyanine compound, for example, when looking at copper phthalocyanine, α, ε, π,
Crystal forms such as χ, ρ, γ, σ, and δ are known, and it is known that these crystal forms can be mutually transformed by mechanical strain, sulfuric acid treatment, organic solvent treatment, heat treatment, or the like. (For example, U.S. Pat. Nos. 2,770,629, 3,160,635, 3,357,989 and 3,708,292). In addition, JP-A-5
With respect to the difference in the crystal type of copper phthalocyanine and the electrophotographic characteristics, 0-38543 discloses that the ε type exhibits the highest sensitivity in comparison of α, β, γ and ε types.

[0004]

However, the conventionally proposed phthalocyanine compound is not yet sufficiently satisfactory in terms of photosensitivity and durability when used as a photoconductive material, and a new crystalline form is not available. The development of the phthalocyanine compound is desired. Therefore, the present invention has been made in view of the above-mentioned circumstances in the prior art, and its object is to provide a metal phthalocyanine compound having a novel crystal form excellent in photosensitivity and durability as a photoconductive material, and It is to provide an electrophotographic photosensitive member having high sensitivity and high durability.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on the relationship between the crystal type of phthalocyanine compounds and the electrophotographic characteristics, and as a result, the following specific space group, lattice constant and crystal The inventors have found that a metal phthalocyanine compound having a molecular arrangement that can be represented by coordinates is highly sensitive and durable as a photoconductive material, and completed the present invention.

That is, the metal phthalocyanine compound of the present invention is represented by the following general formula, the space group is P (-1), and the lattice constant is a = 12.0 ± 2.0 angstrom (hereinafter referred to as physical unit). Is represented by "A"), b = 12.5 ± 2.0A, c = 8.5 ± 2.0.
A, α = 96.0 ± 10.0 °, β = 95.0 ± 10.
0 °, γ = 68.0 ± 10.0 °, and the crystal coordinates of the central metal are x = 0.22 ± 0.05 and y = 0.01 ±.
0.05, z = -0.16 ± 0.05, and the position of the halogen atom bonded to the central metal is the crystal coordinate, and x =
0.31 ± 0.06, y = −0.05 ± 0.06, z =
The position of one nitrogen atom contained in the pyrrole ring bonded to the central metal is −0.30 ± 0.06, and the coordinate is x = 0.08 ± 0.06, y = 0.14 ±. 0.0
6, having a molecular sequence at z = -0.25 ± 0.06. Further, the electrophotographic photosensitive member of the present invention,
A conductive layer is coated with a photosensitive layer containing the above metal phthalocyanine compound.

[0007]

[Chemical 2]

(Where M is aluminum, gallium,
Represents silicon, a metal belonging to the fourth period of the periodic table, a metal belonging to the fifth period or a metal belonging to the sixth period, R represents a halogen atom, and X ₁ , X ₂ , X ₃ and X ₄ are the same. Or they may be different, hydrogen atom, halogen atom,
Represents an alkyl group or an alkoxy group. k, l, m, and n each represent an integer of 1 to 4. ) However,
As shown in FIG. 1, the molecular arrangement of one crystal can be represented in a plurality of ways depending on how the lattice is taken, and one crystal can be represented by a plurality of lattice constants. All metal phthalocyanine crystals in which the crystal lattice is represented by the above molecular arrangement by changing the way of taking the lattice are included in the present invention.

The present invention will be described in detail below. The metal phthalocyanine compound of the present invention in which a halogen atom is bonded to the central metal is, as shown in the above general formula, a metal at the center of four pyrrole rings in the phthalocyanine molecule,
It has a halogen atom in one direction with respect to the pyrrole ring. The configuration of the molecule depends on the central metal M and the halogen atom R bonded thereto, as shown below.

[Chemical 3]

The symbols M, R and X _{1 to} X in the above general formula
Examples of ₄ are as follows.
For example, the atom represented by M is aluminum (A
l), gallium (Ga), silicon (Si), Ti,
Ge, Zr, Sn, Pb, and other metals belonging to the fourth period of the periodic table, V, As, Nb, Sb, Ta, and Bi belonging to the fifth period, Cr, Se, Mo, Te, W, etc. Examples include metals belonging to the sixth period. Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Further, among the substituents represented by X _{1 to} X ₄ , examples of the halogen atom include the above-mentioned atoms, and examples of the alkyl group include a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
A butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, a t-pentyl group, a hexyl group, an octyl group and the like can be mentioned.
Methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-
Examples thereof include butoxy group, t-butoxy group, pentyloxy group and hexyloxy group. Up to 4 of these X _{1 to} X ₄ can be substituted in each benzene nucleus.

