JP3147607B2 - Metal phthalocyanine compound and electrophotographic photoreceptor using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal phthalocyanine compound having a specific crystal form in which an oxygen atom is bonded to a central metal. Further, the present invention relates to an electrophotographic photosensitive member containing the metal phthalocyanine compound in a photosensitive layer, particularly to an electrophotographic photosensitive member which can be effectively used for 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 in electrophotographic photoreceptors. However, these inorganic materials have insufficient electrophotographic properties, are highly toxic, and have problems in terms of disposal. In order to improve such a problem, various organic materials have been included in the photosensitive layer as a photoconductive material. Organic materials have advantages such as non-toxicity, easy processability, and light weight.
Although much research has been done so far, it was not sufficient in 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 of near-infrared semiconductor lasers (780 to 830 nm) and using them as digital recording photoconductors such as laser printers. I have. From this viewpoint, squarylium compounds (JP-A-49-105536 and JP-A-58-21416), triphenylamine-based trisazo compounds (JP-A-61-151659), and phthalocyanine compounds (JP-A-48-34189) And JP-A-57-148745) have been proposed as photoconductive materials for semiconductor lasers. When an organic photoconductive material is used as a photosensitive material for a semiconductor laser, it is required that the photosensitive wavelength range extends to a long wavelength first, and that the formed photosensitive member has good sensitivity and durability. Is done. However, the above-mentioned organic photoconductive material does not sufficiently satisfy these conditions. In order to overcome these drawbacks, the relationship between the crystal type and the electrophotographic characteristics of the organic photoconductive material has been studied, and many reports have been made especially on phthalocyanine compounds.

[0003] In general, phthalocyanine compounds exhibit several crystal forms depending on the difference in the production method and treatment method, and it is known that the difference in crystal form has a great effect on the photoelectric conversion characteristics of the phthalocyanine compound. Regarding the crystal form of the phthalocyanine compound, for example, in the case of 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 transferred by mechanical strain, sulfuric acid treatment, organic solvent treatment, heat treatment, and the like. (For example, U.S. Pat. Nos. 2,770,629, 3,160,635, 3,357,989 and 3,708,292). Also, Japanese Patent Application Laid-Open
JP-A-0-38543 describes that the ε-type shows the highest sensitivity as compared with the α, β, γ and ε-types in terms of the difference in the crystal type of copper phthalocyanine and the electrophotographic properties.

[0004]

However, the phthalocyanine compounds proposed so far are not yet sufficiently satisfactory in terms of photosensitivity and durability when used as a photoconductive material. The development of phthalocyanine compounds is desired. Therefore, the present invention has been made in view of the above-described circumstances in the related art, and its object is to provide a metal phthalocyanine compound having a novel crystal type excellent in photosensitivity and durability as a photoconductive material and An object of the present invention is to provide an electrophotographic photosensitive member having high sensitivity and high durability.

[0005]

The present inventors have conducted intensive studies on the relationship between the crystal form of the phthalocyanine compound and the electrophotographic characteristics, and as a result, the space group has a symmetric operation and an inversion operation. The difference between the two molecules of the proximity inversion is smaller than a predetermined angle, and preferably, a novel metal phthalocyanine compound whose molecular arrangement can be represented by a specific space group, lattice constant and crystal coordinates as shown below, The inventors have found that the conductive material has high sensitivity and excellent durability, and have completed the present invention.

That is, the present invention provides a hydroxyaluminum
Um phthalocyanine, oxomolybdenum phthalocyanine
Or the crystal of hydroxyindium phthalocyanine
The space group has a symmetry operation and a reversal operation, and the difference between two molecules of the proximity inversion is located at the diagonal position in the deviation direction among the four nitrogen atoms contained in the pyrrole ring in the molecule. The direction of the line connecting two nitrogen atoms is defined as one vector, and the deviation angle between this vector and the corresponding vector of the other molecule and the line connecting the respective centers is 57 ° or less. And

[0007]

