JP3475078B2 - Method for producing phthalocyanine compound - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a novel phthalocyanine compound. In particular, it relates to a method for producing a phthalocyanine compound having absorption in the near infrared region and high solubility in a solvent. The phthalocyanine compound obtained by the production method of the present invention is 600 to 10
Since it has absorption in the near-infrared region of 00 nm, a near-infrared absorbing dye or near-infrared sensitizer for writing or reading in an optical recording medium using a semiconductor laser, a liquid crystal display device, an optical character reader, etc. , Thermal transfer, photothermal conversion agent such as thermal paper and thermal stencil, near-infrared absorption filter for PDP, eye fatigue preventing agent, near-infrared absorption material used as photoconductive material, or color separation used for image pickup tube Filter, color filter for liquid crystal display, color CRT selective absorption filter, color toner, toner for flash fixing, inkjet ink, tamperproof bar code ink, microbial inactivating agent, photosensitive dye for tumor treatment, and It also exhibits excellent effects when used as a heat ray shading agent or heat storage heat insulating agent for automobiles or building materials. It is. The phthalocyanine compound obtained by the production method of the present invention is an optical recording medium such as a compact disc, a laser disc, an optical memory disc, an optical card, a color filter for liquid crystal display, and a PD.
It exhibits an excellent effect when used as a near infrared ray absorbing filter for P or the like or a heat ray shielding agent.

[0002]

2. Description of the Related Art In recent years, development of optical recording media such as compact discs, laser discs, optical memory discs and optical cards using a semiconductor laser as a light source has been active. In particular, CD, PHOTO-CD or CD-RO
M is used as a large-capacity, high-speed access digital recording medium for mass storage and reproduction of sounds, images, code data, and the like. All of these systems require so-called near-infrared absorbing dyes that are sensitive to a semiconductor laser, and those dyes having good characteristics are required. Among them, many phthalocyanine-based compounds, which are stable to light, heat, temperature, etc. and have excellent fastness, are being investigated so as to be dissolved in a solvent required depending on the application. That is, in practice, a method for forming a thin film of a dye without using a complicated process such as vapor deposition or dispersion in a resin, using a solvent that does not attack the substrate used in the device, or dissolving it in a resin used together For this reason, there is a demand for dyes that can be dissolved in high concentrations in various solvents according to their respective uses.

There is also a demand for a light-shielding agent which shields heat rays in so-called glazing applications such as buildings and vehicles. Various phthalocyanine compounds have been proposed because of their high heat resistance and light resistance. Further, various phthalocyanine compounds have been proposed for color filter dyes for liquid crystal displays and near infrared cut filters for PDPs.

In the method for synthesizing a phthalocyanine compound using orthophthalonitriles, orthophthalonitrile is reacted with a metal source. As the metal source of the raw material used for these, in general, halides, oxides, organic acid salts, metal powders and the like can be mentioned. Among them, the use of halides is the most common because of their high reactivity. However, the synthesis method using a halide has a problem that a halogen atom is mixed in the phthalocyanine skeleton and a halogen gas is generated in the synthesis process, which requires a manufacturing facility of a special material. Therefore, a method of using an oxide as a metal source has also been proposed. For example, it is an example of the production of vanadyl phthalocyanine from vanadium pentoxide (JP-A-6-256680 and JP-A-7-3620).
5, JP-A-63-210166, JP-A-3
-269063 publication, Japanese Patent Publication No. 7-17851 publication,
JP-A-6-41137). Of these, JP-A-6-2
In Japanese Patent No. 56680 and Japanese Patent Laid-Open No. 7-36205,
Although a synthesis method using α-chloronaphthalene as a solvent is disclosed, this method has a problem that the reactivity is poor and the yield cannot be increased because there is almost no solubility of vanadium pentoxide in α-chloronaphthalene. Was there. On the other hand, JP-A-63-210166 and JP-A-3-26
Japanese Patent Publication No. 9063, Japanese Patent Publication No. 7-17851, and Japanese Patent Laid-Open No. 6-41137 disclose a synthetic method using ethylene glycol as a solvent. In this method, an intermediate from phthalonitrile and ethylene glycol is disclosed. To react via. Certainly, the reactivity is improved by passing through the intermediate, but there was a problem that the selectivity of the phthalocyanine compound produced was poor and the purification process was complicated.

In recent years, the demand for a phthalocyanine compound having a high solvent solubility has increased, but a general method for increasing the solvent solubility is to introduce a bulky substituent on the benzene ring of the phthalocyanine skeleton. There is no example of using a metal oxide as a metal source in the synthesis example of a phthalocyanine compound having a relatively bulky substituent. This is because the orthophthalonitrile compound having a bulky substituent is inferior in reactivity due to steric hindrance or the like as compared with the orthophthalonitrile compound having no substituent or a small substituent. Therefore, the phthalocyanine compound having a relatively bulky substituent has been synthesized using a highly reactive halide. However, the use of a halide has a problem in that the substituent itself reacts with a halogen atom or the halogen atom is mixed in the phthalocyanine skeleton, thereby impairing the original properties of the phthalocyanine compound. For this reason, there is an increasing demand for the development of an efficient synthetic method using a metal oxide as a metal source.

[0006]

Therefore, an object of the present invention is to use a metal oxide as a metal source as a metal source in a method for producing a phthalocyanine compound which may have a substituent, and Disclosed is a novel production method which is carried out in the presence of a compound having a dissociation index pKa of an acid or a conjugate acid of 7.0 or less. In particular, the present invention provides a method useful for producing a phthalocyanine compound having a substituent imparting solubility. Another object of the present invention is to provide a method for producing a phthalocyanine compound which may have a substituent excellent in yield and purity.

[0007]

SUMMARY OF THE INVENTION The present inventors have found that the conventional method of simply using a metal oxide or metal chloride as a metal source provides high purity, high performance and practically significant solvent solubility. It has been found that it cannot be applied to the method for producing a phthalocyanine compound having, and in order to achieve the above-mentioned various objects,
As a result of intensive studies, the present invention has been completed.

That is, the object of the present invention is to: (1) Dissociation index pKa (acid or conjugate logarithm) is 7.0 or less of an organic sulfonic acid compound of the reciprocal of the dissociation constant of the acid and Sari
At least one compound selected from the group consisting of citric acid
This is achieved by a method for producing a phthalocyanine compound, which comprises reacting in the presence of a compound.

Another object of the present invention is to provide (2) the orthophthalonitrile compound which may have a substituent,
It can also be achieved by the method for producing a phthalocyanine compound according to (1), which is an orthophthalonitrile compound having a substituent having a σ _p value smaller than the σ _m value in the Hammett's rule.

Another object of the present invention is (3) in which the substituent having a σ _p value smaller than the σ _m value in the Hammett's rule is a halogen atom, —R ¹ , —NHR ² , —NR.
³ R ⁴ , at least one substituent selected from the group consisting of —OR ⁵ and —SR ⁶ , said R ^{1 to} R ⁶ being an alkyl group or aryl group which may have a substituent. It is also achieved by the method for producing a phthalocyanine compound described in (2).

Still another object of the present invention is (4) the phthalocyanine compound according to any one of (1) to (3), wherein the metal oxide is an oxide of a metal having a valence of 2 or more. It is also achieved by the manufacturing method of.

[0012]

Still another object of the present invention is: (6) Production of the phthalocyanine compound according to any one of (1) to (5), wherein the reaction is carried out in an organic solvent medium. It is also achieved by the method.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing a phthalocyanine compound according to the present invention, a metal oxide is used as a metal source.
No. 80, No. 7-36205, No. 63
-210166, JP-A-3-269063, JP-B-7-17851), it is not practically sufficient, and there is no production example in which a bulky substituent is introduced on the phthalocyanine skeleton. It was discovered and a new manufacturing method was found.

That is, in the method for producing a phthalocyanine compound of the present invention, a dissociation index pKa (acid or conjugate acid) of an acid or a conjugate acid in an aqueous solution at 25 ° C. of an orthophthalonitrile compound which may have a substituent and a metal oxide is used. The logarithm of the reciprocal of the dissociation constant of the conjugate acid) is 7.0 or less, and is selected from the group consisting of organic sulfonic acid compounds and salicylic acid.
It is characterized by reacting in the presence of at least one compound . Preferably, the orthophthalonitrile compound is an orthophthalonitrile compound having a substituent having a σ _p value smaller than the σ _m value in Hammett's rule.

In the present production method, an organic solvent having an acid or conjugate acid dissociation index pKa (logarithm of reciprocal of dissociation constant of acid or conjugate acid) in an aqueous solution at 25 ° C. of 7.0 or less is used .
Selected from the group consisting of rufonic acid compounds and salicylic acid
The present invention has been completed by the present inventors finding that the compound formed by acting as a catalyst and generating an active species with a metal oxide enhances the reactivity with orthophthalonitrile. is there.

