JPH07304991A - Production of gallium phthalocyanine compound and crystal thereof - Google Patents

Abstract

PURPOSE:To produce a new gallium phthalocyanine compound and stably produce a gallium phthalocyanine crystal having excellent properties as a photoconductive material. CONSTITUTION:A metal amide represented by the general formula: MNHR (wherein M is an alkali metal selected from among Li, Na and K; and R is 1-4C alkyl or hydrogen) is reacted with a gallium halide, and the obtained product is reacted with a reagent for forming a phthalocyanine skeleton to produce a gallium phthalocyanine compound. The obtained compound is treated with an acid paste to obtain a gallium phthalocyanine crystal having strong diffraction peaks at Bragg angles (2theta+ or -0.2 deg.) of 6.9 deg., 13.2 deg.-14.2 deg., 16.5 deg. and 26.4 deg. or at Bragg angles of 7.0 deg., 13.4 deg., 16.6 deg., 26.0 deg. and 26.7 deg.. This compound is further treated with a solvent to effect crystal transition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a gallium phthalocyanine compound useful as a photoconductive material and a method for producing a novel gallium phthalocyanine crystal.

[0002]

BACKGROUND OF THE INVENTION Phthalocyanine compounds are useful materials as paints, printing inks, catalysts or electrophotographic materials, and in recent years, they have been extensively studied as materials for electrophotographic photoreceptors, optical recording materials and photoelectric conversion materials. ing. Regarding electrophotographic photoreceptors, in recent years, the photosensitive wavelength range of conventionally proposed organic photoconductive materials has been extended to the wavelength (780 nm to 830 nm) of near-infrared semiconductor lasers, and as a photoreceptor for digital recording such as laser printers. There is an increasing demand for use, and from this viewpoint, a squarylium compound (JP-A-49-105536 and JP-A-58-21416) and a triphenylamine-based trisazo compound (JP-A-61-151659). ), A phthalocyanine compound (JP-A-48-34189).
JP-A-57-148745 and JP-A-57-148745) have been proposed as photoconductive materials for semiconductor lasers. When an organic photoconductive material is used as a photoconductor for a semiconductor laser, first, the photosensitivity wavelength range extends to a long wavelength, and then the photoconductor formed has good sensitivity and durability. Is required. The organic photoconductive material described above does not fully satisfy these conditions. In order to overcome these drawbacks, the relationship between the crystal type and electrophotographic characteristics of the organic photoconductive material has been studied, and many reports have been made on phthalocyanine compounds.

Generally, it is known that phthalocyanine compounds show a large number of crystal types depending on the difference in production method and treatment method, and this difference in crystal type is known to greatly affect the photoelectric conversion characteristics of phthalocyanine. ing. Regarding the crystal form of the phthalocyanine compound, for example, when looking at copper phthalocyanine, in addition to the stable β form, α,
Crystal forms such as π, χ, ρ, γ, and δ are known (for example, US Pat. Nos. 2,770,629 and 3,160,635).
Nos. 3,708,292 and 3,357,989). Further, JP-A-50-38543 and the like describe the relationship between the difference in crystal type of copper phthalocyanine and electrophotographic sensitivity. Regarding the crystal form and electrophotographic characteristics of gallium phthalocyanine using the acid pasting method, JP-A-1-221459 describes two types. Further, the present inventors have previously found that those having five types of crystal forms described in Japanese Patent Application No. 4-118524 have excellent electrophotographic characteristics. Regarding the method for producing these crystals, the acid pasting method as described in Bull. Soc. Chim. France, 23 (1962) is adopted, and after metastable gallium phthalocyanine is obtained, a solvent conversion treatment is performed. It is obtained by doing. The gallium phthalocyanine used in the acid pasting method,
Chlorogallium phthalocyanine (eg DCR Aca
d. Sci., 242, 1026 (1956), JP-B-3-30854, JP-A-1-221459, Inorg. Chem.,
19, 3131 (1980)), bromogallium phthalocyanine (for example, JP-A-59-133551), iodogallium phthalocyanine (for example, JP-A-60-59354).
No. gazette) and the like.