[0008] The hydroxyaluminum phthalocyan of the present invention
Anine, oxomolybdenum phthalocyanine or hydro
The crystal of xindium phthalocyanine is preferably
The space group is P (-1) and the lattice constant is a = 12.0
± 2.0 angstroms (angstroms in physical units are represented by “A”), b = 12.5 ± 2.0 A,
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 ± 0.0
5, y = 0.01 ± 0.05, z = −0.16 ± 0.0
5, the position of the oxygen atom bonded to the central metal is the crystal coordinate, 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 a crystal coordinate, x = 0.08 ± 0.06, y = 0.
It has a molecular sequence represented by 14 ± 0.06, z = −0.25 ± 0.06. However, as shown in FIG. 1, the molecular arrangement of one crystal can be represented by a plurality of methods depending on how to form a lattice, and one crystal can be represented by a plurality of lattice constants. All crystal the crystal lattice by changing the way of taking grating you express by the molecular arrangement is encompassed by the present invention. Further, the electrophotographic photoreceptor of the present invention includes the above hydroxyaluminum phthalocyanine,
Oxomolybdenum phthalocyanine or hydroxyin
It is characterized in that a photosensitive layer containing crystals of diphthalic phthalocyanine is coated on a conductive support.

Hereinafter, the present invention will be described in detail. The hydroxyaluminum of the present invention having an oxygen atom bonded to the central metal
Um phthalocyanine, oxomolybdenum phthalocyanine
Or crystals of hydroxyindium phthalocyanine (hereinafter referred to as
Below, these are referred to as “metal phthalocyanine compound crystals”.
U. ) Is a metal in the center of the four pyrrole rings in the phthalocyanine molecule are those having an oxygen atom or a hydroxyl group in one direction relative to the pyrrole ring. The configuration of the molecule differs depending on the central metal M and the functional group R bonded thereto, as shown below.

Embedded image

[0010]

Here, the deviation angle referred to in the present invention will be described below. Two sets of two close-in molecules that are inversion symmetry with each other can be considered a back-to-back and a belly-to-back pair. The arrangement of the two nearby metal-phthalocyanine molecules is shown below.

Embedded image

In the present invention, the degree of deviation of the two closest molecules, which are back to back, is defined by an angle. As shown in FIG. 2, one of the four nitrogen atoms contained in the pyrrole ring in the molecule is a line direction connecting two nitrogen atoms at diagonal positions in the shift direction, and this vector and the other are used. An angle between a line connecting the corresponding vector of the numerator and each center is defined as a shift angle θ. That is, in the metal phthalocyanine compound crystal of the present invention, the deviation angle θ determined by the above definition is 57 ° or less.

In addition, the molecular arrangement of the metal phthalocyanine compound of the present invention will be described. The crystal structure of the metal phthalocyanine compound has a space group, a lattice constant, the positions of atoms constituting molecules, and the number of molecules in a unit cell. If it is understood, 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. Although there is a slight change depending on the size of the central metal, the molecular structure itself hardly changes. Further, the pyrrole ring of the metal phthalocyanine in which an oxygen atom is bonded to the central metal has four symmetrical structures centering on the central metal.
Therefore, if the position of the central metal, the position of the oxygen 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, all the atoms constituting the molecule are determined. The position can be determined.

The preferred molecular arrangement of the crystal 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 ± 2.0A α = 96.0 ± 10.0
° b = 12.5 ± 2.0A β = 95.0 ± 10.0
° c = 8.5 ± 2.0A 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 Oxygen atom bonded to 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 According to the above definition, the metal phthalocyanine compound having such a molecular arrangement has a deviation angle of about 40 °,
It has particularly excellent properties as a photoconductive material.

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 (Al or In) chloride in a solvent, the reaction product is filtered, washed and dried to obtain a metal having a chlorine atom bonded to the metal. A phthalocyanine crystal is obtained. In this case, when a metal alkoxide is used instead of a metal chloride as a raw material, a metal phthalocyanine crystal in which an alkoxy group is bonded to a metal can be obtained. Next, these crystals are dissolved in concentrated sulfuric acid, and a concentrated sulfuric acid solution is dropped into water while cooling to precipitate crystals. After washing and drying the crystals, hydroxyaluminum having a hydroxyl group bonded to a metal is obtained.
Crystals Um phthalocyanine or hydroxy indium phthaloyl <br/> cyanine is obtained. Further, after heating the 1,3-diiminoisoindoline or phthalonitrile and Mo complex carbon monoxide as a ligand in a solvent, the reaction product was filtered, washed and dried, the oxygen atom of Mo combine with the oxo molybdenum phthalocyanine crystals are obtained.