In the production method of the present invention, both an unsubstituted orthophthalonitrile compound and a substituted orthophthalonitrile compound can be used. The substituent is not particularly limited and includes, for example, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, amino group (including substituted amino group), alkoxy group, aryloxy group, acylamino group, Aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, sulfonylamino group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, A silyloxy group, an aryloxycarbonyl group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group or the like can be used.

The substituent is preferably a substituent having a σ _p value in Hammett's rule smaller than a σ _m value. Such a substituent is not particularly limited, for example,
Halogen atom, alkyl group, aryl group, heterocyclic group,
Hydroxy group, amino group (including substituted amino group), alkoxy group, aryloxy group, acylamino group, aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino group, carbamoyl And substituents such as a group, a sulfamoyl group, a heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an imide group, and a heterocyclic thio group. The type of the substituent in the orthophthalonitrile compound having the substituent may be one type or two or more types, and the number of the substituent may be any integer in the range of 1 to 4.

The orthophthalonitrile compound having a substituent having a σ _p value smaller than the σ _m value in the Hammett's rule preferably has 1 to 4 substituents, and the substituents are the same or different. Good halogen,-
^{R 1, -NHR 2, -NR 3} R 4, -OR 5 and -S
It is at least one substituent selected from the group consisting of R ⁶ , and R ^{1 to} R ⁶ are orthophthalonitrile compounds which are alkyl groups or aryl groups which may have a substituent.

Here, the halogen means fluorine, chlorine, bromine and iodine. Of these, chlorine or fluorine is preferable, and fluorine is particularly preferable.

Here, the alkyl group which may have a substituent and is represented by R ^{1 to} R ⁶ has 1 carbon atoms.
~ 20 straight chain, branched chain or cyclic alkyl group and halogen atom, alkoxy group, nitro group, amino group, alkoxycarbonyl group, halogenated alkoxy group, halogenated alkyl group, halogenated alkoxycarbonyl group,
Those alkyl groups having a substituent such as an aryl group, preferably a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms and a halogen atom, an alkoxy group, a nitro group, an amino group, An alkyl group having a substituent such as an alkoxycarbonyl group, a halogenated alkoxycarbonyl group and an aryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, and n.
-Propyl group, isopropyl group, n-butyl group, ter
t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, lauryl group, stearyl group, and halogen atom, alkyl group, alkoxy group, halogen Alkyl groups, halogenated alkoxy groups, nitro groups, amino groups, alkylamino groups, alkoxycarbonyl groups, halogenated alkoxycarbonyl groups, aryl groups and other such alkyl groups having a substituent.

Particularly preferably, the total atomic radius of atoms other than hydrogen atoms contained in the alkyl group is 3.0 Å or more. {Here, the atomic radius of the main atom is
The following numbers were used (unit: Å). Carbon = 0.77, oxygen = 0.74, nitrogen = 0.74, fluorine = 0.72, chlorine = 0.99, bromine = 1.14, silicon = 1.17, phosphorus = 1.10, sulfur = 1.04}. It is preferable that the phthalocyanine compound has a practically significant solvent solubility when it is 3.0 Å or more.

On the other hand, the aryl group which may have a substituent represented by R ^{1 to} R ⁶ is specifically a phenyl group, a tolyl group, a xylyl group, a mesityl group,
Aryl groups such as cumenyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group and halogen atoms, alkyl groups, alkoxy groups, halogenated alkyl groups, halogenated alkoxy groups, nitro groups, amino groups, alkylamino groups, alkoxycarbonyl Group, those aryl groups having a substituent such as a halogenated alkoxycarbonyl group and an aryl group, and the like, but preferably having a substituent such as a halogen atom, a halogenated alkyl group and a halogenated alkoxycarbonyl group. And aryl groups having substituents such as an alkoxy group and an aryl group.

Here, examples of the halogen atom which can be substituted on the above alkyl group or aryl group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these, a bromine atom is preferable.

Similarly, the alkyl group which can be substituted on the aryl group is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 8 carbon atoms. It is a branched or cyclic alkyl group. Specifically, straight chain such as methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group or the like Branched pentyl group, linear or branched hexyl group such as n-hexyl group, cyclohexyl group, linear or branched heptyl group, n-
Linear or branched octyl group such as octyl group, 2
-Linear or branched nonyl group such as ethylhexyl group, linear or branched decyl group such as n-decyl group, linear or branched undecyl group, linear or branched dodecyl group, lauryl group, stearyl group, halogen Those having substituents such as atoms, alkyl groups, alkoxy groups, halogenated alkyl groups, halogenated alkoxy groups, nitro groups, amino groups, alkylamino groups, alkoxycarbonyl groups, halogenated alkoxycarbonyl groups, aryl groups, etc. And an alkyl group of

The alkoxy group which can be substituted on the above alkyl group or aryl group is a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, preferably a linear chain having 1 to 8 carbon atoms. , A branched or cyclic alkoxy group. Specifically, methoxy group, ethoxy group, n-
Propyloxy group, isopropyloxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert
A linear or branched pentyloxy group such as a butoxy group or an n-pentyloxy group, a linear or branched hexyloxy group such as an n-hexyloxy group, a cyclohexyloxy group, a linear chain such as an n-heptyloxy group or Straight-chain or branched octyloxy group such as branched heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, straight-chain such as n-nonyloxy group or branched nonyloxy group, straight-chain such as n-decyloxy group Or a branched decyloxy group, a linear or branched undecyloxy group, a linear or branched dodecyloxy group, a methoxyethoxy group, an ethoxyethoxy group, a 3 ', 6'-oxaheptyloxy group,
3 ', 6'-oxaoctyloxy group, 3', 6 ',
9'-oxadecyloxy group, 3 ', 6', 9 ', 1
A 2'-oxatridecyloxy group, a methoxypropyloxy group, an ethoxypropyloxy group, a 4 ', 8'-oxanonyloxy group, a 4', 8'-oxadecyloxy group and the like are shown.

Further, the halogenated alkyl group which can be substituted with the above alkyl group or aryl group has 1 carbon atom.
To a straight chain, branched chain, or cyclic alkyl group having a halogen atom of 20 to 20 and preferably having 1 to 8 carbon atoms.
Is a halogenated part of a straight chain, branched chain or cyclic alkyl group. Particularly preferably, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is partly brominated. Specifically, chloromethyl group, bromomethyl group, dichloromethyl group, dibromomethyl group, trichloromethyl group, tribromomethyl group, 1-chloroethyl group, 1-bromoethyl group, 2-chloroethyl group, 2
-Bromoethyl group, 1,2-dichloroethyl group, 1,2
-Dibromoethyl group, 1,1-dichloroethyl group, 1,
1-dibromoethyl group, 2,2-dichloroethyl group,
2,2-dibromoethyl group, 1,1,2-trichloroethyl group, 1,1,2-tribromoethyl group, 1,2,2
-Trichloroethyl group, 1,2,2-tribromoethyl group, 1-chloropropyl group, 1-bromopropyl group, 2
-Chloro-1-propyl group, 2-bromo-1-propyl group, 3-chloro-1-propyl group, 3-bromo-1-propyl group, 1-chloro-2-propyl group, 1-bromo-
2-propyl group, 2,3-dichloro-1-propyl group,
2,3-dibromo-1-propyl group, 1,3-dichloro-2-propyl group, 1,3-dibromo-2-propyl group, 4-chloro-1-butyl group, 4-bromo-1-butyl group , 1-chloro-1-butyl group, 1-bromo-1-butyl group, 1-chloro-2-butyl group, 1-bromo-2-
Butyl group, 2-chloro-1-butyl group, 2-bromo-1
-Butyl group, 1,3-dichloro-2-butyl group, 1,3
-Dibromo-2-butyl group, 1,4-dichloro-2-butyl group, 1,4-dibromo-2-butyl group, 5-chloro-1-pentyl group, 5-bromo-1-pentyl group, 1-
Chloro-1-pentyl group, 1-bromo-1-pentyl group, 6-chloro-1-hexyl group, 6-bromo-1-hexyl group, 1-chloro-1-hexyl group, 1-bromo-
1-hexyl group, 7-chloro-1-heptyl group, 7-bromo-1-heptyl group, 1-chloro-1-heptyl group,
1-bromo-1-heptyl group, 8-chloro-1-octyl group, 8-bromo-1-octyl group, 1-chloro-1-
Octyl group, 1-bromo-1-octyl group, 9-chloro-1-nonyl group, 9-bromo-1-nonyl group, 1-chloro-1-nonyl group, 1-bromo-1-nonyl group, 10-
Chloro-1-decyl group, 10-bromo-1-decyl group,
1-chloro-1-decyl group, 1-bromo-1-decyl group, 11-chloro-1-undecyl group, 11-bromo-
1-undecyl group, 1-chloro-1-undecyl group, 1
-Bromo-1-undecyl group, 12-chloro-1-dodecyl group, 12-bromo-1-dodecyl group, 1-chloro-
1-dodecyl group, 1-bromo-1-dodecyl group and the like are shown.