The crystal structure of the metal phthalocyanine compound is
If the space group, the lattice constant, the positions of atoms constituting the molecule, and the number of molecules in the unit cell are known, the crystal structure of the molecular crystal is determined, and the crystal structure can be determined by X-ray analysis.
The phthalocyanine molecule has a cyclic structure in which carbon atoms and nitrogen atoms are alternately bonded, and the molecular structure itself hardly changes, although it slightly changes depending on the size of the central metal. In addition, the metal phthalocyanine pyrrole ring in which a halogen atom is bonded to the central metal has four symmetrical structures with the central metal as the center. Therefore, if the position of the central metal, the position of the halogen atom bonded to the central metal, and the position of one nitrogen atom contained in the pyrrole ring bonded to the central metal are determined, The position can be determined.

That is, the crystal structure of the metal phthalocyanine compound of the present invention is represented by the following space group, lattice constant and crystal coordinates. (1) Space group P (-1) (2) Lattice constant a = 12.0 ± 2.0 A α = 96.0 ± 10.0
° b = 12.5 ± 2.0A β = 95.0 ± 10.0
° c = 8.5 ± 2.0 A γ = 68.0 ± 10.0
° (3) Crystal coordinates Central metal x = 0.22 ± 0.05 y = 0.01 ± 0.05 z = −0.16 ± 0.05 Halogen atom bound to the central metal x = 0.31 ± 0.06 y = −0.05 ± 0.06 z = −0.30 ± 0.06 One nitrogen atom contained in the pyrrole ring bonded to the central metal x = 0.08 ± 0.06 y = 0.14 ± 0.06 z = -0.25 ± 0.06

Here, regarding the arrangement of the metal phthalocyanine molecule, the three-dimensional structure of the arrangement of the two closest molecules from two directions is shown below.

[Chemical 4]

The novel crystal of the metal phthalocyanine compound of the present invention can be produced, for example, as follows. After heating 1,3-diiminoisoindoline or phthalonitrile and a metal halide such as a metal chloride or silicon tetrahalide in a solvent, the reaction product is filtered, washed and dried to obtain a halogen atom on the metal. Bonded metal phthalocyanine crystals are obtained. Thereafter, the metal phthalocyanine crystals are pulverized in an automatic mortar or the like, stirred in a solvent, separated from the solvent and dried to obtain metal phthalocyanine compounds each having a predetermined crystal form. As the solvent used in the above treatment, aromatic solvents (toluene, chlorobenzene, etc.), amides (N, N-dimethylformamide (DM
F), N-methylpyrrolidone etc.), alcohols (methanol, ethanol etc.) and polyhydric alcohols (ethylene glycol, glycerin, polyethylene glycol etc.) and the like.

The metal phthalocyanine compound obtained as described above is useful as a photoconductive material, and its functional characteristics will be briefly described. The metal phthalocyanine compound has a structure in which molecules are in contact with each other with a van der Waals radius, and has a very stable crystal structure. Since the intermolecular energy of the molecular crystal is generally considered to be Van der Waals force, the metal phthalocyanine compound of the present invention has a large intermolecular interaction when represented by the above-mentioned molecular arrangement, It is presumed to have a stable crystal structure. Also, since it has a structure in which a halogen atom is directly bonded to the central metal,
It is presumed that high electrophotographic sensitivity can be obtained when the metal phthalocyanine compound of the present invention is used as a photoconductive material due to polarization between the metal atom and the halogen atom. Furthermore, since the molecules of the crystal structure having the above-mentioned physical properties are closely packed in space, the metal phthalocyanine compound of the present invention is presumed to have good moisture resistance.

Next, an electrophotographic photosensitive member using the above metal phthalocyanine compound as a photoconductive material in the photosensitive layer will be described. In the electrophotographic photosensitive member of the present invention, the photosensitive layer coated on the conductive support may have a single-layer structure or a laminated structure composed of a charge generation layer and a charge transport layer. Good. An undercoat layer may be formed between the conductive support and the photosensitive layer.

