JPH08311359A - Production of metal phthalocyanine - Google Patents

Abstract

PURPOSE: To obtain the subject compound useful as a raw material for a photoconductive material as an electrophotographic photoreceptor owing to crystal form conversion function, chemical modification function, etc., by reacting a metal salt with phthalonitrile, etc., in a solvent containing dimethylimidazolidinone. CONSTITUTION: A metal salt such as a metal halide of indium halide, gallium halide, etc., reacts with phthalonitrile or 1,3-diiminoisoindolin in a solvent containing 1,3-dimethyl-2-imidazolidionone to obtain a metal phthalocyanine of the formula [M is a metal; L is a substituent linking to a metal atom or a ligand; n is 0-2; X is a halogen; p, q, r and s are each 0-4].

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing a metal phthalocyanine useful as a photoconductive material.

[0002]

2. Description of the Related Art In recent years, organic photoconductors having sensitivity in the oscillation wavelength region of semiconductor lasers in the near infrared region have been actively developed. Examples of the organic photoconductive material used for such an organic photoreceptor include phthalocyanine compounds, bisazo and trisazo compounds, thiapyrylium compounds, squarylium compounds, azurenium compounds, thiopyrrolopyrrole compounds, and the like. Among organic photoconductive materials, phthalocyanine compounds are
It has been widely studied because of its excellent light resistance.

As a method for producing a metal phthalocyanine in which a metal atom is coordinated to the center of a phthalocyanine compound, for example, JP-A-59-128544 discloses a method in which a metal salt and phthalonitrile are heated without a solvent. Japanese Patent Laid-Open No. 61-45249 and “Inorganic Chemistry” (Vol. 19, 1980, page 3131) disclose a method of heating a metal salt and phthalonitrile in quinoline. It is disclosed in the "Journal of Imaging Science".
Imaging Science) "(1985, Vol. 29, No. 4, 148)
Page) discloses a method of heating a metal salt and 1,3-diiminoisoindoline in quinoline, and JP-A-63-27562 includes 1-methyl-2-pyrrolidinone. Each method of reacting indium bromide with diiminoisoindoline in a solvent is disclosed.

[0004]

However, in the conventionally known method for producing metal phthalocyanine, in order to obtain a photoconductive material having sufficient electrophotographic characteristics, after the synthesis of metal phthalocyanine, vacuum deposition, sublimation purification, and Soxhlet extraction are performed. Since complicated operations such as purification and recrystallization purification are required, it cannot be easily produced.

The problem to be solved by the present invention is to provide a metal phthalocyanine which exhibits sufficient electrophotographic properties as a photoconductive material without requiring complicated operations such as vacuum deposition, sublimation purification, Soxhlet extraction purification, and recrystallization purification. It is to provide a manufacturing method of.

[0006]

Means for Solving the Problems As a result of repeated studies to solve the above problems, the present inventors have found that in a solvent containing 1,3-dimethyl-2-imidazolidinone, a metal salt, By reacting with phthalonitrile or 1,3-diiminoisoindoline, a novel method for producing a metal phthalocyanine useful as a photoconductive material has been found, and the present invention has been completed.

That is, in the present invention, in order to solve the above problems, a metal phthalocyanine is produced by reacting a metal salt (A) with phthalonitrile or 1,3-diiminoisoindoline (B) in a solvent. In the method, a method for producing a metal phthalocyanine using a solvent containing 1,3-dimethyl-2-imidazolidinone as a solvent is provided.

The manufacturing method of the present invention will be described in detail below.

As the metal phthalocyanine obtained by the production method of the present invention, for example, the following general formula [1]

[0010]

Embedded image

(Wherein M represents a metal atom, L represents a substituent or a ligand bonded to the metal atom, and n represents 0 to 2).
Represents an integer, X represents a halogen atom, p, q,
r and s represent the integer of 0-4. ).

Metal salt (A) used in the production method of the present invention
As, for example, metal halides, metal hydroxides,
Examples include metal oxides. As a metal halide,
For example, indium tribromide, indium trichloride, gallium tribromide, gallium trichloride, titanium tetrabromide, titanium tetrachloride, cupric bromide, cupric chloride, vanadium tribromide, vanadium tetrachloride, dichloride. Examples thereof include magnesium bromide and magnesium dichloride. Examples of the metal hydroxide include indium hydroxide, copper hydroxide, magnesium hydroxide and the like. Examples of the metal oxide include indium oxide, titanium dioxide, cupric oxide, vanadium pentoxide, magnesium oxide and the like. Among these, metal halides having high reactivity are preferable, and indium halide and gallium halide are particularly preferable from the viewpoint of obtaining a good photoconductive material.