Further, the halogenated alkoxy group which can be substituted with the above alkyl group or aryl group is one in which a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms is partially halogenated. , Preferably 1 carbon
The straight-chain, branched-chain, or cyclic alkoxy groups of ~ 8 are partially halogenated. Particularly preferably 1 carbon atom
Part of the linear, branched or cyclic alkoxy group of ~ 8 is brominated. Specifically, chloromethoxy group, bromomethoxy group, dichloromethoxy group, dibromomethoxy group, trichloromethoxy group, tribromomethoxy group, 1-chloroethoxy group, 1-bromoethoxy group, 2-chloroethoxy group, 2- Bromoethoxy group,
1,2-dichloroethoxy group, 1,2-dibromoethoxy group, 1,1-dichloroethoxy group, 1,1-dibromoethoxy group, 2,2-dichloroethoxy group, 2,2-dibromoethoxy group, 1, 1,2-trichloroethoxy group, 1,1,2-tribromoethoxy group, 1,2,2-
Trichloroethoxy group, 1,2,2-tribromoethoxy group, 1-chloropropoxy group, 1-bromopropoxy group, 2-chloro-1-propoxy group, 2-bromo-1-
Propoxy group, 3-chloro-1-propoxy group, 3-bromo-1-propoxy group, 1-chloro-2-propoxy group, 1-bromo-2-propoxy group, 2,3-dichloro-1-propoxy group, 2,3-dibromo-1-propoxy group, 1,3-dichloro-2-propoxy group, 1,3-
Dibromo-2-propoxy group, 4-chloro-1-butoxy group, 4-bromo-1-butoxy group, 1-chloro-1-
Butoxy group, 1-bromo-1-butoxy group, 1-chloro-2-butoxy group, 1-bromo-2-butoxy group, 2-
Chloro-1-butoxy group, 2-bromo-1-butoxy group, 1,4-dichloro-2-butoxy group, 1,4-dibromo-2-butoxy group, 5-chloro-1-pentyloxy group, 5- Bromo-1-pentyloxy group, 1-chloro-1-pentyloxy group, 1-bromo-1-pentyloxy group, 6-chloro-1-hexyloxy group, 6-bromo-1-hexyloxy group, 1- Chloro-1-hexyloxy group, 1-bromo-1-hexyloxy group, 7-chloro-1-heptyloxy group, 7-bromo-1-heptyloxy group, 1-chloro-1-heptyloxy group, 1-
Bromo-1-heptyloxy group, 8-chloro-1-octyloxy group, 8-bromo-1-octyloxy group, 1
-Chloro-1-octyloxy group, 1-bromo-1-octyloxy group, 9-chloro-1-nonyloxy group, 9
-Bromo-1-nonyloxy group, 1-chloro-1-nonyloxy group, 1-bromo-1-nonyloxy group, 10-
Chloro-1-decyloxy group, 10-bromo-1-decyloxy group, 1-chloro-1-decyloxy group, 1-bromo-1-decyloxy group, 11-chloro-1-undecyloxy group, 11-bromo-1 -Undecyloxy group, 1-chloro-1-undecyloxy group, 1-bromo-1-undecyloxy group, 12-chloro-1-dodecyloxy group, 12-bromo-1-dodecyloxy group, 1
-Chloro-1-dodecyloxy group, 1-bromo-1-dodecyloxy group, chloromethoxyethoxy group, bromomethoxyethoxy group, 1-chloroethoxyethoxy group, 1
-Bromoethoxyethoxy group, 1-chloro-3 ', 6'
-Oxaheptyloxy group, 1-bromo-3 ', 6'-
Oxaheptyloxy group, 1-chloro-3 ', 6'-oxaoctyloxy group, 1-bromo-3', 6'-oxaoctyloxy group, 1-chloro-3 ', 6', 9'-
Oxadecyloxy group, 1-bromo-3 ', 6', 9 '
-Oxadecyloxy group, 1-chloro-3 ', 6',
9 ', 12'-oxatridecyloxy group, 1-bromo-3', 6 ', 9', 12'-oxatridecyloxy group, chloromethoxypropoxy group, bromomethoxypropoxy group, 1-chloroethoxypropoxy group , 1-bromoethoxypropoxy group, 1-chloro-4 ', 8'-oxanonyloxy group, 1-bromo-4', 8'-oxanonyloxy group, 1-chloro-4 ', 8'-oxadecyl An oxy group, a 1-bromo-4 ′, 8′-oxadecyloxy group and the like are shown.

The alkylamino group which can be substituted on the aryl group is a linear, branched or cyclic alkylamino group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms.
Is a linear, branched or cyclic alkylamino group.
Specifically, methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, tert-butylamino group, n-pentylamino group, n-hexylamino group, cyclohexylamino group , N-octylamino group, 2-ethylhexylamino group, n-decylamino group and the like.

The alkoxycarbonyl group which can be substituted with the above alkyl group or aryl group has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, which may contain a hetero atom in the alkyl group portion of the alkoxy group. Group 3 or carbon atoms which may contain a hetero atom
8 and preferably a cyclic alkoxycarbonyl group having 5 to 8 carbon atoms. Specifically, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, linear or branched. Linear or branched hexyloxycarbonyl group such as pentyloxycarbonyl group, n-hexyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, cyclohexyloxycarbonyl, linear or branched heptyloxycarbonyl group, linear or branched octyl Oxycarbonyl group, straight-chain or branched nonyloxycarbonyl group, straight-chain or branched decyloxycarbonyl group, straight-chain or branched undecyloxycarbonyl group, straight-chain Dodecyloxycarbonyl group Rui branched, methoxyethoxy group, a cyclohexane methoxycarbonyl group, cyclohexane ethoxycarbonyl group, 3-cyclohexyl-1-
Propoxycarbonyl group, tert-butylcyclohexyloxycarbonyl group, phenoxycarbonyl group, 4
-Methylphenoxycarbonyl group, 4-chlorophenoxycarbonyl group, 4-cyclohexylphenoxycarbonyl group, 4-phenylphenoxycarbonyl group, 2-fluorophenoxycarbonyl group, 4-ethoxyphenoxycarbonyl group, ethoxyethoxycarbonyl group, butoxyethoxycarbonyl group , A diethylaminoethoxycarbonyl group, a methylthioethoxycarbonyl group, 3 ',
6'-oxaheptyloxycarbonyl group, 3 ', 6'
-Oxaoctyloxycarbonyl group, 3 ', 6',
9'-oxadecyloxycarbonyl group, 3 ', 6',
9 ', 12'-oxatridecyloxycarbonyl group,
Methoxypropyloxycarbonyl group, ethoxypropyloxycarbonyl group, 4 ', 8'-oxanonyloxycarbonyl group, 4', 8'-oxadecyloxycarbonyl group, 4 ', 8', 12'-oxatridecyloxycarbonyl group Group, tetrahydrofurfuryloxycarbonyl group, pyranoxycarbonyl group, piperidinooxycarbonyl group, piperidinoethoxycarbonyl group, tetrahydropyrroleoxycarbonyl group, tetrahydropyranmethoxycarbonyl group, tetrahydrothiopheneoxycarbonyl group, cyclohexyloxycarbonyl group , Benzyloxycarbonyl group, phenethyloxycarbonyl group, 3-phenyl-1-propoxycarbonyl group, 4-phenyl-1-butoxycarbonyl group, 5-phenyl-1-pentoxycarbo group Nyl group, 6-phenyl-
1-hexyloxycarbonyl group, 2-tetrahydrofuranoxycarbonyl group, 4-tetrahydropyranooxycarbonyl group, 2-pyrrolidinooxycarbonyl group,
2-piperidinooxycarbonyl group, 2-tetrahydrothiopheneoxycarbonyl group, tetrahydrofurfuryloxycarbonyl group, 4-tetrahydropyranooxycarbonyl group, 2-morpholinoethoxycarbonyl group, 2-pyrrolidinoethoxycarbonyl group, 2 -Piperazino ethoxycarbonyl group etc. are shown.