[0004]

By the way, in the acid pasting method as described above, when gallium phthalocyanine is produced by using chlorogallium phthalocyanine, bromogallim phthalocyanine, iodogallium phthalocyanine or the like as the gallium phthalocyanine, a crystal is obtained. Even if the same mold is obtained, when it is used as an electrophotographic photosensitive member, the characteristics, especially the dark decay rate and the environmental fluctuation are large, and stable characteristics are obtained. Was difficult. The present invention is
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel method for producing a gallium phthalocyanine compound. Another object of the present invention is to provide a method for stably obtaining a gallium phthalocyanine crystal used for obtaining a crystal form exhibiting excellent characteristics as a photoconductive material. Still another object of the present invention is to provide a method for obtaining a novel gallium phthalocyanine crystal exhibiting excellent properties as a photoconductive material.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies and as a result, after reacting a specific metal amide with a gallium halide as a raw material which is a precursor for obtaining a gallium phthalocyanine crystal, Using a gallium phthalocyanine crystal obtained by reacting a reagent forming a phthalocyanine skeleton and solvent-treating it, it was found that a gallium phthalocyanine crystal having excellent electrophotographic characteristics was obtained, and the present invention was completed. . That is, a first aspect of the present invention relates to a method for producing a gallium phthalocyanine compound, which comprises the following general formula (I) MNHR (I) (where M is an alkali selected from Li, Na and K). Represents a metal, and R represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) and gallium halide, and then reacts with a phthalocyanine skeleton-forming reagent. To do.

A second aspect of the present invention relates to a method for producing a gallium phthalocyanine crystal used as a raw material for obtaining a crystal form exhibiting excellent characteristics as a photoconductive material, which is represented by the above general formula (I). After reacting the indicated metal amide with gallium halide and then reacting with a reagent for phthalocyanine skeleton to synthesize gallium phthalocyanine, acid pasting treatment was carried out to obtain a Bragg angle to CuKα characteristic X-ray in an X-ray diffraction spectrum. (2θ ± 0.2 °) is (a) 6.9.
°, 13.2 ° to 14.2 °, 16.5 ° and 26.
4 °, or (b) 7.0 °, 13.4 °, 16.6
It is characterized in that gallium phthalocyanine crystals having strong diffraction peaks at °, 26.0 ° and 26.7 ° are obtained.

A third aspect of the present invention relates to a method for producing a novel gallium phthalocyanine crystal exhibiting excellent properties as a photoconductive material, in which the gallium phthalocyanine crystal obtained by the above-mentioned production method is treated with a solvent. By the crystal transition, the Bragg angle (2θ ± 0.2 °) with respect to the CuKα characteristic X-ray is (i) 7.7 °,
16.5 °, 25.1 ° and 26.6 °, (ii) 7.
9 °, 16.5 °, 24.4 ° and 27.6 °, (ii
i) 7.0 °, 7.5 °, 10.5 °, 11.7 °, 1
2.7 °, 17.3 °, 18.1 °, 24.5 °, 2
6.2 ° and 27.1 °, (iv) 7.5 °, 9.9
°, 12.5 °, 16.3 °, 18.6 °, 25.1 °
And 28.3 °, or (v) 6.8 °, 12.8
It is characterized in that gallium phthalocyanine crystals having strong diffraction peaks at °, 15.8 ° and 26.0 ° are obtained.

Impurities in phthalocyanine have a great influence on electrophotographic properties. In the present invention, however, the gallium phthalocyanine crystal used in the above solvent treatment is obtained from an amide compound of gallium, and therefore has high reactivity and is used as a raw material. Impurities are less likely to remain, and even if an amide compound of gallium remains in the reaction solution, it is easily dissolved in water and removed, and finally becomes an amine, so that electrophotographic characteristics are not deteriorated. Therefore, in the present invention, since the gallium phthalocyanine crystal obtained via the gallium amide compound is used, it is considered that the gallium phthalocyanine crystal excellent in electrophotographic characteristics can be obtained.

The manufacturing method of the present invention will be described in detail below. In the method for producing the gallium phthalocyanine compound of the present invention, it can be obtained by first reacting the metal amide represented by the general formula (I) with gallium halide and then reacting with a phthalocyanine skeleton-forming reagent. The metal amide used is one in which R represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom in the general formula (I), and M represents an alkali metal selected from Li, Na, and K. However, among them, the use of sodium amide is preferable because the yield is good. Also,
In the case of a metal amide having an alkyl group, when the alkyl group has 5 or more carbon atoms, it exhibits surface activity during acid pasting described later, hinders recovery of gallium phthalocyanine, and has a solubility in water. Since it decreases, it is difficult to remove it, which causes adverse effects. Therefore, in the case of a metal amide having an alkyl group, the carbon number of the alkyl group needs to be 4 or less. Further, gallium chloride is preferably used as the gallium halide from the viewpoint of manufacturability and the like.