A solvent other than 1,3-dimethyl-2-imidazolidinone may be used in combination with the solvent containing 1,3-dimethyl-2-imidazolidinone used in the method for producing a metal phthalocyanine of the present invention. . As such a solvent, for example, known solvents such as quinoline, 1-methyl-2-pyrrolidinone, α-chloronaphthalene, dimethylformamine, dimethylsulfoxide, etc., which are conventionally used when producing metal phthalocyanines. The kind is mentioned.

The charging molar ratio of the metal salt and phthalonitrile or 1,3-diiminoisoindoline can be set arbitrarily, but a charging molar ratio of 1: 2 to 1: 6 is preferable, and a charging molar ratio of 1: 4 is particularly preferable. Ratios are preferred. When phthalonitrile and 1,3-diiminoisoindoline are used in combination, the molar ratio of metal salt to phthalonitrile and 1,3-diiminoisoindoline is 1: 2 to 1: 6. The molar ratio is preferable.

The amount of 1,3-dimethyl-2-imidazolidinone used is 1 part by weight or more, preferably 3 parts by weight or more, based on 1 part by weight of phthalonitrile or 1,3-diiminoisoindoline, and is economical. Therefore, it is preferable to use it in the range of 3 to 50 parts by weight.

Although the temperature and time during the reaction can be set arbitrarily, increasing the reaction temperature more than necessary and prolonging the reaction time may cause deterioration of the properties due to decomposition of the reaction solvent and products. Therefore, the temperature during the reaction is 80-
The reaction time at 300 ° C. is preferably 10 minutes to 30 hours.

The metal phthalocyanine obtained by the production method of the present invention can be mainly used as a charge generating material for an electrophotographic photoreceptor.

The electrophotographic photoreceptor comprises a photoconductive layer containing a metal phthalocyanine provided on a conductive support.
The structure can take various structures. For example,
(1) A charge generating layer mainly composed of a charge generating material and a charge transporting layer composed of a charge transporting material and a binder resin as necessary for forming the charge generating layer are sequentially laminated on a conductive support. A photoconductive layer is provided, (2) A photoconductive layer is formed by sequentially stacking a charge transport layer and a charge generation layer on a conductive support, and (3) Charge is provided on the conductive support. And a photoconductive layer in which a generating material is dispersed in a charge transfer medium.

In the case of the electrophotographic photoreceptors of (1) and (2), the charge generating material contained in the charge generating layer generates charges, while the charge transporting layer receives injection of the charge and transports it. Do. That is, the charges required for light attenuation are generated in the charge generating material, and the charges are transported in the charge transport medium. In the electrophotographic photoreceptor of (3) above, the charge generating material generates charges with respect to light, and the charge transfer medium moves the charges.

In the electrophotographic photoreceptor of the above (1), fine particles of the charge generating material are dispersed in a solvent in which a binder resin is dissolved, if necessary, and the resulting dispersion is applied and dried, and then applied. It can be produced by applying a solution in which the charge transporting material is used alone or, if necessary, together with a binder resin and dissolved, and coating and drying.

In the electrophotographic photosensitive member of the above (2), a solution in which a charge transport material is used alone or, if necessary, a binder resin is used together and dissolved, is applied on a conductive support, dried and then applied. It can be produced by coating fine particles of the charge generating material in a solvent or a binder resin solution, and applying and drying the resulting dispersion.

In the electrophotographic photoreceptor of the above (3), fine particles of the charge generating material are dispersed in a solution in which the charge transporting material is used alone or, if necessary, a binder resin is also used in combination, and this is electroconductively supported. It can be produced by coating on the body and drying.

In the case of the electrophotographic photoreceptors (1) and (2), the thickness of the photoconductive layer is 5 μm or less, preferably 0.01 to 2 μm. The thickness of the charge transport layer is 3 to 50 μm, preferably 5 to 30 μm
m. In the case of the electrophotographic photoreceptor of (3) above, the thickness of the photoconductive layer is 3 to 50 μm, preferably 5 to 30 μm.
m.