The halogenated alkoxycarbonyl group which can be substituted with the above alkyl group or aryl group has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, which may contain a hetero atom in the alkyl group portion of the alkoxy group. Part of the alkoxycarbonyl group is halogenated or part of the cyclic alkoxycarbonyl group having 3 to 8 carbon atoms, preferably 5 to 8 carbon atoms, which may contain a hetero atom is halogenated. . Specifically, a chloromethoxycarbonyl group, a bromomethoxycarbonyl group, a 2-chloroethoxycarbonyl group, a 2-bromoethoxycarbonyl group, a 3-chloro-1-propoxycarbonyl group, 3
-Bromo-1-propoxycarbonyl group, 2-chloro-
1-propoxycarbonyl group, 2-bromo-1-propoxycarbonyl group, 1-chloro-2-propoxycarbonyl group, 1-bromo-2-propoxycarbonyl group,
2,3-dichloro-1-propoxycarbonyl group, 2,
3-dibromo-1-propoxycarbonyl group, 1,3-
Dichloro-2-propoxycarbonyl group, 1,3-dibromo-2-propoxycarbonyl group, 1-chloro-2-
Butoxycarbonyl group, 1-bromo-2-butoxycarbonyl group, 2-chloro-1-butoxycarbonyl group, 2
-Bromo-1-butoxycarbonyl group, 4-chloro-1
-Butoxycarbonyl group, 4-bromo-1-butoxycarbonyl group, 1,4-dichloro-2-butoxycarbonyl group, 1,4-dibromo-2-butoxycarbonyl group,
5-chloro-1-pentyloxycarbonyl group, 5-bromo-1-pentyloxycarbonyl group, 6-chloro-
1-hexyloxycarbonyl group, 6-bromo-1-hexyloxycarbonyl group, 7-chloro-1-heptyloxycarbonyl group, 7-bromo-1-heptyloxycarbonyl group, 8-chloro-1-octyloxycarbonyl group , 8-bromo-1-octyloxycarbonyl group, 9-chloro-1-nonyloxycarbonyl group, 9-
Bromo-1-nonyloxycarbonyl group, 10-chloro-1-decyloxycarbonyl group, 10-bromo-1-
Decyloxycarbonyl group, 11-chloro-1-undecyloxycarbonyl group, 11-bromo-1-undecyloxycarbonyl group, 12-chloro-1-dodecyloxycarbonyl group, 12-bromo-1-dodecyloxycarbonyl group Etc.

The aryl group which may be substituted on the above alkyl group or aryl group is an aryl group which may have a substituent. Specifically, phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-ethylphenyl group, m-ethylphenyl group,
p-ethylphenyl group, o-propylphenyl group, m-
Propylphenyl group, p-propylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group,
p-isopropylphenyl group, o-butylphenyl group,
m-butylphenyl group, p-butylphenyl group, ot
ert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl Group, p-ethoxyphenyl group, o-propoxyphenyl group, m-propoxyphenyl group, p-propoxyphenyl group, o-isopropoxyphenyl group, m-isopropoxyphenyl group, p-isopropoxyphenyl group, o-butoxy group Phenyl group, m-butoxyphenyl group, p-butoxyphenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenyl group, 2,6-dipropylphenyl group, 2,6-diisopropylphenyl group,
2,6-dibutylphenyl group, 2,6-ditert-butylphenyl group, 2,6-dimethoxyphenyl group, 2,
6-diethoxyphenyl group, 2,6-dipropoxyphenyl group, 2,6-diisopropoxyphenyl group, 2,6
-Dibutoxyphenyl group, 2-fluorophenyl group, 2
-Chlorophenyl group, 2-bromophenyl group, 2-iodophenyl group, 3-fluorophenyl group, 3-chlorophenyl group, 3-bromophenyl group, 3-iodophenyl group, 4-fluorophenyl group, 4-chlorophenyl group,
4-bromophenyl group, 4-iodophenyl group, 2,3
-Difluorophenyl group, 2,3-dichlorophenyl group, 2,4-difluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,5-difluorophenyl group, 2,5-dichlorophenyl group,
2,6-difluorophenyl group, 2,6-dichlorophenyl group, 2,6-dibromophenyl group, 3,4-difluorophenyl group, 3,4-dichlorophenyl group, 3,5
-Difluorophenyl group, 3,5-dichlorophenyl group, 2,3,4-trifluorophenyl group, 2,3,4
-Trichlorophenyl group, 2,3,5-trifluorophenyl group, 2,3,5-trichlorophenyl group, 2,
3,6-trifluorophenyl group, 2,3,6-trichlorophenyl group, 2,4,6-trifluorophenyl group, 2,4,6-trichlorophenyl group, 2,4,6-
A tribromophenyl group, a 2,4,6-triiodophenyl group, a 2,3,5,6-tetrafluorophenyl group, a pentafluorophenyl group, a pentachlorophenyl group and the like are shown.

The type of the substituent of the alkyl group or the aryl group having the above-mentioned substituent may be one type or two or more types.

On the benzene nucleus of the orthophthalonitrile compound, the above-mentioned --R ¹ , --NHR ² , --NR ³ R ⁴ ,
When it is substituted with 1 to 3 substituents represented by —OR ⁵ and —SR ⁶ , the residue is preferably halogen. Of these, a fluorine atom or a chlorine atom is preferable, and a fluorine atom is particularly preferable.

Specific examples of the above-mentioned orthophthalonitrile compound include orthophthalonitrile, 3-nitrophthalonitrile, 3- (2-ethoxy) carbonylphthalonitrile, 3-trifluoromethylphthalonitrile and tetrafluorophthalonitrile. Nitrile, 3,4,5-trifluorophthalonitrile, 3,4,6-trifluorophthalonitrile, 3,4-difluorophthalonitrile,
3,5-difluorophthalonitrile, 3,6-difluorophthalonitrile, 4,5-difluorophthalonitrile, 3-fluorophthalonitrile, 4-fluorophthalonitrile, tetrachlorophthalonitrile, 3,4,5-
Trichlorophthalonitrile, 3-chloro-4-fluorophthalonitrile, 4-tert-butylphthalonitrile, 4-hydroxyphthalonitrile, 4-aminophthalonitrile, 3,5,6-trifluoro-4-methylaminophthalonitrile, 4-ethylamino-3,5,6-trifluorophthalonitrile, 4-butylamino-3,
5,6-Trifluorophthalonitrile, 4-anilino-
3,5,6-trifluorophthalonitrile, 3,5,6
-Trifluoro-4- (o-toluidino) phthalonitrile, 3,5,6-trifluoro-4- (p-toluidino) phthalonitrile, 3,5,6-trifluoro-4-
(2,4-xylidino) phthalonitrile, 3,5,6-
Trifluoro-4- (2,6-xylidino) phthalonitrile, 4- (o-chloroanilino) -3,5,6-trifluorophthalonitrile, 4- (p-chloroanilino)
-3,5,6-trifluorophthalonitrile, 4-
(2,4-Dichloroanilino) -3,5,6-trifluorophthalonitrile, 4- (2,6-dichloroanilino) -3,5,6-trifluorophthalonitrile, 4-
(O-Fluoroanilino) -3,5,6-trifluorophthalonitrile, 4- (p-fluoroanilino) -3,
5,6-trifluorophthalonitrile, 4- (2,3,
5,6-Tetrafluoroanilino) -3,5,6-trifluorophthalonitrile, 3,5,6-trifluoro-
4-methoxyphthalonitrile, 4-ethoxy-3,5
6-trifluorophthalonitrile, 4-butoxy-3,
5,6-trifluorophthalonitrile, 3,5,6-trifluoro-4-phenoxyphthalonitrile, 3,5,5
6-trifluoro-4- (o-methylphenoxy) phthalonitrile, 3,5,6-trifluoro-4- (p-methylphenoxy) phthalonitrile, 3,5,6-trichloro-4- (p-methyl) Phenoxy) phthalonitrile,
3,5,6-Trifluoro-4- (2,4-dimethylphenoxy) phthalonitrile, 3,5,6-trifluoro-4- (2,6-dimethylphenoxy) phthalonitrile, 4- (o-chloro Phenoxy) -3,5,6-trifluorophthalonitrile, 4- (p-chlorophenoxy) -3,5,6-trifluorophthalonitrile, 4-
(2,4-dichlorophenoxy) -3,5,6-trifluorophthalonitrile, 4- (2,6-dichlorophenoxy) -3,5,6-trifluorophthalonitrile, 4
-(O-Fluorophenoxy) -3,5,6-trifluorophthalonitrile, 4- (p-fluorophenoxy)
-3,5,6-trifluorophthalonitrile, 4-
(2,3,5,6-tetrafluorophenoxy) -3,
5,6-trifluorophthalonitrile, 3,5,6-trifluoro-4- (2,6-dimethoxyphenoxy) phthalonitrile, 3,5,6-trifluoro-4- (2-
Methyl-6-methoxyethoxycarbonylphenoxy)
Phthalonitrile, 3,5,6-trifluoro-4- (2
-Methoxy-6-methoxyethoxycarbonylphenoxy) phthalonitrile, 3,5,6-trifluoro-4-
(2-Ethoxy-6-methoxyethoxycarbonylphenoxy) phthalonitrile, 3,5,6-trifluoro-
4- (2-methyl-6-tetrahydrofurfuryloxycarbonylphenoxy) phthalonitrile, 3,5,6-
Trifluoro-4- (2-methyl-6-methoxyethoxyethoxycarbonylphenoxy) phthalonitrile,
3,5,6-trifluoro-4- (2,6-dimethoxyethoxycarbonylphenoxy) phthalonitrile, 3,
5,6-trifluoro-4- (2-methoxyethoxycarbonyl-6-phenylphenoxy) phthalonitrile,
3,5,6-Trifluoro-4- (2-methoxyethoxyethoxycarbonyl-6-phenylphenoxy) phthalonitrile, 3,5,6-trifluoro-4- (2-tetrahydrofurfuryloxycarbonyl-6-phenyl Phenoxy) phthalonitrile, 3,5,6-trifluoro-4- (2- (2-propoxycarbonyl) -6-phenylphenoxy) phthalonitrile, 3,5,6-trifluoro-4- (2- (3 -Pentoxycarbonyl)-
6-phenylphenoxy) phthalonitrile, 3,5,6
-Trichloro-4- (2- (2-methoxyethoxy) carbonyl-6-methylphenoxy) phthalonitrile,
3,5,6-Trifluoro-4- (2- (2,4-dimethyl-3-pentoxycarbonyl) -6-phenylphenoxy) phthalonitrile, 3,5,6-trifluoro-
4- (2- (2,6-dimethyl-4-heptyloxycarbonyl) -6-phenylphenoxy) phthalonitrile, 4- (2- (1,3-dibromo-2-propoxycarbonyl) -6-phenyl) phenoxy -3, 5, 6-
Trifluorophthalonitrile, 4- (2-bromoethoxycarbonyl-6-phenyl) phenoxy-3,5,6
-Trifluorophthalonitrile, 4- (2,4-di (6
-Bromohexyloxycarbonyl) -6-phenyl)
Phenoxy-3,5,6-trifluorophthalonitrile, 4- (2- (1-bromo-2-propoxycarbonyl) -6-phenyl) phenoxy-3,5,6-trifluorophthalonitrile, 4- (2 -(1,4-Dibromo-2-butoxycarbonyl) -6-phenyl) phenoxy-3,5,6-trifluorophthalonitrile, 4-
(6- (Bromophenyl) -2- (2-propoxycarbonyl)) phenoxy-3,5,6-trifluorophthalonitrile, 4- (bromo-2- (2-propoxycarbonyl) -6-phenyl) phenoxy- 3,5,6-trifluorophthalonitrile, 3,6-difluoro-4,
5-bismethylthiophthalonitrile, 3,6-difluoro-4,5-bisethylthiophthalonitrile, 3,6-
Difluoro-4,5-bisbutylthiophthalonitrile,
3,6-difluoro-4,5-bis (tert-butylthio) phthalonitrile, 3,6-difluoro-4,5-
Bisphenylthiophthalonitrile, 4,5-bisethylphenylthio-3,6-difluorophthalonitrile,
3,6-Difluoro-4,5-bispropylphenylthiophthalonitrile, 4,5-bisbutylphenylthio-
3,6-difluorophthalonitrile, 3,6-difluoro-4,5-bis (tert-butylphenylthio) phthalonitrile, 3,6-difluoro-4,5-bis (o
-Tolylthio) phthalonitrile, 3,6-difluoro-
4,5-bis (p-tolylthio) phthalonitrile, 3,
6-difluoro-4,5-bis (m-tolylthio) phthalonitrile, 3,6-difluoro-4,5-bis (2,2
4-xylylthio) phthalonitrile, 3,6-difluoro-4,5-bis (2,3-xylylthio) phthalonitrile, 3,6-difluoro-4,5-bis (2,6-xylylthio) phthalonitrile, 4 , 5-bis (o-chlorophenylthio) -3,6-difluorophthalonitrile, 4,5-bis (p-chlorophenylthio) -3,6
-Difluorophthalonitrile, 4,5-bis (2,4-
Dichlorophenylthio) -3,6-difluorophthalonitrile, 4,5-bis (2,6-dichlorophenylthio) -3,6-difluorophthalonitrile, 3,6-difluoro-4,5-bis (o-fluorophenyl) Thio)
Phthalonitrile, 3,6-difluoro-4,5-bis (p-fluorophenylthio) phthalonitrile, 3,6
-Difluoro-4,5-bis (2,3,5,6-tetrafluorophenylthio) phthalonitrile, 4-anilino-5-phenylthio-3,6-difluorophthalonitrile, 4-anilino-5-butoxy-3 , 6-Difluorophthalonitrile, 4-butylthio-5-phenoxy-
3,6-difluorophthalonitrile, 4-butoxy-5
-Phenoxy-3,6-difluorophthalonitrile, 4
-Anilino-5- (o-toluidino) -3,6-difluorophthalonitrile, 3-fluoro-4,5,6-triphenoxyphthalonitrile, 3,4,5,6-tetraphenylthiophthalonitrile, 4- Phenylthio-3,
5,6-Trifluorophthalonitrile, 4- (2-ethoxycarbonyl-6-methyl) phenoxy-3,5,6
-Trifluorophthalonitrile, 4- (2-phenyl)
Examples thereof include phenoxy-3,5,6-trifluorophthalonitrile and 4,5-diphenoxy-3,6-difluorophthalonitrile.