Further, as the phthalocyanine skeleton-forming reagent, phthalonitrile, 4-methylphthalonitrile,
4,5-dimethylphthalonitrile, 4-chlorophthalonitrile, 4,5-dichlorophthalonitrile, 4-nitrophthalonitrile, 4,5-dinitrophthalonitrile, 3
-Methylphthalonitrile, 3-chlorophthalonitrile,
3-nitrophthalonitrile, diiminoisoindoline,
5-methyldiiminoisoindoline, 5,6-dimethyldiiminoisoindoline, 5-chlorodiiminoisoindoline, 5,6-dichlorodiminoisoindoline, 5-
Nitrodiiminoisoindoline, 5,6-dinitrodiiminoisoindoline, 5-cyanodiiminoisoindoline, 5,6-dicyanodiiminoisoindoline, 4-methyldiiminoisoindoline, 4-chlorodiiminoisoindoline, 4-nitrodiiminoisoindoline, 4-
Examples include cyanodiiminoisoindoline. Among these, phthalonitrile and diiminoisoindoline are preferably used when a new gallium phthalocyanine crystal described later is prepared.

In the present invention, as the organic solvent used for the reaction of the metal amide and the gallium halide, ketones such as acetone and methyl ethyl ketone, ethyl acetate,
Examples thereof include esters such as butyl acetate, halogenated hydrocarbons such as dichloromethane, chloroform, and aromatic hydrocarbons such as toluene and xylene. The reaction temperature is -15
C. to 150.degree. C., preferably -5.degree. C. to 100.degree. Examples of the organic solvent used in the reaction between the reaction product of the metal amide and the gallium halide and the reagent forming the phthalocyanine skeleton include alcohols such as butanol, glycols such as ethylene glycol, glycerin and polyethylene glycol. To be The reaction temperature in this reaction is 100 ° C to 230 ° C, preferably 1
It is set in the range of 60 ° C to 210 ° C. The gallium phthalocyanine compound obtained by the above reaction is isolated and then treated by the acid pasting method,
It is possible to obtain a gallium phthalocyanine compound having a desired crystal form.

In the present invention, in the X-ray diffraction spectrum, the Bragg angle (2θ ± 2) with respect to the CuKα characteristic X-ray is used.
0.2 °) of 6.9 °, 13.2 ° to 14.2 °, 1
6.5 ° and 26.4 °, or (b) 7.0 °, 1
In order to obtain gallium phthalocyanine crystals having strong diffraction peaks at 3.4 °, 16.6 °, 26.0 ° and 26.7 °, phthalonitrile or diimino is used as a phthalocyanine skeleton-forming reagent in the above reaction. The gallium phthalocyanine compound obtained by using isoindoline may be acid pasted. The acid pasting process can be performed as follows. That is, to prepare an acid paste solution of gallium phthalocyanine obtained by the above reaction, while stirring the acid paste solution in alkaline water, or a mixed solution of alkaline water and an organic solvent, while maintaining the liquid temperature below the boiling point. When dropped, gallium phthalocyanine crystals are produced. The obtained gallium phthalocyanine crystal is purified by washing with water or the like. In this case, when acid pasting is performed using alkaline water, in the X-ray diffraction spectrum, the Bragg angle (2θ ± 0.2 °) of 6.9 °, 13.2 ° to 1 with respect to the CuKα characteristic X-ray.
A gallium phthalocyanine crystal having strong diffraction peaks at 4.2 ° and 16.5 ° was obtained, and when acid pasting was performed using a mixed solution of alkaline water and an organic solvent, CuKα characteristic X was observed in an X-ray diffraction spectrum. Bragg angle (2θ ± 0.2 °) to line 7.0 °, 1
A gallium phthalocyanine crystal having strong diffraction peaks at 3.4 °, 16.6 °, 26.0 ° and 26.7 ° is obtained.

When performing the above acid pasting,
Examples of the acid used for preparing the acid paste solution include sulfuric acid, hydrochloric acid, hydrobromic acid, trifluoroacetic acid, and the like.
Concentrated sulfuric acid is preferable because it has high solubility and is easy to handle. In the case of concentrated sulfuric acid, 5 to 1 against gallium phthalocyanine
It is used in the range of 00 times, but is preferably in the range of 15 to 40 times.