[0016] Thereafter, a metal phthalocyanine crystals to metallic water group or oxygen atom is bound pulverized in an automatic mortar or the like, after stirring in a solvent, separated from the solvent and dried, respectively predetermined crystal A metal phthalocyanine crystal having a shape can be obtained. Solvents used in the above treatment include aromatics (toluene, chlorobenzene, etc.), amides (N, N-dimethylformamide (DMF), N-methylpyrrolidone, etc.), alcohols (methanol, ethanol, etc.) and And polyhydric alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.).

The above metal phthalocyanine crystal is
It is useful as a photoconductive material, and its functional characteristics will be described briefly. The metal phthalocyanine compound has a structure in which molecules come into contact with each other at a van der Waals radius, and has a very stable crystal structure. Since the energy between molecules of a molecular crystal is generally considered to be van der Waals force, the above-mentioned misalignment angle is 57 ° or less, and in particular, the molecule represented by the above-mentioned space group, lattice constant and crystal coordinates. It is presumed that the metal phthalocyanine compound of the present invention having a sequence has a large interaction between molecules and has a stable crystal structure. In addition, since the structure has a structure in which an oxygen atom is directly bonded to the central metal, polarization occurs between the metal atom and the oxygen atom, whereby the metal phthalocyanine compound crystal of the present invention is used as a photoconductive material. It is considered that high electrophotographic sensitivity can be obtained. Further, in the crystal structure having the above-mentioned physical properties, since the molecules are densely packed spatially, it is presumed that the metal phthalocyanine compound crystal of the present invention has good moisture resistance.

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

The conductive support may be any as long as it can be used as an electrophotographic photosensitive member. The undercoat layer is effective for preventing unnecessary charge injection from the conductive support, and has an effect of increasing the chargeability of the photosensitive layer. Further, it also has the effect of increasing the adhesion between the photosensitive layer and the conductive support. Examples of the material constituting the undercoat layer include polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl pyridine, cellulose ethers, cellulose esters, polyamide, polyurethane, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, polyacrylic acid, Examples 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 to 2 μm
About m is appropriate.

When the electrophotographic photosensitive member has a laminated structure, the charge generation layer is composed of the metal phthalocyanine crystal 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 And insulating resins such as polyvinyl pyridine, cellulosic resins, urethane resins, epoxy resins, casein, polyvinyl alcohol, and polyvinylpyrrolidone. Further, it can be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, and polyvinylpyrene.

The charge generation layer is formed by dispersing the metal phthalocyanine crystal in a solution obtained by dissolving the binder resin in an organic solvent to prepare a coating solution, coating the solution on a conductive support, and drying. can do. In that case,
The composition ratio of the metal phthalocyanine crystal and the binder resin used is 100: 1 to 1:10 by weight, preferably 1: 1.
The range is from 0: 1 to 1: 4. If the ratio of the metal phthalocyanine crystal is too high, the stability of the coating solution is reduced,
If the ratio is too low, the sensitivity is lowered, so that the above composition ratio is appropriate.

The solvent to be used is preferably selected from those which do not dissolve the undercoat layer formed as required. Specific organic solvents include methanol, ethanol, alcohols such as 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 and ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, methylene chloride, chloroform, carbon tetrachloride, dichloroethylene, trichloroethylene and other aliphatic halogenated hydrocarbons , Aromatic hydrocarbons such as benzene, toluene and xylene, aromatic halogenated hydrocarbons such as monochlorobenzene and dichlorobenzene, and petroleum refining solvents such as ligroin. The coating solution 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, and a curtain coating method. Drying after application is 30 ~
It can be carried out at a temperature of 200 ° C. for 5 minutes to 2 hours in a stationary or blown state. The thickness of the formed charge generation layer is usually appropriate 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. As the charge transporting material, for example, anthracene-based, pyrene-based, polycyclic aromatic compounds such as phenanthrene-based, indole-based, carbazole-based, imidazole-based,
Compounds such as pyrazoline-based nitrogen-containing heterocyclic compounds, hydrazone-based compounds, triphenylmethane-based compounds, triphenylamine-based compounds, enamine-based compounds, and stilbene-based compounds can be used. Furthermore, poly-N
-Vinyl carbazole, halogenated poly-N-vinyl carbazole, polyvinyl anthracene, polyvinyl phenyl acenaphthylene, polyglycidyl carbazole, pyrene-formaldehyde resin, ethyl carbazole-photoconductive polymer such as formaldehyde resin, and the like.
These may form layers by themselves. Further, as the binder resin, the same insulating resin as that used for the charge generation layer described above can be used. The composition ratio of the charge transport material to the binder resin is suitably in the range of 5: 1 to 1: 5 by weight. The charge transport layer is prepared by using the same charge transport material and binder resin and the same organic solvent as described above which does not dissolve the charge generation layer, and then applied by the same method as described above, followed by drying. Can be formed. Further, the thickness of the charge transport layer is usually appropriately 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 crystal, a charge transport material and a binder resin, and the charge transport material and the binder resin are the same as those described above. Is used. The composition ratio between the metal phthalocyanine crystal and the charge transport material and the binder resin is 1:20 to 5: 1 by weight, and the composition ratio between the metal phthalocyanine crystal and the charge transport material is 1: 1 by weight.
A range from 0 to 10: 1 is appropriate. Then, in the same manner as described above, a photosensitive layer is formed by preparing a coating solution, coating and drying.