The metal oxide used in the present invention is not particularly limited, and vanadium, titanium, iron, magnesium, nickel, cobalt, copper, silver,
Examples thereof include oxides such as palladium, zinc, germanium, tin, silicon and lithium. Specifically, vanadium monoxide, vanadium trioxide, vanadium tetroxide, vanadium pentoxide, titanium dioxide, iron monoxide, iron sesquioxide, ferric tetroxide, manganese oxide, nickel monoxide, cobalt monoxide, sesquioxide. Cobalt, cobalt dioxide, cuprous oxide,
Cupric oxide, copper sesquioxide, palladium oxide, zinc oxide,
Examples thereof include oxides such as germanium monoxide, germanium dioxide, stannous oxide, stannic oxide, silicon monoxide, silicon dioxide and lithium oxide. It is preferably a metal oxide having a valence of 2 or more, more preferably a metal oxide having a valence of 3 or more, such as titanium oxide and vanadium oxide, and particularly preferably vanadium oxide. Examples of vanadium oxides include vanadium trioxide, vanadium tetraoxide, vanadium pentoxide, and the like. Of these, lower oxides are preferable, and vanadium trioxide is particularly preferable. The use of the metal oxide has an advantage that chlorine atoms are not mixed in the phthalocyanine skeleton as compared with the conventional method for producing phthalocyanine using chloride as the metal salt.

The amount of the metal oxide blended with respect to the orthophthalonitrile compound may be a stoichiometric amount or more, but the metal oxide is preferably used in an amount of 1 to 2 equivalents, preferably 4 equivalents of the orthophthalonitrile compound. Is 1.1 to 1.5
It is desirable to mix in the equivalent range. If the amount of the metal oxide is less than 1 equivalent to 4 equivalents of the orthophthalonitrile compound, it is not preferable because the metal oxide is insufficient in terms of stoichiometry and a metal-free phthalocyanine compound is produced as a by-product. Oxide is orthophthalonitrile compound 4
When the amount is more than 2 equivalents relative to the equivalent amount, a large amount of unreacted metal oxide remains, which is uneconomical, and it is not preferable because it takes time to recover or remove these in the purification step.

In the production method of the present invention, an organic sulfonic acid compound having an acid or conjugate acid dissociation index pKa (logarithm of reciprocal of dissociation constant of acid or conjugate acid) in an aqueous solution at 25 ° C. of 7.0 or less. And from the group consisting of salicylic acid
Although it is carried out in the presence of the selected compound , p
In the case of Ka 7.0 or less, multi-step dissociation is performed, and even if the pKa exceeds 7.0 in the second and subsequent dissociation stages, 1
It is selected from the group consisting of an organic sulfonic acid compound having a pKa of the dissociation stage of 7.0 or less and salicylic acid.
Compounds are also included. Preferably, an organic sulfonic acid compound and salicyl having a pKa of 7.0 or less in all dissociation stages
It is at least one compound selected from the group consisting of acids . More preferably, the organic sulfonic acid compound and salicylic acid are compounds having a pKa in the range of -5.0 to 5.0 .
It is carried out in the presence of a compound selected from the group consisting of That is, when synthesizing a phthalocyanine compound by reacting an orthophthalonitrile compound and a metal oxide, an organic sulfonic acid compound and a saponification compound having a dissociation index pKa of an acid or a conjugate acid in an aqueous solution at 25 ° C. of 7.0 or less are used.
It has been found that the presence of a compound selected from the group consisting of lithic acid acts as an extremely useful catalyst. The organic sulfonic acid compound and Sa
When the pKa of the compound selected from the group consisting of lithic acid exceeds 7.0, the activity as a catalyst is insufficient and the phthalocyanination reaction does not proceed easily, which is not preferable.