Examples of the alkali used in the alkaline water include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and various ammonium hydroxide salts. As the organic solvent used, alcohols such as methanol, ethylene glycol, glycerin, glycols such as polyethylene glycol, acetone, ketones such as methyl ethyl ketone,
Esters such as ethyl acetate and butyl acetate, halogenated hydrocarbons such as dichloromethane, chloroform, toluene,
Examples thereof include aromatic hydrocarbons such as xylene. The amount of the organic solvent used is 10 times or less, preferably 5 times or less, that of water. The alkaline water or the mixed solution is
1 to gallium phthalocyanine acid paste solution
It is used in a range of 100 times, preferably 3 to 20 times. Acid pasting is carried out at a treatment temperature in the range of -15 ° C to 100 ° C, but when a mixed solvent is used, it is preferably carried out at a temperature below its boiling point.

The gallium phthalocyanine crystals obtained as described above are solvent treated according to the present invention. Thereby, crystal transition is performed, and the following novel gallium phthalocyanine crystal can be obtained. That is, in the X-ray diffraction spectrum, the Bragg angle (2θ ± 0.2 °) with respect to the CuKα characteristic X-ray is (i) 7.7 °, 16.5 °, 25.1 ° and 26.
6 ° (see FIG. 6); (ii) 7.9 °, 16.5 °, 24.4 ° and 27.
6 ° (see FIG. 7); (iii) 7.0 °, 7.5 °, 10.5 °, 11.7
°, 12.7 °, 17.3 °, 18.1 °, 24.5
°, 26.2 ° and 27.1 ° (see FIG. 8); (iv) 7.5 °, 9.9 °, 12.5 °, 16.3 °,
18.6 °, 25.1 ° and 28.3 ° (see FIG. 5); and (v) 6.8 °, 12.8 °, 15.8 ° and 26.
One having a strong diffraction peak at 0 ° (see FIG. 9) can be mentioned.

In the present invention, examples of the solvent used for the solvent treatment include the following. 1) In the X-ray diffraction spectrum, a Bragg angle (2θ ± 0.2 °) of 7.7 ° with respect to the CuKα characteristic X-ray, 1
Solvents used in producing gallium phthalocyanine crystals having strong diffraction peaks at 6.5 °, 25.1 ° and 26.6 ° include aliphatic alcohols (methanol, ethanols), polyhydric alcohols ( Examples thereof include ethylene glycol, glycerin, polyethylene glycol, etc.), sulfoxides (dimethyl sulfoxide, etc.), aromatics (toluene, chlorobenzene, etc.), etc., and further treatment with methanol is required for a long time.

2) In the X-ray diffraction spectrum, CuK
Used in producing gallium phthalocyanine crystals having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of α characteristic X-rays of 7.9 °, 16.5 °, 24.4 ° and 27.6 °. Examples of the solvent include amides (N, N
-Dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), organic amines (pyridine, piperidine, etc.), sulfoxides (dimethylsulfoxide, etc.), etc., and it is necessary to treat with methanol for a short time. .

3) In the X-ray diffraction spectrum, CuK
Bragg angles (2θ ± 0.2 °) of α characteristic X-rays of 7.0 °, 7.5 °, 10.5 °, 11.7 °, 12.
7 °, 17.3 °, 18.1 °, 24.5 °, 26.2
Aromatic alcohols (benzyl alcohol, etc.) and the like can be mentioned as a solvent used when producing a gallium phthalocyanine crystal having a strong diffraction peak at 2 ° and 27.1 °.

4) In the X-ray diffraction spectrum, CuK
Bragg angles (2θ ± 0.2 °) of α characteristic X-rays of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.
As the solvent used when producing the gallium phthalocyanine crystal having strong diffraction peaks at 6 °, 25.1 ° and 28.3 °, amides (N, N-dimethylformamide, N, N-dimethylacetamide, N -Methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc.), organic amines (morpholine, etc.), esters (ethyl acetate, n-butyl acetate, iso-amyl acetate, etc.),
Ketones (acetone, methyl ethyl ketone, methyl is
Examples thereof include o-butyl ketone) and sulfoxides (dimethyl sulfoxide).

5) In the X-ray diffraction spectrum, CuK
Used for producing gallium phthalocyanine crystals having strong diffraction peaks at 6.8 °, 12.8 °, 15.8 ° and 26.0 ° of Bragg angle (2θ ± 0.2 °) with respect to α characteristic X-ray. Examples of the solvent to be used include polyhydric alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.) and the like. When polyhydric alcohols are used, heat treatment (for example, 100 ° C. for 7 hours) is performed.