The proportion of the charge transport material in the charge transport layer in the electrophotographic photoreceptors (1) and (2) is 5 to 10.
It can be selected in a timely manner within the range of 0% by weight, preferably 40
It can be selected in the range of up to 80% by weight. The proportion of the charge generating material in the charge generating layer of the electrophotographic photosensitive member of the above (1) and (2) can be appropriately selected within the range of 5 to 100% by weight, and preferably within the range of 40 to 80% by weight. You can choose. In the electrophotographic photosensitive member of the above (3), the proportion of the charge transport material in the photoconductive layer can be appropriately selected within the range of 5 to 99% by weight, and the proportion of the charge generating material is 1 to
It is 50% by weight, preferably 3 to 20% by weight. In addition,
A plasticizer and a sensitizer can be used together with the binder resin in the production of any electrophotographic photoreceptor.

The conductive support used in the electrophotographic photosensitive member of the present invention includes, for example, aluminum, copper, zinc,
Stainless steel, chrome, titanium, nickel, molybdenum,
Metals or alloys such as vanadium, indium, gold and platinum,
Alternatively, a conductive polymer, a conductive compound such as indium oxide; a paper, a plastic film, a ceramic, or the like, which is coated, vapor-deposited or laminated with a metal or alloy such as aluminum, palladium, or gold, and the like, may be a conductive support. The body surface may be subjected to chemical or physical treatment.

The shape of the electrophotographic photosensitive member varies depending on the support used, but various shapes such as a drum shape, a flat plate shape, a sheet shape and a belt shape are possible.

As the charge generating material, the metal phthalocyanine obtained by the production method of the present invention may be used in combination with other charge generating materials, if necessary.

Examples of the charge generating material which can be used in combination with the metal phthalocyanine obtained by the production method of the present invention include azo pigments such as monoazo pigments, disazo pigments and trisazo pigments; other than metal phthalocyanine obtained by the production method of the present invention. Phthalocyanine pigments such as various metal phthalocyanines, metal-free phthalocyanines, and naphthalocyanines;
Examples thereof include condensed polycyclic pigments such as perinone pigments, perylene pigments, anthraquinone pigments, and quinacridone pigments; squarylium dyes; azurenium dyes; thiapyrylium dyes; cyanine dyes. The charge generating materials used in combination are not limited to those described here, and when used, they may be used alone or in combination with 2
A mixture of more than one type can be used.

The charge transport material can be broadly classified into low molecular weight compounds and high molecular weight compounds.

Examples of the charge transporting material of the low molecular weight compound include pyrene; carbazoles such as N-ethylcarbazole, N-isopropylcarbazole and N-phenylcarbazole; N-methyl-N-phenylhydrazino-3.
-Methylidene-9-ethylcarbazole, N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, p- (N, N-dimethylamino) benzaldehyde diphenylhydrazone, p- (N, N-diethylamino) benzaldehyde diphenyl Hydrazone, p-
(N, N-diphenylamino) benzaldehyde diphenylhydrazone, 1- [4- (N, N-diphenylamino) benzylideneimino] -2,3-dimethylindoline, N-ethylcarbazole-3-methylidene-N-aminoindoline, Hydrazones such as N-ethylcarbazole-3-methylidene-N-aminotetrahydroquinoline; 2,5-bis (p-diethylaminophenyl)-
Oxadiazoles such as 1,3,4-oxadiazole; 1-phenyl-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [quinolyl- (2)]-3 Pyrazolines such as-(p-diethylaminophenyl) pyrazolin; tri-p
-Tolylamine, N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-
Aryl amines such as 4,4′-diamine; butadienes such as 1,1-bis (p-diethylaminophenyl) -4,4-diphenyl-1,3-butadiene; 4- (2,
2-diphenylethenyl) -N, N-diphenylbenzenamine, 4- (1,2,2-triphenylethenyl)
Examples thereof include styryls such as -N, N-diphenylbenzenamine.

Examples of the charge transport material of the polymer compound include poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinylpyrene,
Examples thereof include polyvinyl anthracene, polyvinyl acridine, poly-9-vinylphenyl anthracene, pyrene-formamide resin, ethylcarbazole-formaldehyde resin, triphenylmethane polymer, and polyphenylalkylsilane.

The charge transport material is not limited to those described here, and may be used alone or in combination of two or more when used.

As the binder resin which can be used if necessary, it is preferable to use a hydrophobic and electrically insulating polymer compound capable of forming a film. Examples of such high molecular weight polymers include polycarbonate, polyester, methacrylic resin, acrylic resin, polyvinyl chloride,
Polyvinylidene chloride, polystyrene, polyvinyl acetate, polyvinyl butyral, styrene-butadiene copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, Examples thereof include poly-N-vinylcarbazole, polyvinyl formal, and polysulfone.