[0025]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, "parts" 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. Filtering the reaction product,
After washing with acetone and methanol, drying was performed to obtain 25 parts of chloroaluminum phthalocyanine crystals. 5 parts of the obtained chloroaluminum phthalocyanine crystal was concentrated in concentrated sulfuric acid 1
The solution was dissolved in 00 parts at 0 ° C. and dropped into 600 parts of distilled water at 5 ° C. to precipitate crystals. After washing with distilled water and diluted ammonia water, drying was performed to obtain 4 parts of hydroxyaluminum phthalocyanine crystals. Next, 4 parts of these crystals were ground in an automatic mortar for 5 hours, stirred in 100 parts of DMF for 30 hours, and then centrifuged to recover 3 parts of hydroxyaluminum phthalocyanine crystals. The powder X-ray diffraction pattern is shown in FIG. As a result of X-ray analysis of this crystal powder, the space group was P (−1), the deviation angle θ was 39.4 °, and the lattice constants were a = 11.5 A, b = 12.5 A, and c = 8. .
6A, α = 95.9 °, β = 96.1 °, γ = 68.2
°, the crystal coordinates of the central metal are x = 0.23, y = 0.
01, z = −0.16, the position of the oxygen atom bonded to the central metal is the crystal coordinates, x = 0.30, y = −
0.06, z = −0.31, and the position of one nitrogen atom contained in the pyrrole ring bonded to the central metal is crystal coordinates, x = 0.08, y = 0.15, z = −0.24
Was in

[0026]

Example 2 40 parts of phthalonitrile and 10 parts of hexacarbonylmolybdenum Mo (CO) ₆ were added to 200 parts of toluene, and heated to 180 ° C. to obtain 15 parts of oxomolybdenum phthalocyanine. The crystals (3 parts) were ground in an automatic mortar for 5 hours, stirred in DMF (100 parts) for 30 hours, and then centrifuged to recover 2 parts of oxomolybdenum phthalocyanine crystals. The powder X-ray diffraction diagram shown in FIG. As a result of X-ray analysis of this crystal powder, the space group was P (-1)
And the shift angle θ is 39.9 °, and the lattice constant is a = 1.
2.2A, b = 12.8A, c = 9.0A, α = 94.
6 °, β = 97.2 °, γ = 68.9 °, and the crystal coordinates of the central metal are x = 0.23, y = 0.0, z = −0.1
5 where the position of the oxygen atom bonded to the central metal is the crystal coordinates, x = 0.31, y = −0.04, z = −0.
30 and the position of one nitrogen atom contained in the pyrrole ring bonded to the central metal is a crystal coordinate, x = 0.0
8, y = 0.15, z = -0.26.

Example 3 40 parts of 1,3-diiminoisoindoline and 10 parts of indium trichloride were added to 200 parts of distilled quinoline and heated at 200 ° C. for 3 hours. Filtering the reaction product,
After washing with acetone and methanol, drying was performed to obtain 25 parts of chloroindium phthalocyanine crystals. 5 parts of the obtained chloroindium phthalocyanine crystal was heated under reflux with a mixed solvent of concentrated aqueous ammonia and pyridine for 20 hours, and then dried to obtain 4.5 parts of hydroxyindium phthalocyanine crystal. The powder X-ray diffraction diagram shown in FIG. Results The crystalline powder was subjected to X-ray, space group P2 ₁ / c
And the shift angle θ is 36.5 °, and the lattice constant is a = 1.
3.5A, b = 13.3A, c = 14.1A, β = 10
At 3.8 °, the crystal coordinates of the central metal are x = 0.26, y
= 0.49, z = 0.30, the position of the oxygen atom bonded to the central metal is the crystal coordinates, x = 0.24, y =
0.49, z = 0.18, and the position of one nitrogen atom contained in the pyrrole ring bonded to the central metal is crystal coordinates, x = 0.43, y = 0.35, z = 0 .35.