The solvent used for producing each gallium phthalocyanine crystal may be a mixed system in which two or more of them are mixed, a mixed system of water and these solvents, or the like.
As the method of solvent treatment, for example, not only a normal recrystallization treatment, but also any method as long as it is a treatment operation in which a solvent is used, such as washing, wet pulverization, dipping, suspension stirring, etc. Good. Further, the solvent treatment may be performed in an appropriate container while standing or stirring. When using wet grinding,
Ball mill, mortar, sand mill, kneader, attritor and the like can be performed using a predetermined solvent, when crushed, salt, inorganic compounds such as sodium sulfate and glass beads,
Grinding media such as steel beads and alumina beads may be used. As the solvent treatment conditions, the amount of the solvent used is appropriately 1 to 200 parts, preferably 10 to 100 parts, relative to 1 part of gallium phthalocyanine, and the treatment temperature is 0.
˜150 ° C., preferably room temperature to 100 ° C. By the solvent treatment as described above, a preferable novel crystal of gallium phthalocyanine having a better crystallinity and a uniform grain size can be produced.

The gallium phthalocyanine crystal produced by the above method of the present invention can be used as a charge generating material in an electrophotographic photoreceptor. Hereinafter, the electrophotographic photosensitive member using the gallium phthalocyanine crystal manufactured by the above method of the present invention will be described. The electrophotographic photosensitive member of the present invention may have a single-layer structure of the photosensitive layer or a laminated structure in which the charge generation layer and the charge transport layer are functionally separated. When the photosensitive layer has a laminated structure, the charge generation layer is composed of the gallium phthalocyanine crystal and the binder resin. In the electrophotographic photoreceptor, a photosensitive layer comprising a charge generating layer and a charge transport layer laminated thereon is coated on a conductive support, and an undercoat layer is interposed between the photosensitive layer and the conductive support. It is desirable to put it.

The charge generating layer in the electrophotographic photosensitive member of the present invention is prepared by dispersing the above-mentioned gallium phthalocyanine crystals, which are the charge generating material, in a solution containing a binder resin in an organic solvent to prepare a coating solution, which is prepared as a conductive support. It is formed by applying on top. A wide variety of resins such as polyvinyl butyral resin and polyvinyl formal resin are used as the binder resin. Further, as a solvent for dissolving the binder resin,
It is preferable to select from those that do not dissolve the undercoat layer.
The compounding ratio (weight) of the gallium phthalocyanine crystal and the binder resin is appropriately in the range of 40: 1 to 1:20.
As a method for dispersing the gallium phthalocyanine crystal, a usual method such as a ball mill dispersion method, an attritor dispersion method, or a sand mill dispersion method can be adopted.
The coating liquid can be applied by 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, an air knife coating method, or a curtain coating method. Further, the film thickness of the charge generation layer is preferably about 0.05 to 5 μm. The charge transport layer in the electrophotographic photoreceptor of the present invention comprises N, N'-diphenyl-N, N-bis- (m-
Tolyl) benzidine, 4-diethylaminobenzaldehyde-2,2-diphenylhydrazone, p- (2,2-
It is formed by incorporating a known charge transporting material such as diphenylvinyl) -N, N'-diphenylaniline in a suitable binder resin.

For the charge transport layer, a coating solution is prepared by using a charge transport material and a binder resin and an organic solvent similar to those used for forming the charge generation layer, and then the same coating method as described above is used. The charge generating layer can be formed by applying the coating liquid by means of a means. At this time, the compounding ratio (weight) of the charge transport material and the binder resin is preferably 10: 1 to 1: 5. The thickness of the charge transport layer is generally 5 to 50.
About μm is appropriate.

When the photosensitive layer of the present invention has a single layer structure, the photosensitive layer comprises a photoconductive layer in which the gallium phthalocyanine crystal is dispersed in a charge transport material and a binder resin. The charge transport material and the binder resin are the same as those used when the photosensitive layer has a laminated structure, and the photoconductive layer is formed by the same method as described above. In that case, the compounding ratio (weight) of the charge transport material and the binder resin is 1:10 to 1
It is preferably set to about 0: 1.