The binder resin is not limited to those described here, and may be used alone or as a mixture of two or more kinds when used.

Further, the electrophotographic photosensitive member has film-forming properties, flexibility,
In order to improve mechanical strength, well-known additives such as a plasticizer and a surface modifier may be used together with these binder resins.

Examples of the plasticizer include biphenyl, biphenyl chloride, o-terphenyl, p-terphenyl,
Dibutyl phthalate, diethyl glycol phthalate,
Examples thereof include dioctyl phthalate, triphenyl phosphoric acid, methylnaphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene and various fluorohydrocarbons.

Examples of the surface modifier include silicone oil and fluorine resin.

Any known sensitizer can be used as the sensitizer which is optionally used in the photoconductive layer.

Examples of the sensitizer include chloranil, tetracyanoethylene, methyl violet, rhodamine B, cyanine dye, merocyanine dye, pyrylium dye and thiapyrylium dye.

Further, in the electrophotographic photosensitive member, in order to improve storage stability, durability and environmental resistance, a deterioration preventing agent such as an antioxidant or a light stabilizer may be contained in the photoconductive layer. it can. Examples include phenolic compounds,
Examples thereof include hydroquinone compounds and amine compounds.

Further, in the electrophotographic photosensitive member, in order to improve the adhesiveness between the conductive support and the photoconductive layer and to prevent the injection of free charges from the conductive support into the photoconductive layer,
If necessary, an adhesive layer or a barrier layer can be provided between the conductive support and the photoconductive layer.

Materials used for these layers include polymer compounds used for the binder resin, casein, gelatin, ethyl cellulose, nitrocellulose,
Carboxy-methyl cellulose, vinylidene chloride-based polymer latex, styrene-butadiene-based polymer latex, polyvinyl alcohol, polyamide, polyurethane, phenol resin, aluminum oxide, tin oxide,
Titanium oxide and the like are mentioned, and the film thickness is preferably 5 μm or less.

When the laminated electrophotographic photosensitive member is formed by coating, the solvent that dissolves the binder resin varies depending on the type of the binder resin, but it is desirable to select from those that do not dissolve the lower layer. Specific examples of the organic solvent include alcohols such as methanol, ethanol and n-propanol; acetone, methyl ethyl ketone,
Ketones such as cyclohexanone; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; ethers such as tetrahydrofuran, dioxane, methylcellosolve; esters such as methyl acetate, ethyl acetate; dimethyl sulfoxide, sulfolane, etc. Sulfoxides and sulfones; dichloromethane, chloroform,
Aliphatic halogenated hydrocarbons such as carbon tetrachloride and trichloroethane; aromatics such as benzene, toluene, xylene, monochlorobenzene, and dichlorobenzene.

Examples of the coating method include dip coating method, spray coating method, spinner coating method, bead coating method, wire bar coating method, blade coating method, roller coating method and curtain coating method. In order to obtain a more uniform coating thickness, it is desirable to use the dip coating method.

[0045]

The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Example 1 20.0 parts by weight of phthalonitrile, 16.6 parts by weight of indium tribromide and 150 parts by weight of 1,3-dimethyl-2-imidazolidinone were placed in a reactor and stirred. The temperature was raised and the reaction was carried out at 220 ° C. for 5 hours. After the reaction was completed, the reaction mixture was cooled to 100 ° C,
The reaction product was collected by filtration while hot. The obtained reaction product was added to 100 parts by weight of methanol, stirred at room temperature for 30 minutes, and filtered. This washing operation with methanol was performed twice, and after vacuum drying at 50 ° C., 8.5 parts by weight of indium phthalocyanine bromide was obtained.

Infrared spectrophotometer IR-81 manufactured by JASCO Corporation for the indium phthalocyanine bromide thus obtained.
1 shows an infrared spectrum diagram (KBr tablet method) according to No. 0, and FIG. 2 shows an X-ray diffraction diagram by Cu-Kα line by an X-ray diffractometer RAD-B system manufactured by Rigaku Denki Co., Ltd.

Example 2 In a reactor, 25.2 parts by weight of 1,3-diiminoisoindoline and 1 part of indium tribromide were added.
5.3 parts by weight and 150 parts by weight of 1,3-dimethyl-2-imidazolidinone were taken, the temperature was raised with stirring under a nitrogen atmosphere, and the reaction was carried out at 200 ° C. for 6 hours. After completion of the reaction, the reaction mixture was cooled to 100 ° C., filtered while hot, and the reaction product was collected by filtration. The reaction product obtained was methanol 1
In addition to 00 parts by weight, the mixture was stirred at room temperature for 30 minutes and filtered. This methanol washing operation was performed twice, and after vacuum drying at 50 ° C., indium phthalocyanine bromide 11.1 was added.
Parts by weight were obtained.