Example 4 An aluminum substrate was prepared as a conductive support. On the other hand, 1 part of the hydroxyaluminum phthalocyanine crystal obtained in Example 1 was mixed with 1 part of polyvinyl butyral (ESLEC BM-1, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts of cyclohexanone, and the mixture was treated with glass beads for 1 hour using a paint shaker. And dispersed. The obtained coating solution is applied on the aluminum substrate by a dip coating method, and dried by heating at 100 ° C. for 5 minutes to form a film having a thickness of 0.2 μ
m of the charge generation layer was formed. X-ray diffraction measurement was performed after the formation of the film, and it was confirmed that the phthalocyanine did not undergo crystal transition. Next, it is composed of 2 parts of N, N'-diphenyl-N, N '-(m-tolyl) benzidine represented by the following chemical formula and a structural unit represented by the following structural formula.
That poly - dissolving (cyclohexylidene bis -p- phenylene carbonate) 3 parts 20 parts of monochlorobenzene, and the resulting coating composition was applied by dip coating on the charge generating layer 1 hour heating at 120 ° C. Dry and film thickness 2
A 0 μm charge transport layer was formed. As described above, an electrophotographic photoreceptor containing the novel crystal of the metal phthalocyanine compound in the charge generation layer was manufactured.

[0030]

Embedded image

Example 5 Instead of hydroxyaluminum phthalocyanine crystal,
An electrophotographic photoreceptor was manufactured in the same manner as in Example 4 , except that the oxomolybdenum phthalocyanine crystal obtained in Example 2 was used. Example 6 Instead of hydroxyaluminum phthalocyanine crystal,
An electrophotographic photoreceptor was manufactured in the same manner as in Example 4 , except that the hydroxyindium phthalocyanine crystal obtained in Example 3 was used.

Comparative Example 1 One arm of an H-shaped tube was filled with 1,2,4-trichlorobenzene in which nickel phthalocyanine was dispersed, and the other arm was filled with bromine to seal the tube. Then
After heating the side containing nickel phthalocyanine to 150 ° C., a part of the tube was cooled to obtain bromonickel phthalocyanine crystals. FIG. 6 shows the powder X-ray diffraction pattern. As a result of X-ray analysis of this crystal powder, the space group was P4
/ Mcc, the deviation angle θ is 90.0 °, and the lattice constants are a = 13.79A, b = 13.79A, and c = 6.4.
3A, α = β = γ = 90.0 °, the nickel atom is at the origin, the position of the bromine atom bonded to nickel is the crystal coordinates, and x = 0.5, y = 0.5, z = 0.25, the position of one nitrogen atom contained in the pyrrole ring bonded to nickel is a crystal coordinate, x = 0.240, y
= 0.0590, z = 0.0. Next, Example 1 was repeated except that the bromonickel phthalocyanine crystal was used instead of the hydroxyaluminum phthalocyanine crystal.
In the same manner as in No. 4 , an electrophotographic photosensitive member containing a metal phthalocyanine crystal in the charge generation layer was manufactured.

Comparative Example 2 One arm of an H-shaped tube was filled with 1-chloronaphthalene in which iron phthalocyanine and excess iodine were dispersed,
Heating to 110 ° C. yielded iodoiron phthalocyanine crystals. The powder X-ray diffraction diagram shown in Fig. As a result of X-ray analysis of the crystal powder, the space group was P4 / mcc, the deviation angle θ was 90.0 °, and the lattice constant was a = 13.84.
A, b = 13.84A, c = 6.77A, α = β = γ =
At 90.0 °, the iron atom is at the origin, and the position of the iodine atom bonded to iron is the crystal coordinates, x = 0.5, y = 0.
5, the position of one nitrogen atom contained in the pyrrole ring bonded to iron at z = 0.25 is a crystal coordinate, and x =
0.1235, y = 0.0598, z = 0.0. Next, an electrophotographic photosensitive member containing a metal phthalocyanine crystal in the charge generation layer was manufactured in the same manner as in Example 4 except that the iodoiron phthalocyanine crystal was used instead of the hydroxyaluminum phthalocyanine crystal.