As the conductive support, any support can be used as long as it can be used as an electrophotographic photoreceptor. In the present invention, a polyamide resin, a polycarbonate resin, a zirconium chelate compound is provided between the conductive support and the photosensitive layer in order to prevent unnecessary injection of charges from the conductive support to the photosensitive layer during charging of the photosensitive layer. An undercoat layer containing a titanyl chelate compound or the like may be interposed. If necessary, the surface of the photosensitive layer may be coated with a protective layer. This protective layer not only prevents the charge-transporting layer from chemically deteriorating during charging in the photosensitive layer having a laminated structure, but also improves the mechanical strength of the photosensitive layer.

[0027]

EXAMPLES The present invention will be specifically described below with reference to examples. In the following examples, “part” means “part by weight”. Example 1 8.0 parts of sodium amide and 50 ml of toluene were stirred and suspended under a nitrogen atmosphere, and then a solution of 10 parts of gallium chloride dissolved in 50 ml of toluene was added to the solution. It was stirred. This mixture was cooled to room temperature, 29.1 parts of phthalonitrile and 150 ml of ethylene glycol were further added, and the mixture was stirred at 180 ° C. for 24 hours under a nitrogen atmosphere while removing low-boiling substances. The product was filtered, washed successively with N, N-dimethylformamide, distilled water and methanol and dried to obtain 30.2 parts of gallium phthalocyanine. The powder X-ray diffraction pattern is shown in FIG.

Example 2 16.2 parts of lithium butyramide, 50 ml of toluene
Was stirred and suspended under a nitrogen atmosphere, and then 50 m of toluene was added.
A solution prepared by dissolving 25.6 parts of gallium iodide in 1 is added to
The mixture was stirred at 70 ° C. for 10 minutes under a nitrogen atmosphere. The mixture is cooled to room temperature and then diiminoisoindoline 3
3.0 parts and 150 ml of ethylene glycol were added, and the mixture was stirred at 180 ° C. for 24 hours in a nitrogen atmosphere while removing low-boiling substances. The product was filtered, washed with N, N-dimethylformamide, distilled water, and methanol in that order, and dried to obtain 30.8 parts of gallium phthalocyanine. The powder X-ray diffraction pattern is shown in FIG.

Example 3 10 parts of gallium phthalocyanine obtained in Example 1 was dissolved in 250 parts of concentrated sulfuric acid, stirred for 2 hours, and then added dropwise to a mixed liquid of 870 ml of ice-cooled distilled water and 530 ml of concentrated ammonia water. To precipitate crystals. The precipitated crystal was thoroughly washed with distilled water and dried to obtain 9 parts of gallium phthalocyanine crystal. The powder X-ray diffraction spectrum of this crystal is shown in FIG.
Shown in. This crystal has a Bragg angle (2θ ± 0.2 °)
Had strong diffraction peaks at 6.9 °, 13.2 ° to 14.2 °, 16.5 ° and 26.4 °.

Example 4 10 parts of gallium phthalocyanine obtained in Example 2 was dissolved in 250 parts of concentrated sulfuric acid, stirred for 2 hours and then added to a mixed solution of 375 ml of ice-cooled distilled water, 375 ml of concentrated ammonia water and 2250 ml of dichloromethane. The crystals were deposited by dropping. The precipitated crystal was thoroughly washed with distilled water and dried to obtain 9 parts of gallium phthalocyanine crystal. The powder X-ray diffraction spectrum of this crystal is shown in FIG. This crystal is
Bragg angle (2θ ± 0.2 °) of 7.0 °, 13.4
It had strong diffraction peaks at °, 16.6 °, 26.0 ° and 26.7 °. Example 5 2250 ml of the dichloromethane of Example 4 was replaced with acetone 75
The same process as in Example 4 was carried out except that 0 ml was used to obtain 9 parts of a gallium phthalocyanine crystal. Powder X of this crystal
The line diffraction spectrum was the same as in FIG. Example 6 In order to investigate the variation in electrophotographic characteristics of the obtained gallium phthalocyanine crystal, the operation of Example 5 was repeated to produce another gallium phthalocyanine crystal. The powder X-ray diffraction spectrum of the obtained crystal was similar to that shown in FIG.

Comparative Example 1 29.1 parts of phthalonitrile, 9.2 parts of gallium trimethoxide and 150 ml of ethylene glycol were stirred under a nitrogen atmosphere at 200 ° C. for 24 hours, and then the product was filtered. Next, N, N-dimethylformamide and methanol were sequentially washed and dried to obtain 23.0 parts of gallium phthalocyanine. Comparative Example 2 100 ml of α-chloronaphthalene and 1 gallium trichloride
0 parts and 29.1 parts of phthalocyanine were added, and after stirring at 200 ° C. for 24 hours under a nitrogen atmosphere, the product was filtered. Then, N, N-dimethylformamide and methanol were sequentially washed and dried to obtain 28.9 parts of gallium phthalocyanine.