Infrared spectrophotometer IR-81 manufactured by JASCO Corporation for the indium phthalocyanine bromide thus obtained.
3 shows an infrared spectrum diagram (KBr tablet method) according to No. 0, and FIG. 4 shows an X-ray diffraction diagram by Cu-Kα ray by an X-ray diffractometer RAD-B system manufactured by Rigaku Denki Co., Ltd.

(Comparative Example 1) Indium phthalocyanine bromide was obtained according to the production example disclosed in JP-A-63-27562. That is, to a three-necked flask equipped with a stirrer and a condenser, 15 g of diiminoisoindoline, 57 g of anhydrous indium tribromide and 123 ml of 1-methyl-2-pyrrolidinone were added, and then heated to a reflux temperature under a nitrogen stream at the same temperature. And reacted for 5 hours. The reaction mixture was filtered while hot under a nitrogen stream and then cooled to room temperature.
The residue was separated and slurried with 61 ml of ethanol for 0.5 hours, and this operation was repeated. The same operation was replaced with ethanol, and 61 ml of distilled water was added twice, and 61 ml of acetone was added.
, And dried in a vacuum oven at 110 ° C. for 24 hours to obtain 4.6 g of bluish violet crystalline indium phthalocyanine bromide.

This indium phthalocyanine bromide Cu-based by Rigaku RAD-B system manufactured by Rigaku Denki Co., Ltd.
The X-ray diffraction pattern by Kα ray is shown in FIG.

(Comparative Example 2) In Example 1, 1,3-
The reaction was performed in the same manner as in Example 1 except that α-chloronaphthalene was used instead of dimethyl-2-imidazolidinone. Methanol was used for the washing operation after the synthesis.
4.7 parts by weight of indium phthalocyanine bromide was obtained.

FIG. 6 shows an X-ray diffraction diagram of the thus obtained indium phthalocyanine bromide by Cu-Kα ray by an X-ray diffractometer RAD-B system manufactured by Rigaku Denki Co., Ltd.

(Example 3) In a reactor, 18.8 parts by weight of 1,3-diiminoisoindoline and 1 gallium tribromide were added.
0.0 parts by weight and 150 parts by weight of 1,3-dimethyl-2-imidazolidinone were taken, and the temperature was raised with stirring under a nitrogen atmosphere, and the reaction was carried out at 210 ° C. for 5.5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered, and the reaction product was collected by filtration. The obtained reaction product was added to methanol 100
In addition to parts by weight, the mixture was stirred at room temperature for 30 minutes and filtered. This methanol washing operation was performed twice and vacuum drying was performed at 50 ° C. to obtain 13.1 parts by weight of gallium phthalocyanine bromide.

2.0 parts by weight of gallium phthalocyanine bromide thus obtained was ground in an agate ball for 10 hours using a planetary mill. FIG. 7 shows an X-ray diffraction diagram of the collected material by Cu-Kα ray by the X-ray diffractometer RAD-B system manufactured by Rigaku Denki KK.

(Electrophotographic Characteristics) The characteristics of the metal phthalocyanine as a photoconductive material by the manufacturing method of the present invention were evaluated by the electrophotographic characteristics.

1 part by weight of polyvinyl butyral resin (trade name S-REC BH-3: manufactured by Sekisui Chemical Co., Ltd.) was mixed with 49.4 parts by weight of methylene chloride and 32.9 parts by weight of 1,1,2-trichloroethane to prepare a mixed solvent. After dissolving, and mixing 1 part by weight of the indium phthalocyanine bromide obtained in Example 1 with this solution, glass beads were added, and the mixture was pulverized and mixed for 2 hours with a paint shaker to obtain a paint. This paint was applied on a polyethylene terephthalate film on which aluminum was vapor-deposited using a bar coater, and then at 100 ° C. for 1 hour.
It was dried for 0 minutes to form a charge generation layer having a thickness of 0.5 μm.