The conductive support may be any one as long as it can be used as an electrophotographic photoreceptor. The undercoat layer is effective in preventing unnecessary injection of charges from the conductive support, and has the function of enhancing the chargeability of the photosensitive layer. Further, it also has the function of enhancing the adhesion between the photosensitive layer and the conductive support. As the material constituting the undercoat layer, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl pyridine, cellulose ethers, cellulose esters, polyamide, polyurethane, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, polyacrylic acid, Examples thereof include polyacrylamide, zirconium chelate compounds, zirconium alkoxide compounds, other organic zirconium compounds, titanium chelate compounds, titanium alkoxide compounds, other organic titanium compounds, and silane coupling agents. The thickness of the undercoat layer is 0.05-2μ
m is suitable.

When the electrophotographic photosensitive member has a laminated structure, the charge generation layer is composed of the metal phthalocyanine compound and a binder resin. The binder resin can be selected from a wide range of insulating resins. Preferred binder resins include polyvinyl butyral, polyarylate (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate, polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, acrylic resin, polyacrylamide. Insulating resins such as polyvinyl pyridine, cellulosic resin, urethane resin, epoxy resin, casein, polyvinyl alcohol, and polyvinylpyrrolidone. It can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene and polyvinylpyrene.

For the charge generation layer, a coating solution is prepared by dispersing the metal phthalocyanine compound having a halogen atom bound to a central metal in a solution prepared by dissolving the above-mentioned binder resin in an organic solvent, and preparing a coating solution for the conductive support. It can be formed by applying it on the body and drying. In that case, the composition ratio of the metal phthalocyanine compound and the binder resin used is 400: 1 to 1:10 by weight, preferably 10: 1 to 1: 1.
The range is 4. When the ratio of the metal phthalocyanine compound is too high, the stability of the coating solution is lowered, and when it is too low, the sensitivity is lowered, so that the above composition ratio is appropriate.

The solvent used is preferably selected from those which do not dissolve the undercoat layer formed as the case requires. Specific organic solvents include alcohols such as methanol, ethanol and isopropanol, acetone,
Ketones such as methyl ethyl ketone and cyclohexanone,
Amides such as DMF, N, N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, methylene chloride, chloroform, tetrachloride Carbon, aliphatic halogenated hydrocarbons such as dichloroethylene and trichloroethylene, aromatic hydrocarbons such as benzene, toluene and xylene, aromatic halogenated hydrocarbons such as monochlorobenzene and dichlorobenzene, petroleum refining solvents such as ligroin Is mentioned. The coating liquid can be applied by a coating method such as a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method or a curtain coating method. Drying after application is 30 to 200
It can be carried out at a temperature of ° C for 5 minutes to 2 hours while still or under blowing air. Further, the film thickness of the charge generation layer to be formed is usually suitable in the range of 0.05 to 5 μm.

When the electrophotographic photoreceptor has a laminated structure, the charge transport layer is composed of a charge transport material and a binder resin. Examples of the charge transport material include polycyclic aromatic compounds such as anthracene-based, pyrene-based, phenanthrene-based, indole-based, carbazole-based, imidazole-based,
Nitrogen-containing heterocyclic compounds such as pyrazoline compounds, hydrazone compounds, triphenylmethane compounds, triphenylamine compounds, enamine compounds, stilbene compounds and the like can be used. Further, photoconductive polymers such as poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinylanthracene, polyvinylphenylacenaphthylene, polyglycidylcarbazole, pyrene-formaldehyde resin and ethylcarbazole-formaldehyde resin can be mentioned. , They may form the layer by themselves. Further, as the binder resin, the same insulating resin as that used for the charge generating layer can be used. The composition ratio of the charge transport material and the binder resin is preferably in the range of 5: 1 to 1: 5 by weight. The charge-transporting layer is prepared by preparing a coating solution using the above-mentioned charge-transporting material and binder resin and an organic solvent similar to the above, which does not dissolve the charge-generating layer, and then applying by the same method as described above, followed by drying. Can be formed. Further, the film thickness of the charge transport layer is usually appropriate in the range of 5 to 50 μm.