It is selected from the group consisting of organic sulfonic acid compounds and salicylic acid having a dissociation index pKa of the acid or conjugate acid in an aqueous solution of 25 ° C. used in the present invention.
The compound formed by Bale, is not particularly limited, for example, m - aniline sulfonic acid, p- aniline sulfonic acid, p - toluenesulfonic acid, salicylic acid, meta <br/> Nsuruhon acid, ethanesulfonic Acid, 1,2-ethanedisulfonic acid, trifluoromethanesulfonic acid, 3-hydroxypropanesulfonic acid, 1,3-propanedisulfonic acid, heptadecafluorooctanesulfonic acid, benzenesulfonic acid, p-phenolsulfonic acid, 2-nitrobenzene Sulfonic acid, 3-nitrobenzenesulfonic acid, 4
-Nitrobenzenesulfonic acid, 4-chlorobenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, 2,5
-Dichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid, picrylsulfonic acid, 5-sulfosalicylic acid, 4-nitrotoluene-2-sulfonic acid,
4-sulfophthalic acid, 4-ethylbenzenesulfonic acid,
m-xylene-4-sulfonic acid, p-xylene-2-sulfonic acid, mesitylenesulfonic acid, dodecylbenzenesulfonic acid, 2-naphthalenesulfonic acid, pyridine-3-
Sulfonic acid, 2,5-dichlorosulfanilic acid, 4-chloroaniline-3-sulfonic acid, 2-amino-4-chlorophenol-6-sulfonic acid, 3-nitroaniline-
4-sulfonic acid, 2-aminobenzenesulfonic acid, 3-
Aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-aminophenol-4-sulfonic acid, 4-amino-2-chlorotoluene-5-sulfonic acid, 5-amino-2-chlorotoluene-4-sulfonic acid, 2 (2-pyridyl) ethanesulfonic acid, 2 (4-pyridyl) ethanesulfonic acid, m-toluidine-4-sulfonic acid, p-toluidine-2-sulfonic acid, o-anisidine-5-sulfonic acid, p-anisidine 2-sulfonic acid, p-anisidine-3-sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3-cyclohexylaminopropanesulfonic acid, 8-anilino-1-naphthalenesulfonic acid and the like can be used. Organic sulfonic acid compound
And a compound selected from the group consisting of salicylic acid, when an organic solvent is used in the production of phthalocyanine, the solubility in the organic solvent used is higher than that of the inorganic compound, and the reaction promoting effect is improved. Therefore, it is preferable. Organic sulfonic acid compounds and salicyl
Among the compounds selected from the group consisting of acids, organic sulfonic acid compounds are more preferable. Among the organic sulfonic acid compounds, methanesulfonic acid, ethanesulfonic acid, 1,2-ethanedisulfonic acid, trifluoromethanesulfonic acid, 3-hydroxypropanesulfonic acid,
1,3-propanedisulfonic acid, heptadecafluorooctanesulfonic acid, benzenesulfonic acid, p-phenolsulfonic acid, p-toluenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-nitrobenzenesulfonic acid, 4
-Nitrobenzenesulfonic acid, 4-chlorobenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, 2,5
-Dichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid, picrylsulfonic acid, 5-sulfosalicylic acid, 4-nitrotoluene-2-sulfonic acid,
4-sulfophthalic acid, 4-ethylbenzenesulfonic acid,
m-xylene-4-sulfonic acid, p-xylene-2-sulfonic acid, mesitylenesulfonic acid, dodecylbenzenesulfonic acid, 2-naphthalenesulfonic acid and the like are preferable,
Particularly, p-toluenesulfonic acid is preferable because it can be easily obtained when industrialized. The amount of the compound used is
Since it is not included in the stoichiometric reaction formula for the reaction system because it is used as a catalyst, the existing amount before and after the reaction does not change.For example, when the reaction is performed in a batch system, the amount of orthophthalonitrile is Sufficient catalytic action can be obtained by charging 0.05 to 5 mol%.

In the method for producing a phthalocyanine compound of the present invention, the above-mentioned orthophthalonitrile compound and the above-mentioned metal oxide are used as an organic sulfonic acid compound having a pKa of 7.0 or less .
And the reaction is carried out in the presence of a compound selected from the group consisting of salicylic acid, and the reaction conditions at this time are a reaction temperature of 30 to 250 ° C., preferably 80 to 20.
It is 0 ° C. When the reaction temperature is lower than 80 ° C., the reaction rate is remarkably slowed due to a decrease in catalytic activity and the time required for synthesis is remarkably prolonged, which is not economical.
Further, when the synthesis is carried out at a high temperature exceeding 200 ° C., the amount of by-products produced increases, which is not preferable.

In the production method of the present invention, the above metal oxide and an organic sulfonic acid compound having a pKa of 7.0 or less and
It is also possible to use a method in which a compound selected from the group consisting of bismuth acid and salicylic acid is mixed in advance, and after a certain period of time, the above-mentioned orthophthalonitrile compound is added to start the reaction. When this method is used, the active species of the reaction are generated before the addition of the orthophthalonitrile compound, so that the reaction may proceed faster.

Further, in the manufacturing method of the phthalocyanine compound of the present invention, the pKa of 7.0 or less of the organic sul
Selected from the group consisting of phosphonic acid compounds and salicylic acid
In the presence of the compound, the reaction of the orthophthalonitrile compound and the metal oxide can be performed in the absence of a solvent,
Preference is given to using organic solvents. Any organic solvent may be used as long as it is an inert solvent which does not react with the starting material, and examples thereof include nitromethane, nitroethane, nitrobenzene, triethylamine, tri-n-butylamine, and the like.
Nitrogen compound solvents such as N, N-dimethylformamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, acetonitrile and benzonitrile, and hydrocarbon-based solvents such as benzene, toluene, xylene, naphthalene and 1-methylnaphthalene. Solvent, monochlorobenzene,
Halogenated hydrocarbon solvents such as dichlorobenzene, trichlorobenzene and 1-chloronaphthalene, alcohol solvents such as n-octanol and ethylene glycol,
A sulfur compound-based solvent such as dimethyl sulfoxide or sulfolane can be used, preferably a nitrogen compound-based solvent, a hydrocarbon-based solvent or a halogenated hydrocarbon-based solvent, and particularly, an organic sulfone having a pKa of 7.0 or less. A compound selected from the group consisting of acid compounds and salicylic acid
Enhance the catalytic ability of a product, preferably nitrogen compound-based solvent because it has the effect of accelerating the generation of active species, especially benzonitrile are preferred.

Further, in the production method of the present invention, when the orthophthalonitrile compound contains a chlorine atom, a fluorine atom or the like, hydrochloric acid gas or hydrofluoric acid gas may be generated in the production process. These gases may cause problems such as corrosion of manufacturing equipment depending on the amount generated. Therefore, these gas trapping agents may be mixed. As such a trapping agent, oxides, hydroxides, carbonates and the like of alkaline earth metals are preferable, and carbonates of alkaline earth metals are particularly preferable.

A desired phthalocyanine compound can be synthesized by the above-mentioned manufacturing method, but preferably has absorption in the near infrared region and uses an optical recording medium using a semiconductor laser, a liquid crystal display device, a near infrared absorption. Dyes, near-infrared sensitizers, photothermal conversion agents for heat transfer, near-infrared absorbing materials such as near-infrared absorbing filters for PDPs, color separation filters, liquid crystal display color filters, optical color filters, plasma display display colors. filter,
Color cathode ray tube selective absorption filter, color toner,
It is desirable to synthesize a phthalocyanine compound having an excellent effect on an ink jet ink, a heat ray shielding agent, a heat storage heat retaining fiber and the like. The central metal of such a phthalocyanine compound is not particularly limited as long as it is selected from a metal and a metal oxide, but an oxymetal containing a divalent metal atom or a tetravalent metal is preferable. Examples of the oxymetal containing a divalent metal atom or a tetravalent metal include iron,
Magnesium, nickel, cobalt, copper, palladium,
An oxymetal containing a divalent metal atom such as zinc and a tetravalent metal such as titanyl and vanadyl can be mentioned, but an oxymetal containing a tetravalent metal is particularly preferable, and vanadyl is particularly preferable.

Specific examples of the phthalocyanine compound synthesized by the production method of the present invention include the following compounds.

Tetra-tert-butyl copper phthalocyanine, copper phthalocyanine, titanyl phthalocyanine, tetrakis nitro nickel phthalocyanine, tetrakis (n
-Butoxy) cobalt phthalocyanine, tetrakis (methoxycarbonyl) vanadyl phthalocyanine, octakisbutylthiooctafluorovanadyl phthalocyanine,
Tetrabutoxide dodecafluorozinc phthalocyanine and the like can be mentioned, but a phthalocyanine compound having a somewhat bulky substituent is preferable.

Such a phthalocyanine compound is a phthalocyanine compound having a bulky substituent represented by the following general formula (1).