Next, 1 part by weight of 1- [4- (N, N-diphenylamino) benzylideneimino] -2,3-dimethylindoline and a polycarbonate resin (trade name Iupilon Z-200: manufactured by Mitsubishi Gas Chemical Co., Inc.) 1 Part by weight was dissolved in a mixed solvent composed of 6.9 parts by weight of methylene chloride and 4.6 parts by weight of chlorobenzene to prepare a coating material. This coating material is applied onto the charge generation layer using a bar coater, and then dried at 110 ° C. for 1 hour to form a charge transport layer having a thickness of 20 μm, which has the layer structure shown in FIG. An electrophotographic photoconductor of was prepared.

A laminated electrophotographic photosensitive member was obtained in the same manner except that the metal phthalocyanines obtained in Examples 2 and 3 and Comparative Examples 1 and 2 were used in place of the metal phthalocyanines obtained in Example 1. Obtained.

(Evaluation of Electrophotographic Photosensitive Member) The electrophotographic photosensitive member thus obtained was subjected to a corona discharge of −6.0 KV in a dark place using an Electrostatic Paper Analyzer SP-428 manufactured by Kawaguchi Electric Co., Ltd. The negatively charged surface potential (V ₀ ) was measured and then left in the dark for 10 seconds 10
The surface potential retention rate (V ₁₀ / V ₀ ) after 2 seconds was measured. Further, the exposure energy obtained through the monochromator is 1 μJ
The photosensitivity E _1/2 was measured by the method of irradiating monochromatic light having a wavelength of 780 nm / cm ² and a wavelength of 780 nm, and measuring the time until the surface potential decreased to V 1/2 of V ₁₀ . Furthermore, the surface potential 15 seconds after the start of exposure, that is, the residual potential V _r15 (V) was measured.
The results are summarized in Table 1.

[0061]

[Table 1]

From the results shown in Table 1, the characteristics of the obtained metal phthalocyanine as a photoconductive material differ depending on the type of the solvent used in the production of the metal phthalocyanine, and the metal phthalocyanines obtained in Examples 1, 2 and 3 were V ₁₀ /
It showed excellent characteristics with a large value of V _0, a high potential holding ratio in a dark place, a small value of E _{1/2 and} a high sensitivity, and a small residual potential V _r15 . In the production method using 1,3-dimethyl-2-imidazolidinone of the present invention, the cause of improving the characteristics is not clear, but the raw material phthalonitrile or 1,3-
The solubility of diiminoisoindoline and by-products at the time of production, which adversely affects the properties, in 1,3-dimethyl-2-imidazolidinone is high, and the purity of the product can be improved without performing a special purification operation as in the conventional method. It is presumed that a high metal phthalocyanine is obtained. As a result, according to the present invention, a metal phthalocyanine useful as a photoconductive material can be obtained without performing a special refining operation.

[0063]

Industrial Applicability As described above, according to the production method of the present invention, a metal phthalocyanine having excellent photoconductivity can be easily produced, and the metal phthalocyanine obtained by the production method of the present invention is electrophotographic. As a photoconductor material for
Further, it can be applied as a raw material for various photoconductive materials derived from metal phthalocyanine by crystal type conversion, chemical modification and the like.

[Brief description of drawings]

FIG. 1 is an infrared spectrum diagram of metal phthalocyanine obtained in Example 1.

2 is an X-ray diffraction pattern of the metal phthalocyanine obtained in Example 1. FIG.

FIG. 3 is an infrared spectrum diagram of the metal phthalocyanine obtained in Example 2.

4 is an X-ray diffraction pattern of the metal phthalocyanine obtained in Example 2. FIG.

5 is an X-ray diffraction diagram of metal phthalocyanine obtained in Comparative Example 1. FIG.

6 is an X-ray diffraction diagram of metal phthalocyanine obtained in Comparative Example 2. FIG.

7 is an X-ray diffraction diagram of metal phthalocyanine obtained in Example 3. FIG.

FIG. 8 is a schematic cross-sectional view showing the layer structure of a laminated electrophotographic photosensitive member prepared to evaluate the metal phthalocyanine obtained in each of Examples and Comparative Examples.

Claims (4)

[Claims] 1. A method for producing a metal phthalocyanine by reacting a metal salt (A) with phthalonitrile or 1,3-diiminoisoindoline (B) in a solvent,
A method for producing a metal phthalocyanine, which comprises using a solvent containing 1,3-dimethyl-2-imidazolidinone as a solvent. 2. The method for producing a metal phthalocyanine according to claim 1, wherein the metal salt (A) is a metal halide. 3. The method for producing a metal phthalocyanine according to claim 2, wherein the metal halide is indium halide. 4. The method for producing a metal phthalocyanine according to claim 2, wherein the metal halide is gallium halide.