JP2000169743A - Production of phthalocyanine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a phthalocyanine compound capable of preventing or reducing to an extremely low level the corrosion of a reactor due to a hydrophoric and generated as a by-product in the process of the phthalocyamine reaction in the industrial production of a phthalocyanine compound. SOLUTION: In the process of producing a phthalocyanine compound from a halogen-containing phthalonitrile compound and a metal oxide, an alkaline earth metal compound is permitted to coexist in the process and be reacted together. Alternatively, an alkaline earth metal compound is permitted to coexist and be reacted together in the process of producing a phthalocyanine compound from a halogen-containing phthalonitrile compound and a metal oxide in the presence of a compound forming in the aqueous solution thereof at 25 deg.C an acid or a conjugated acid having a dissociation index pKa (the logarithmic value of the reciprocal of the dissociation constant of the acid or the conjugated acid) of not more than 7.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing a phthalocyanine compound. In particular, the present invention relates to a method for producing a phthalocyanine compound having high solubility in a solvent. Since the phthalocyanine compound obtained by the production method of the present invention has an absorption in the near-infrared region of 600 to 1000 nm, the optical recording medium using a semiconductor laser, a liquid crystal display, an optical character reader or the like for writing or reading. -Infrared absorbing dyes, near-infrared sensitizers, thermal transfer agents, photothermal conversion agents such as thermal paper / thermosensitive stencils, near-infrared absorbing filters for plasma display (PDP), eye strain inhibitor, photoconductive Near-infrared absorbing material used as material, or color separation filter used for image pickup tube, color filter for liquid crystal display, selective absorption filter for color CRT, color toner, dye for flash fixing toner, ink for inkjet, anti-tampering Barcode inks, microbial deactivators, photosensitive dyes for treating tumors, Heat ray shielding agent of an automobile or building material, in which further exhibits an excellent effect when used as a resin segmentation determination agent.

[0002]

2. Description of the Related Art The need for near-infrared absorbing dyes has been increasing as their fields of use have expanded, and they have been required for writing or reading in optical recording media using semiconductor lasers, liquid crystal displays, optical character readers, and the like. Near-infrared absorbing dyes, near-infrared sensitizers, thermal transfer, light-to-heat conversion agents such as thermal paper / thermosensitive stencils, near-infrared absorbing filters, anti-eye strain agents, and near-infrared absorbing materials used as photoconductive materials Or color separation filters for LCD tubes, color filters for liquid crystal displays, color CRT selective absorption filters, color toners, ink-jet inks, tamper-proof counterfeiting barcode inks, microbial deactivators, and photosensitivity for tumor treatment Dyes, as well as near-infrared absorbing dyes used in heat-ray shielding agents for automobiles and building materials, Materials that satisfy all properties such as heat resistance, heat resistance, and solubility (or compatibility with resin) are required. Various properties such as light resistance, heat resistance, and solubility (or compatibility with resin) are required. Have not existed or been developed.

For example, phthalocyanine dyes are excellent in light resistance and heat resistance but low in solubility, and have a short absorption wavelength.

[0004] However, phthalocyanine compounds are
Various types have been proposed because of their high heat resistance and light resistance, and a number of production methods have been proposed. Among them, a method of reacting a phthalonitrile compound with a metal source in an organic solvent is generally used.

[0005] As a metal source of the raw material used for these, generally, halides, oxides, organic acid salts, metal powders and the like can be mentioned. Of these, the use of halides is most common because of its high reactivity. However, the synthesis method using a halide has a problem that a halogen atom is mixed into the phthalocyanine skeleton, and a halogen gas is generated in the synthesis step, so that a special material manufacturing facility is required. Therefore, a method using an oxide as a metal source has been proposed. Japanese Patent Application Laid-Open No. 6-25
No. 6,680, JP-A-7-36205 discloses a synthesis method using vanadium pentoxide and α-chloronaphthalene. However, in this method, vanadium pentoxide has almost no solubility in α-chloronaphthalene. There was a problem that the reactivity was poor and the yield did not increase. On the other hand, JP-A-63-210166, JP-A-3-269063, JP-B-7-17851 and JP-A-6-41137 disclose a synthesis method using vanadium pentoxide and ethylene glycol. However, in this method, the reaction is carried out via an intermediate from phthalonitrile and ethylene glycol. Although the reactivity is certainly improved by passing through the intermediate, there is a problem that the selectivity of the phthalocyanine compound to be produced is poor and the purification step becomes complicated.