[0048]

[Chemical 1]

(In the formula, X and Y-R represent a substituent substituting at any of 16 substitutable positions of the benzene nucleus of the phthalocyanine skeleton, and M represents a metal, a metal oxide or a halogen. Represents a metal oxide, Y is O,
Represents either one selected from S and NH, and R
Represents an alkyl group or an aryl group which may have a substituent, X represents a hydrogen atom or a halogen atom (preferably a halogen atom), and m is an integer of 0 to 16 (preferably 4 to 16). , N is an integer of 0 to 16 (preferably 0 to 12), m + n is an integer of 16 or less, and the total atomic radius of atoms other than hydrogen atoms contained in R is 4.0 Å or more. ) Examples of such a phthalocyanine compound include hexadecafluorovanadyl phthalocyanine, hexadecachlorovanadyl phthalocyanine, tetrakis (2-phenyl-6- (2-propyl) phenoxy) dodecafluorozinc phthalocyanine, tetrakis (2,6-diphenylphenoxy). Dodecafluorovanadyl phthalocyanine,
Tetrakis (2,4-diphenylphenoxy) dodecafluorotitanyl phthalocyanine, tetrakis (2,4,
6-triphenylphenoxy) dodecafluorovanadyl phthalocyanine, tetrakis (4- (2- (2-methoxyethoxy) carbonyl-6-methylphenoxy)) dodecafluorovanadyl phthalocyanine, tetrakis (2
-Isopropoxycarbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine, tetrakis (2- (3-pentoxy) carbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine,
Tetrakis (2- (3-pentoxy) carbonyl-4-
Phenylphenoxy) dodecafluorocopper phthalocyanine, tetrakis (2-tertbutoxycarbonyl-6)
-Phenylphenoxy) dodecafluorovanadyl phthalocyanine, tetrakis (2,4-diisopropoxycarbonyl-6-phenylphenoxy) dodecafluoroiron phthalocyanine, tetrakis (2- (2-butoxy) carbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine , Tetrakis (2- (2-pentoxy) carbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine, tetrakis (2- (3-
Methoxypropoxy) carbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine, tetrakis (2,4-di (2-methoxyethoxy) carbonyl-6-phenylphenoxy) dodecafluoronickel phthalocyanine, tetrakis (2-ethoxy-6-phenylphenoxy) ) Dodecafluorovanadyl phthalocyanine, tetrakis (2,4-diethoxy-6-phenylphenoxy) dodecafluoropalladium phthalocyanine,
Tetrakis (2-benzyloxycarbonyl-6-phenylphenoxy) dodecafluorotitanyl phthalocyanine, tetrakis (2-phenethyloxycarbonyl-6)
-Phenylphenoxy) dodecafluorozinc phthalocyanine, tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-6-phenylphenoxy) dodecafluorotitanyl phthalocyanine, tetrakis (4-
(2-Tetrahydrofurfuryloxy) carbonyl-6
-Phenylphenoxy) dodecafluoropalladium phthalocyanine, tetrakis (2,4-di (2-tetrahydrofurfuryloxy) carbonyl-6-phenylphenoxy) dodecafluorocobalt phthalocyanine, tetrakis (6- (bromophenyl) -2-isopropoxycarbonyl Phenoxy) dodecafluorovanadyl phthalocyanine, tetrakis (bromo-2-isopropoxycarbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine, tetrakis (6- (4-bromomethylphenyl) -2- (2-tetrahydrofurfuryloxy) carbonyl Phenoxy) dodecafluorotitanyl phthalocyanine, tetrakis (6- (4-bromomethoxyphenyl) -2- (2-isopropoxycarbonylphenoxy) dodeca Le Oro vanadyl phthalocyanine, tetrakis (2- (1,3-dibromo-2-propoxycarbonyl) -6-phenylphenoxy) dodecafluoro vanadyl phthalocyanine, tetrakis (2,4-di (6
-Bromohexyloxycarbonyl) -6-phenylphenoxy) dodecafluorocopper phthalocyanine, tetrakis (2- (2-bromoethyl) -6-phenylphenoxy) dodecafluorovanadyl phthalocyanine, tetrakis (4- (2-bromoethoxy) -2- Isopropoxycarbonyl-6-phenylphenoxy) dodecafluoroiron phthalocyanine, tetrakis (2- (2-bromoethoxy) -6-phenylphenoxy) dodecafluorovanadyl phthalocyanine, tetrakis (2- (2-bromoethoxy) carbonyl-6-phenyl Phenoxy) dodecafluorovanadyl phthalocyanine, tetrakis (2-
(1-Bromo-2-propoxycarbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine, tetrakisanilinodododecafluoroiron phthalocyanine, octakisphenylthiooctafluorovanadyl phthalocyanine, tetrakis (p-methylphenoxy) dodecafluorocopper phthalocyanine, octakis (2,4-
Xylylthio) octafluoronickel phthalocyanine, tetrakis (2,3,5,6-tetrafluorophenoxy) dodecafluoroiron phthalocyanine, tetrakis (2,6-dichloroanilino) titanyl phthalocyanine, octaphenoxyoctafluorovanadyl phthalocyanine, and tetrakis (4 Examples include-(p-methylphenoxy))-dodecachlorovanadyl phthalocyanine.

[0050]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

Example 1 [Tetrakis (2- (2-propoxy) carbonyl-6]
-Phenylphenoxy) dodecafluorovanadyl phthalocyanine production] In a 100 ml four neck flask,
5,6-trifluoro-4- (2- (2-propoxy))
Carbonyl-6-phenylphenoxy) phthalonitrile 4.36 g (0.01 mol), vanadium trioxide 0.2
25 g (1.5 mmol), 0.029 g (0.15 mmol) of p-toluenesulfonic acid monohydrate and 15 ml of benzonitrile were charged and reacted at 190 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to give the desired green cake (tetrakis (2- (2-propoxy) carbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine). 3.62 g was obtained. The yield was 80% based on phthalonitrile. The visible absorption spectrum, solubility, and elemental analysis results of the obtained target product are shown in Table 1 below.

[0052]

[Table 1]

Example 2 [Preparation of tetrakis (2- (1,3-dibromo-2-propoxy) carbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine] 3,5,6-in a 100 ml four-necked flask. Trifluoro-4- (2-
(1,3-dibromo-2-propoxy) carbonyl-6
-Phenylphenoxy) phthalonitrile 5.94 g
(0.01 mol), vanadium trioxide 0.210 g
(1.4 mmol), p-toluenesulfonic acid monohydrate 0.057 g (0.3 mmol) and benzonitrile 15 ml were charged and reacted at 190 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to give the desired green cake (tetrakis (2- (1,3-dibromo-2-propoxy) carbonyl-6-phenylphenoxy). ) Dodecafluorovanadyl phthalocyanine) (4.59 g) was obtained. The yield was 75% based on phthalonitrile. The visible absorption spectrum, solubility, and elemental analysis results of the obtained target product are shown in Table 2 below.

[0054]

[Table 2]

Example 3 [Preparation of tetrakis (2- (2-methoxyethoxy) carbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine] 3,5,6-trifluoro-4-in a 100 ml four-necked flask. 4.52-g (0.01 mol) of (2- (2-methoxyethoxy) carbonyl-6-phenylphenoxy) phthalonitrile, 0.225 g (1.5 mmol) of vanadium trioxide, 0.041 g (0.3 mmol) of salicylic acid and 15 ml of benzonitrile was charged and reacted at 190 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to give the target green cake (tetrakis (2- (2-methoxyethoxy) carbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine. ) 1.97 g were obtained. The yield was 42% based on phthalonitrile. The visible absorption spectrum, solubility, and elemental analysis results of the obtained target product are shown in Table 3 below.

[0056]

[Table 3]

[0057]

[0058]

Example 5 [Preparation of tetrakis (2- (2-methoxyethoxy) carbonyl-6-methylphenoxy) dodecafluorovanadyl phthalocyanine] 3,5,6-trifluoro-4-in a 100 ml four-necked flask. (2- (2-Methoxyethoxy) carbonyl-6-methylphenoxy) phthalonitrile 3.90 g (0.01 mol), vanadium pentoxide 0.273 g (1.5 mmol), p-toluenesulfonic acid monohydrate 0 0.057 g (0.3 mmol) and 15 ml of benzonitrile were charged and reacted at 190 ° C. for 6 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to give the target green cake (tetrakis (2- (2-methoxyethoxy) carbonyl-6-methylphenoxy) dodecafluorovanadyl phthalocyanine. ) 1.75 g were obtained. The yield was 43% based on phthalonitrile. The visible absorption spectrum, solubility, and elemental analysis results of the obtained target product are shown in Table 5 below.

[0060]

[Table 5]

[0061]

[0062]

Example 7 [Production of hexadecafluorovanadyl phthalocyanine] 1
Tetrafluorophthalonitrile 2.00 g (0.01 mol), vanadium trioxide 0.225 g (1.5 mmol), p-toluenesulfonic acid monohydrate 0.086 g (0.45 mmol) in a 00 ml four-necked flask. ) And 15 ml of benzonitrile were charged and reacted at 190 ° C. for 20 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to obtain 1.52 g of the desired green cake (hexadecafluorovanadyl phthalocyanine). The yield was 70% based on phthalonitrile. The visible absorption spectrum and elemental analysis results of the obtained target product are shown in Table 7 below.

[0064]

[Table 7]

Example 8 [Production of hexadecafluorovanadyl phthalocyanine] 1
Tetrafluorophthalonitrile 2.00 g (0.01 mol), vanadium pentoxide 0.236 g (1.3 mmol), p-toluenesulfonic acid monohydrate 0.086 g (0.45 mmol) in a 00 ml four-necked flask. ) And 15 ml of benzonitrile were charged and reacted at 190 ° C. for 10 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to obtain 1.00 g of a target green cake (hexadecafluorovanadyl phthalocyanine). The yield was 46% based on phthalonitrile. The visible absorption spectrum and elemental analysis results of the obtained target product are shown in Table 8 below.