Comparative Example 3 The procedure of Example 3 was repeated except that the gallium phthalocyanine crystal obtained in Comparative Example 1 was used to obtain 9 parts of a gallium phthalocyanine crystal. The powder X-ray diffraction pattern was the same as in FIG. Comparative Example 4 The procedure of Example 4 was repeated except that the gallium phthalocyanine crystal obtained in Comparative Example 2 was used, to obtain 9 parts of a gallium phthalocyanine crystal. The powder X-ray diffraction pattern was the same as in FIG.

Examples 7 to 10 Gallium phthalocyanine crystals 1 obtained in Examples 3 to 6
15 parts of N, N-dimethylformamide and 1 m in diameter
After milling with 30 parts of m glass beads for 24 hours, the crystals were separated, washed with n-butyl acetate and dried to obtain 0.9 parts of gallium phthalocyanine crystals, respectively. All of their powder X-ray diffraction patterns were similar to those shown in FIG.

Comparative Example 5 0.9 part of a gallium phthalocyanine crystal was obtained in the same manner as in Example 7, except that the gallium phthalocyanine crystal obtained in Comparative Example 3 was used. The powder X-ray diffraction diagram is shown in FIG.
Was similar to. Comparative Example 6 The procedure of Example 7 was repeated except that the gallium phthalocyanine crystal obtained in Comparative Example 4 was used to obtain 0.9 part of a gallium phthalocyanine crystal. The powder X-ray diffraction pattern was the same as in FIG.

Examples 11 to 13 0.5 parts of the galimphthalocyanine crystals obtained in Example 4 were milled with 15 parts of the solvent shown in Table 1 and 30 parts of glass beads having a diameter of 1 mm for 24 hours, and then the crystals were formed. Separated, washed with methanol, and dried to obtain 0.4 parts of gallium phthalocyanine crystal, respectively. The powder X-ray diffraction patterns thereof are shown in FIGS.

[Table 1]

Example 14 0.5 part of the galimphthalocyanine crystal obtained in Example 4 was added to 5 parts of ethylene glycol and stirred at 100 ° C. for 7 hours, then the crystal was separated, washed with methanol and dried. Thus, 0.4 part of gallium phthalocyanine crystal was obtained. The powder X-ray diffraction pattern is shown in FIG.

Application Examples 1 to 4 10 parts of a zirconium compound (Organotex ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and a silane compound (trade name: A1110, manufactured by Nippon Unicar) on an aluminum substrate.
A solution consisting of 1 part, 40 parts of i-propanol and 20 parts of butanol was applied by a dip coating method, and the temperature was 150 ° C.
Was heated and dried for 10 minutes to form an undercoat layer having a thickness of 0.2 μm. Then, 1 part of the gallium phthalocyanine crystal obtained in Examples 7 to 10 was mixed with 1 part of polyvinyl butyral (S-Rex BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts of n-butyl acetate, and the mixture was mixed with glass beads to paint. The mixture was treated with a shaker for 1 hour and dispersed. The obtained coating liquid was applied onto the above-mentioned undercoat layer by a dip coating method, and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a film thickness of about 0.2 μm. A coating liquid obtained by dissolving 2 parts of the following charge transporting material represented by the following structural formula (1) and 3 parts of a polycarbonate resin including a repeating unit represented by the following structural formula (2) in 20 parts of chlorobenzene. Was applied on an aluminum substrate having a charge generation layer formed thereon by a dip coating method, and dried by heating at 120 ° C. for 1 hour to form a charge transport layer having a film thickness of 20 μm.

[Chemical 1]

The electrophotographic characteristics of the electrophotographic photosensitive member thus obtained were measured as follows. Using a flat plate scanner, normal temperature and humidity (20 ℃, 40%
RH), the photoreceptor is charged to an initial surface potential V0 (V) by a corona discharge of -2.5 μA, left for 1 second to measure VDDP (V), and the dark decay rate DDR (%) [ D
DR = 100 (V0-VDDP) / V0] was calculated. After that, the light from the tungsten lamp was split into monochromatic light of 780 nm using a monochromator, adjusted to 0.25 μW / cm ² on the surface of the photoconductor, and irradiated.
The initial sensitivity dV / dE (V · cm ² / erg) was measured. The measurement results are shown in Table 2.