When the electrophotographic photosensitive member has a single-layer structure, the photosensitive layer is composed of the metal phthalocyanine compound having a halogen atom bound to the central metal, the charge transporting material and the binder resin. The same binder resin as described above is used. The composition ratio of the metal phthalocyanine compound and the charge transport material to the binder resin is
The weight ratio is 1:20 to 5: 1, and the composition ratio of the metal phthalocyanine compound and the charge transport material is 1:10 to 1 by weight ratio.
A range of 0: 1 is suitable. Then, in the same manner as described above, a photosensitive layer is formed by preparing a coating solution, then coating and drying it.

[0023]

The present invention will be described in more detail with reference to the following examples. In addition, "part" in Examples and Comparative Examples
Means "parts by weight". Example 1 40 parts of 1,3-diiminoisoindoline and 10 parts of aluminum trichloride were added to 200 parts of distilled quinoline, and heated at 200 ° C. for 3 hours. The reaction product is filtered,
After washing with acetone and methanol, it was dried to obtain 25 parts of chloroaluminum phthalocyanine crystal. Then
4 parts of these crystals were crushed in an automatic mortar for 5 hours to obtain DMF100.
After stirring for 30 hours in the unit, by centrifuging,
3 parts of chloroaluminum phthalocyanine crystals were recovered. The powder X-ray diffraction pattern is shown in FIG. As a result of X-ray analysis of this powder crystal, the space group was P (-1), and the lattice constants were a = 11.8A, b = 12.6A, c = 8.4A,
With α = 95.8 °, β = 96.2 °, γ = 68.1 °,
The crystal coordinates of the central metal (Al) are x = 0.23, y =
0.01, z = -0.16, the position of the chlorine atom bonded to the central metal is in crystal coordinates, x = 0.30, y =
The position of one nitrogen atom contained in the pyrrole ring bonded to the central metal is −0.06, z = −0.31, and x = 0.08, y = 0.15, z. = -0.2
Was in 4.

Example 2 30 parts of 1,3-diiminoisoindoline and 7 parts of gallium trichloride were added to 200 parts of distilled quinoline, and 2 parts were added.
Heated at 00 ° C. for 3 hours. The reaction product was filtered, washed with acetone and methanol, and then dried to obtain 20 parts of chlorogallium phthalocyanine crystal. Then this crystal 3
Parts in an automatic mortar for 5 hours and 30 parts in 100 parts DMF
After stirring for 2 hours, 2 parts of chlorogallium phthalocyanine crystal was collected by centrifugation. The powder X-ray diffraction pattern is shown in FIG. As a result of X-ray analysis of this powder crystal, the space group is P (-1) and the lattice constant is a = 12.2.
A, b = 12.8A, c = 8.8A, α = 95.9 °,
Central metal (Ga) at β = 96.2 °, γ = 69.5 °
The crystal coordinates of x = 0.21, y = 0.01, z =-
At 0.16, the position of the chlorine atom bonded to the central metal is in crystal coordinates, x = 0.31, y = −0.06, z =
The position of one nitrogen atom contained in the pyrrole ring bonded to the central metal at −0.31 is in crystal coordinates, and x =
The values were 0.07, y = 0.13, and z = -0.25.

Example 3 5 parts of the chloroaluminum phthalocyanine crystal obtained in Example 1 was added to a mixed solution of 100 parts of a concentrated aqueous ammonium hydroxide solution and 40 parts of pyridine, and the mixture was refluxed for 7 hours. The obtained reaction product is washed with pyridine, a concentrated aqueous solution of ammonium hydroxide and hot water, dried at 110 ° C., and a solid containing hydroxyaluminum phthalocyanine is obtained.
5 parts were obtained. Then, this solid is reacted with hydrofluoric acid in a hot bath, and the obtained reaction product is water, methanol,
Washed with pyridine and acetone, dried at 110 ° C.,
Further, by sublimation purification at 540 ° C., 3.5 parts of fluoroaluminum phthalocyanine crystal was obtained. 3 parts of this crystal was crushed in an automatic mortar for 5 hours, stirred in 100 parts of DMF for 30 hours, and then centrifuged to recover 2 parts of fluoroaluminum phthalocyanine crystal. The powder X-ray diffraction pattern is shown in FIG. As a result of X-ray analysis of this powder crystal, the space group is P (-1) and the lattice constant is a =
11.6A, b = 12.4A, c = 8.4A, α = 9
At 4.6 °, β = 97.2 °, γ = 68.9 °, the crystal coordinates of the central metal (Al) are x = 0.23, y = 0.0.
0, z = -0.15, the position of the fluorine atom bonded to the central metal is in crystal coordinates, x = 0.31, y =-
At 0.04, z = -0.30, the position of one nitrogen atom contained in the pyrrole ring bonded to the central metal is in crystal coordinates, and x = 0.08, y = 0.15, z = -0.26
There was