[0066]

[Table 8]

Example 9 [Production of tetrakis (2- (2-methoxyethoxy) carbonyl-6-methylphenoxy) dodecachlorovanadyl phthalocyanine] 3,5,6-trichloro-4- (in a 100 ml four-necked flask. 2- (2-methoxyethoxy) carbonyl-6-methylphenoxy) phthalonitrile 4.40 g (0.01 mol), vanadium trioxide 0.225 g (1.5 mmol), p-toluenesulfonic acid monohydrate 0.1. 095 g (0.5 mmol) and 15 ml of benzonitrile were charged and reacted at 190 ° C. for 6 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to give the desired green cake (tetrakis (2- (2-methoxyethoxy) carbonyl-6-methylphenoxy) dodecachlorovanadyl phthalocyanine. ) 3.16 g were obtained. The yield was 72% based on phthalonitrile. The visible absorption spectrum and elemental analysis results of the obtained target product are shown in Table 9 below.

[0068]

[Table 9]

Example 10 [Synthesis of octakisphenylthiooctafluorovanadyl phthalocyanine (abbreviation: VOPc (PhS) ₈ F ₈ )] 3,6-difluoro-4,5-bisphenylthio was placed in a 100 ml four-necked flask. Phthalonitrile 10g
(26.2 mmol), vanadium trioxide 0.6 g (4
Mmol), p-toluenesulfonic acid monohydrate 0.19
g (1 mmol) and 50 ml of benzonitrile were charged, and then the mixture was reacted at 190 ° C. for 5 hours. After cooling, the resulting green solid is filtered, washed with acetone and VO
31.5 g of Pc (PhS) ₈ F ₈ was obtained. Yield 3,6
-76% with respect to difluoro-4,5-bisphenylthiophthalonitrile. The visible absorption spectrum and elemental analysis results of the obtained target product are shown in Table 10 below.

[0070]

[Table 10]

Example 11 [Synthesis of octaphenoxyoctafluorovanadyl phthalocyanine (abbreviation: VOPc (PhO) ₈ F ₈ )] 10
In a 0 ml 4-necked flask, 3,6-difluoro-4,
9.12 g of 5-bisphenoxyphthalonitrile (26.
2 mmol), vanadium trioxide 0.6 g (4 mmol), p-toluenesulfonic acid monohydrate 0.19 g (1
(Mmol) and benzonitrile (50 ml) were added, and the mixture was reacted at 190 ° C for 5 hours. After cooling, the green solid obtained was filtered, washed with acetone and washed with VOPc.
27.8 g of (PhO) ₈ F ₈ was obtained. The yield was 73% based on 3,6-difluoro-4,5-bisphenoxyphthalonitrile. The visible absorption spectrum and elemental analysis results of the obtained target product are shown in Table 11 below.

[0072]

[Table 11]

Example 12 [Production of hexadecachlorovanadyl phthalocyanine] 10
In a 0 ml four-necked flask, 2.66 g (0.01 mol) of tetrachlorophthalonitrile, vanadium trioxide (0.1 mol) were added.
194 g (1.3 mmol) p-toluenesulfonic acid-
A hydrate (0.095 g, 0.50 mmol) and benzonitrile (15 ml) were charged and reacted at 190 ° C for 10 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to obtain the desired green cake (hexadecachlorovanadyl phthalocyanine).
2.12 g was obtained. Yield is 75 based on phthalonitrile
%Met. The visible absorption spectrum and elemental analysis results of the obtained target product are shown in Table 12 below.

[0074]

[Table 12]

Example 13 [Production of titanyl phthalocyanine] 1.28 g (0.01) of orthophthalonitrile was placed in a 100 ml four-necked flask.
Mol), 0.240 g of titanium dioxide (3.0 mmo
l), p-toluenesulfonic acid monohydrate 0.095 g
(0.50 mmol) and 15 ml of benzonitrile were charged and reacted at 190 ° C. for 10 hours. After the reaction was completed, the solvent was distilled off, and the resulting solid content was methyl alcohol 200 m.
By washing with l, 0.86 g of the target green cake (titanyl phthalocyanine) was obtained. The yield was 60% based on phthalonitrile. The visible absorption spectrum and elemental analysis results of the obtained target product are shown in Table 13 below.

[0076]

[Table 13]

Example 14 [Production of tetrakis (2-ethoxyethoxy) dodecafluorovanadyl phthalocyanine] 0.225 g (1.5 m) of vanadium trioxide was placed in a 100 ml four-necked flask.
mol), p-toluenesulfonic acid monohydrate 0.076
g (0.40 mmol) and benzonitrile 15 ml
Was charged for 1 hour at 190 ° C., 2.70 g (0.01 mol) of 3,5,6-trifluoro-4- (2-ethoxyethoxy) phthalonitrile was charged, and the mixture was further reacted at 190 ° C. for 8 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to obtain a target green cake (tetrakis (2-ethoxyethoxy) dodecafluorovanadyl phthalocyanine) .2.
05 g was obtained. The yield was 75% based on phthalonitrile. The visible absorption spectrum and elemental analysis results of the obtained target product are shown in Table 14 below.

[0078]

[Table 14]

Comparative Example 1 3,5,6-trifluoro-4- (2- (2-propoxy) carbonyl-6-in a 100 ml four-necked flask.
Phenylphenoxy) phthalonitrile 4.36 g (0.
01 mol), 0.273 g of vanadium pentoxide (1.5 m
mol) and 15 ml of α-chloronaphthalene were charged and reacted at 200 ° C. for 4 hours, but the desired phthalocyanine compound was not obtained at all.

Comparative Example 2 3,5,6-trifluoro-4- (2- (1,3-dibromo-2-propoxy) carbonyl-6-phenylphenoxy) phthalonitrile in a 100 ml four-necked flask. 94 g (0.01 mol), 0.273 g (1.5 mmol) of vanadium pentoxide and 15 ml of ethylene glycol were charged and reacted at 190 ° C. for 4 hours, but the desired phthalocyanine compound was not obtained at all.

Comparative Example 3 The same preparation and reaction as in Comparative Example 1 except that vanadium trioxide was used instead of vanadium pentoxide in Comparative Example 1, but the desired phthalocyanine compound was not obtained at all.

Comparative Example 4 The procedure of Comparative Example 1 was repeated except that vanadium trichloride was used instead of vanadium pentoxide. The desired phthalocyanine compound was obtained in a low yield of 8%. As a result of elemental analysis, the obtained phthalocyanine compound contained 2% of chlorine atoms.

[0083]

INDUSTRIAL APPLICABILITY In the production method of the present invention, a metal oxide (particularly vanadium trioxide (V ₂ O ₃ )) is used as a raw material for a metal salt, and a new catalyst, p
Ka (the logarithm of the reciprocal of the dissociation constant of an acid or a conjugate acid) is 7.0 or less, and an organic sulfonic acid compound and salicylic acid
By using a compound selected from the group consisting of (preferably an organic sulfonic acid compound, especially p-toluenesulfonic acid), orthophthalonitrile having a relatively bulky substituent which has conventionally been low in reactivity. The phthalocyanine compound can be produced in high yield from the compounds, the reaction progresses quickly, and purification is complicated because impurities such as halogen atoms other than the designed substituents are not mixed in the phthalocyanine compound. Nonetheless, it has a peculiar effect that a high-purity phthalocyanine compound can be obtained at a relatively low cost as compared with a conventional synthesis method.

Continuation of the front page (56) Reference JP-A-63-210166 (JP, A) JP-A-6-256680 (JP, A) JP-A-3-269063 (JP, A) JP-A-7-36205 (JP , A) Japanese Patent Publication 7-17851 (JP, B2) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09B 47/067 G03G 5/06

Claims (5)

(57) [Claims] 1. A dissociation index pKa of an acid or a conjugate acid in an aqueous solution of an orthophthalonitrile compound which may have a substituent and a metal oxide at 25 ° C. (logarithm of reciprocal of dissociation constant of acid or conjugate acid). ) Is 7.0 or less, selected from the group consisting of organic sulfonic acid compounds and salicylic acid.
A method for producing a phthalocyanine compound, which comprises reacting in the presence of a compound. 2. The orthophthalonitrile compound which may have a substituent has a σ _p value of σ _{m according to} Hammett's rule.
The method for producing a phthalocyanine compound according to claim 1, which is an orthophthalonitrile compound having a substituent smaller than the above value. 3. The substituent having a σ _p value smaller than the σ _m value in the Hammett's rule is a halogen atom, —R ¹ , —NHR ² ,
At least one substituent selected from the group consisting of —NR ³ R ⁴ , —OR ⁵ and —SR ⁶ , wherein R ^{1 to} R ⁶ are an alkyl group or an aryl group which may have a substituent. A method for producing the phthalocyanine compound according to claim 2. 4. The method for producing a phthalocyanine compound according to claim 1, wherein the metal oxide is an oxide of a metal having a valence of 2 or more. 5. The method for producing a phthalocyanine compound according to claim 1, wherein the reaction is carried out in an organic solvent medium.