The electrical characteristics of each of the electrophotographic photosensitive members manufactured in Examples 4 to 6 and Comparative Examples 1 and 2 were measured as follows. Electrostatic copying paper tester (EPA-810
0, manufactured by Kawaguchi Electric Co., Ltd.) at normal temperature and normal humidity (20 ° C.,
In an environment of 50% RH), a corona discharge of -6 kV is performed,
After charging the surface of the photoreceptor, the light of the tungsten lamp was divided into monochromatic light of 800 nm by a monochromator, adjusted to 1 μW / cm ² on the surface of the photoreceptor, and irradiated. Then, the exposure E _1/2 (erg / cm ² ) until the initial surface potential V ₀ (volts) becomes _１ ／ was measured, and then 10 lux tungsten light was irradiated on the surface of the photoreceptor for 1 second. And the residual potential V _R (volt) was measured. Further, V ₀ , E _1/2 and V _R after repeating the above charging and exposure 1000 times were measured. Table 1 shows the results.

[0035]

[Table 1]

[0036]

According to the present invention, hydroxyaluminum phthalocyanine having an oxygen atom bonded to the central metal , oxomo
Ribdenphthalocyanine and hydroxyindium fu
Talocyanine is a novel crystal, and the electrophotographic photoreceptor manufactured using this crystal as a photoconductive material has characteristics of high sensitivity, high chargeability, low residual potential, and excellent repetition stability. I have. Furthermore, since the sensitivity is high in the range of 750 to 800 nm, it is suitable for a printer or the like using a semiconductor laser.

[Brief description of the drawings]

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

FIG. 2 is a view for explaining a misalignment angle of two closest molecules of a metal phthalocyanine defined in the present invention.

FIG. 3 shows a powder X-ray diffraction pattern of the hydroxyaluminum phthalocyanine crystal obtained in Example 1 of the present invention.

FIG. 4 shows oxomolybdenum obtained in Example 2 of the present invention.
1 shows an X-ray powder diffraction pattern of an unphthalocyanine crystal .

FIG. 5 shows hydroxyin obtained in Example 3 of the present invention.
1 shows a powder X-ray diffraction diagram of a diium phthalocyanine crystal .

FIG. 6 shows bromonickel phthalocyanine obtained in Comparative Example 1 .
1 shows a powder X-ray diffraction pattern of an anine crystal .

FIG. 7 shows iodoiron phthalocyanine obtained in Comparative Example 2 .
1 shows a powder X-ray diffraction pattern of an anine crystal .

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-93150 (JP, A) JP-A-5-263007 (JP, A) Patent 2541030 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 487/22 C09B 67/50 G03G 5/06 371 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A space group having a symmetry operation and a reversal operation, and a difference between two molecules of the proximity reversal is a diagonal position in a deviation direction among four nitrogen atoms contained in a pyrrole ring in the molecule. Is defined as one vector, and the deviation angle between this vector, the corresponding vector of the other molecule, and the line connecting the respective centers is 57 ° or less. Characteristic hydroxyal
Minium phthalocyanine, oxomolybdenum phthalocyanine
Of nin or hydroxyindium phthalocyanine
Akira . 2. A space group is P (−1), and a lattice constant is a = 12.0 ± 2.0 angstroms, b = 1
2.5 ± 2.0 angstroms, c = 8.5 ± 2.0
Angstrom, α = 96.0 ± 10.0 °, β = 9
5.0 ± 10.0 °, γ = 68.0 ± 10.0 °, and the crystal coordinates of the central metal are x = 0.22 ± 0.05,
y = 0.01 ± 0.05, z = −0.16 ± 0.05, and the position of the oxygen atom bonded to the central metal is the crystal coordinate, 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 a crystal coordinate, x = 0.08 ± 0.06, y = 0.14
2. The hide according to claim 1, wherein the hide has a molecular sequence represented by ± 0.06, z = −0.25 ± 0.06.
Roxy aluminum phthalocyanine, oxomolybdenum
Phthalocyanine or hydroxyindium phthalocyanine
Nin crystals . 3. The hydroxya according to claim 1 or 2.
Luminium phthalocyanine, oxomolybdenum phthalocyanine
Anine or hydroxyindium phthalocyanine
An electrophotographic photosensitive member, characterized in that a photosensitive layer containing crystals is coated on a conductive support.