Example 4 An aluminum substrate was prepared as a conductive support. On the other hand, 1 part of the chloroaluminum phthalocyanine crystal obtained in Example 1 was mixed with polyvinyl butyral (S-REC BM).
-1, 1 part of Sekisui Chemical Co., Ltd.) and 100 parts of cyclohexanone were mixed and treated with glass beads for 1 hour on a paint shaker and dispersed. The obtained coating solution is applied onto the aluminum substrate by a dip coating method, and 1
It was heated and dried at 00 ° C. for 5 minutes to form a charge generation layer having a thickness of 0.2 μm. When X-ray diffraction measurement was performed after the film formation, it was confirmed that the phthalocyanine did not undergo crystal transition. Next, N, N ′ represented by the following chemical formula
-Diphenyl-N, N '-(m-tolyl) benzidine 2
Parts and 3 parts of poly (cyclohexylidene-bis-p-phenylene carbonate) represented by the following structural formula are dissolved in 20 parts of monochlorobenzene, and the obtained coating solution is applied onto the charge generation layer by a dip coating method. By heating and drying at 120 ° C. for 1 hour, a charge transport layer having a film thickness of 20 μm was formed. As described above, an electrophotographic photosensitive member containing a chloroaluminum phthalocyanine crystal in the charge generation layer was manufactured.

[0027]

[Chemical 5]

Example 5 An electrophotographic photosensitive member was produced in the same manner as in Example 4 except that the chlorogallium phthalocyanine crystal obtained in Example 2 was used instead of the chloroaluminum phthalocyanine crystal. Example 6 An electrophotographic photosensitive member was produced in the same manner as in Example 4 except that the fluoroaluminum phthalocyanine crystal obtained in Example 3 was used instead of the chloroaluminum phthalocyanine crystal.

Comparative Example 1 10 parts of 1,3-diiminoisoindoline and 7 parts of gallium trichloride were added to 100 parts of distilled quinoline, and 2 parts were added.
Heated at 00 ° C. for 3 hours. The reaction mixture was filtered, washed with acetone and methanol, and then dried to obtain 6 parts of chlorogallium phthalocyanine crystal. The powder X-ray diffraction pattern is shown in FIG. As a result of X-ray analysis of this powder crystal, the space group is P (-1), the lattice constant is a = 9.3A, b = 1.
1.3A, c = 13.1A, α = 105.5 °, β = 1
At 05.5 °, γ = 96.8 °, the crystal coordinates of gallium are at x = 0.06, y = 0.18, z = 0.20, and the position of the chlorine atom bonded to gallium is In crystal coordinates, x = −0.06, y = 0.31, z = 0.29, and the position of one nitrogen atom contained in the pyrrole ring bonded to gallium is crystal coordinates and x = 0. .08, y =
It was 0.15 and z = −0.26. Next, an electrophotographic photosensitive member containing a chlorogallium phthalocyanine crystal in the charge generation layer was produced in the same manner as in Example 4 except that the chlorogallium phthalocyanine crystal was used instead of the chloroaluminum phthalocyanine crystal.

Comparative Example 2 30 parts of phthalonitrile and 10 parts of Mo (CO) ₆ were added to 150 parts of toluene and heated to 180 ° C. in vacuum to obtain 10 parts of oxomolybdenum phthalocyanine. The powder X-ray diffraction pattern is shown in FIG. As a result of X-ray analysis of this powder crystal, the space group is P2 _{1 / c} and the lattice constant is a = 1.
3.4A, b = 13.3A, c = 14.0A, β = 10
At 3.8 °, the crystal coordinate of molybdenum is x = 0.26,
y = 0.49, z = 0.30, the position of the oxygen atom bonded to molybdenum is in crystal coordinates, x = 0.24,
At y = 0.49, z = 0.18, the position of one nitrogen atom contained in the pyrrole ring bonded to molybdenum is the crystal coordinate, and x = 0.34, y = 0.35, z = 0.3
Was in 5. Next, an electrophotographic photosensitive member containing an oxomolybdenum phthalocyanine crystal in the charge generation layer was produced in the same manner as in Example 4 except that the above oxomolybdenum phthalocyanine crystal was used instead of the chloroaluminum phthalocyanine crystal.