Reference Examples 1 and 2 An electrophotographic photosensitive member was prepared in the same manner as in Application Example 1 except that the gallium phthalocyanine obtained in Comparative Examples 5 and 6 was used, and electrophotographic characteristics were measured in the same manner. It was The results are shown in Table 2.

[Table 2]

[0040]

EFFECTS OF THE INVENTION Since the present invention has the above-mentioned constitution, it is possible to easily produce a high-purity gallium phthalocyanine compound and a gallium phthalocyanine crystal which have high reactivity, are easy to remove impurities, and have a low impurity content. You can Therefore, the gallium phthalocyanine crystal produced according to the present invention is used as a photoconductive material,
It is useful for producing an electrophotographic photoreceptor having high photosensitivity. That is, the electrophotographic photosensitive member produced by using the gallium phthalocyanine crystal obtained by the present invention shows stable electrophotographic characteristics without variations in charging property, dark decay rate and high sensitivity, and uses a semiconductor laser. It exhibits excellent image quality characteristics in printers and the like, and a copied image having excellent image quality can be obtained.

[Brief description of drawings]

1 shows a powder X-ray diffraction pattern of gallium phthalocyanine obtained in Example 1. FIG.

FIG. 2 shows a powder X-ray diffraction pattern of gallium phthalocyanine obtained in Example 2.

3 shows a powder X-ray diffraction pattern of the gallium phthalocyanine crystal obtained in Example 3. FIG.

FIG. 4 shows a powder X-ray diffraction pattern of the gallium phthalocyanine crystal obtained in Example 4.

FIG. 5 shows a powder X-ray diffraction diagram of gallium phthalocyanine crystals obtained in Examples 7 to 10.

6 shows a powder X-ray diffraction pattern of the gallium phthalocyanine crystal obtained in Example 11. FIG.

7 shows a powder X-ray diffraction pattern of the gallium phthalocyanine crystal obtained in Example 12. FIG.

8 shows a powder X-ray diffraction pattern of the gallium phthalocyanine crystal obtained in Example 13. FIG.

9 shows a powder X-ray diffraction pattern of the gallium phthalocyanine crystal obtained in Example 14. FIG.

Claims (3)

[Claims] 1. The following general formula (I) MNHR (I) (wherein M represents an alkali metal selected from Li, Na and K, and R represents an alkyl group having 1 to 4 carbon atoms or hydrogen). A metal amide represented by an atom) is reacted with a gallium halide, and then a reagent for forming a phthalocyanine skeleton is reacted with the gallium phthalocyanine compound. 2. The following general formula (I) MNHR (I) (wherein M represents an alkali metal selected from Li, Na and K, and R represents an alkyl group having 1 to 4 carbon atoms or hydrogen). In the X-ray diffraction spectrum, CuKα was obtained by reacting a metal amide represented by an atom) with gallium halide and then reacting with a reagent for a phthalocyanine skeleton to synthesize gallium phthalocyanine, followed by acid pasting treatment. The Bragg angle (2θ ± 0.2 °) to the characteristic X-ray is (a) 6.9.
°, 13.2 ° to 14.2 °, 16.5 ° and 26.
4 °, or (b) 7.0 °, 13.4 °, 16.6
A method for producing a gallium phthalocyanine crystal, which comprises obtaining a gallium phthalocyanine crystal having strong diffraction peaks at °, 26.0 ° and 26.7 °. 3. A gallium phthalocyanine crystal obtained by the manufacturing method according to claim 2 is treated with a solvent,
In the X-ray diffraction spectrum, the Bragg angle (2θ ± 0.2 °) with respect to the CuKα characteristic X-ray is (i) 7.7.
°, 16.5 °, 25.1 ° and 26.6 °, (ii)
7.9 °, 16.5 °, 24.4 ° and 27.6 °,
(Iii) 7.0 °, 7.5 °, 10.5 °, 11.7
°, 12.7 °, 17.3 °, 18.1 °, 24.5
°, 26.2 ° and 27.1 °, (iv) 7.5 °,
9.9 °, 12.5 °, 16.3 °, 18.6 °, 2
5.1 ° and 28.3 °, or (v) 6.8 °, 1
A method for producing a gallium phthalocyanine crystal, which comprises obtaining a gallium phthalocyanine crystal having strong diffraction peaks at 2.8 °, 15.8 ° and 26.0 °.