The electrical characteristics of the electrophotographic photosensitive members produced in Examples 4 to 6 and Comparative Examples 1 and 2 were measured as follows. Electrostatic Copy Paper Testing Device (EPA-810
0, manufactured by Kawaguchi Electric Co., Ltd., at room temperature and normal humidity (20 ° C.,
-6kV corona discharge under 50% RH environment,
After charging the surface of the photoconductor, the light of the tungsten lamp was split into monochromatic light of 800 nm by a monochromator, adjusted to 1 μW / cm ² on the surface of the photoconductor, and irradiated. Then, the exposure amount E _1/2 (erg / cm) until it becomes 1/2 of the initial surface potential V ₀ (volt)
² ) was measured, and then 10 lux of tungsten light was irradiated on the surface of the photoconductor for 1 second to obtain the residual potential V _R (volt).
Was measured. Further, V ₀ , E _1/2 and V _R were measured after repeating the above charging and exposure 1000 times. The results are shown in Table 1.

[0032]

[Table 1]

[0033]

INDUSTRIAL APPLICABILITY The metal phthalocyanine compound in which a halogen atom is bonded to the central metal of the present invention is a novel crystal, and an electrophotographic photosensitive member produced by using this crystal as a photoconductive material is highly sensitive and can be charged. It has high properties, low residual potential, and excellent repeated stability. Furthermore, 75
Since the sensitivity is high in the range of 0 to 800 nm, it is suitable for a printer using a semiconductor laser.

[Brief description of drawings]

FIG. 1 is a drawing showing how to form a plurality of crystal lattices for one crystal.

FIG. 2 shows a powder X-ray diffraction pattern of the chloroaluminum phthalocyanine crystal obtained in Example 1 of the present invention.

FIG. 3 shows a powder X-ray diffraction pattern of the chlorogallium phthalocyanine crystal obtained in Example 2 of the present invention.

FIG. 4 shows a powder X-ray diffraction diagram of a fluoroaluminum phthalocyanine crystal obtained in Example 3 of the present invention.

5 shows a powder X-ray diffraction pattern of the chlorogallium phthalocyanine crystal obtained in Comparative Example 1. FIG.

FIG. 6 shows a powder X-ray diffraction pattern of the oxomolybdenum phthalocyanine crystal obtained in Comparative Example 2.

Claims (2)

[Claims] 1. The space group is P (-1), the lattice constant is a = 12.0 ± 2.0 angstrom, and b = 1.
2.5 ± 2.0 Å, c = 8.5 ± 2.0
Angstrom, α = 96.0 ± 10.0 °, β = 9
5.0 ± 10.0 °, γ = 68.0 ± 10.0 °, the crystal coordinate of the central metal is x = 0.22 ± 0.05,
y = 0.01 ± 0.05, z = −0.16 ± 0.05, and the position of the halogen atom bonded to the central metal is in crystal coordinates, and x = 0.31 ± 0.06, y = -0.05 ±
0.06, z = −0.30 ± 0.06, and the position of one nitrogen atom contained in the pyrrole ring bonded to the central metal is crystal coordinates, and x = 0.08 ± 0.06, y = 0.
A metal phthalocyanine compound represented by the following general formula, which has a molecular arrangement of 14 ± 0.06 and z = −0.25 ± 0.06. [Chemical 1] (In the formula, M represents aluminum, gallium, silicon, a metal belonging to the fourth period of the periodic table, a metal belonging to the fifth period or a metal belonging to the sixth period, R represents a halogen atom, X ₁ , X _2, X ₃ and X ₄ may be the same or different, .k represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, l, m and n, an integer of 1-4 respectively .) 2. An electrophotographic photoreceptor comprising a conductive support and a photosensitive layer containing the metal phthalocyanine compound according to claim 1 coated on the conductive support.