[0006] In recent years, there has been an increasing demand for phthalocyanine compounds having high solvent solubility. A general method for increasing the solvent solubility is to introduce a somewhat bulky substituent on the benzene ring of the phthalocyanine skeleton. There is no synthesis example of a phthalocyanine compound having a relatively bulky substituent, using a metal oxide as a metal source. The reason for this is that the orthophthalonitrile compound having a bulky substituent has lower reactivity due to steric hindrance and the like than the unsubstituted or orthophthalonitrile compound having a small substituent. For this reason, synthesis of a phthalocyanine compound having a relatively bulky substituent has been performed using a halide having high reactivity. However, there has been a problem that the use of a halide causes the substituent itself to react with a halogen atom or the halogen atom to be mixed into the phthalocyanine skeleton, thereby impairing the inherent characteristics of the phthalocyanine compound. For these reasons, there is an increasing demand for the development of an efficient synthesis method using a metal oxide as a metal source. However, when a phthalonitrile compound containing a halogen atom is used as a raw material, there has been a problem that a part of the halogen atom is eliminated during the reaction and the reaction apparatus is corroded.

[0007]

In view of the above-mentioned problems, an object of the present invention is to provide a wide variety of phthalocyanine compounds, particularly near-infrared absorbing dyes or precursors thereof, higher dyes, etc., from halogen-containing phthalonitrile compounds and metal oxides. Fields, for example, optical recording media having absorption in the near-infrared region and using a semiconductor laser, liquid crystal display, near-infrared absorbing dye, near-infrared sensitizer, photothermal conversion agent such as thermal transfer, near-infrared absorbing filter, etc. Near-infrared absorbing material, color separation filter, liquid crystal display color filter, optical color filter,
In the industrial production of useful phthalocyanine compounds that can be used in color filters for plasma display displays, color CRT selective absorption filters, color toners, inkjet inks, etc., hydrofluoric acid by-produced during the phthalocyanine conversion reaction It is an object of the present invention to provide a method for producing a phthalocyanine compound which can prevent or reduce the corrosion of a reactor caused by hydrohalic acid to a very low level.

Another object of the present invention is to provide a method for producing a phthalocyanine compound from a halogen-containing phthalonitrile compound and a metal oxide in a wide range of fields as a near-infrared absorbing dye, a precursor thereof, a higher dye, and the like. , An optical recording medium that has absorption in the near infrared region and uses a semiconductor laser, a liquid crystal display device, a near infrared absorbing dye, a near infrared sensitizer,
Light-to-heat conversion agents such as thermal transfer, near-infrared absorbing materials such as near-infrared absorbing filters, color separation filters, liquid crystal display color filters, optical color filters, plasma display color filters, color CRT selective absorption filters, color toners, An object of the present invention is to provide a method capable of producing a useful phthalocyanine compound which can be used for an ink-jet ink or the like at a yield equivalent to a laboratory scale even on an industrial scale.

An object of the present invention is to provide a method for producing a phthalocyanine compound which may have a substituent from a halogen-containing phthalonitrile compound and a metal source, wherein a metal oxide is used as a metal source and the halogen-containing phthalonitrile compound is used as a raw material. It is intended to provide a novel production method which can enhance the reactivity with a compound and is not only practically sufficient compared to the conventional method but also can introduce a bulky substituent on a phthalocyanine skeleton. . In particular, the present invention provides a method useful for producing a phthalocyanine compound having a substituent that imparts solubility.

Another object of the present invention is to provide a method for producing a phthalocyanine compound which may have a substituent which is excellent in yield and purity.

[0011]

Means for Solving the Problems Accordingly, the present inventors have:
In the conventional method using only a metal oxide or a metal halide as a metal source, it is difficult to produce a phthalocyanine compound having high purity, high performance, and practically significant solvent solubility while preventing corrosion of the reactor. It has been found that the present invention is impossible, and as a result of intensive studies to achieve the above objects, the present invention has been completed.

That is, an object of the present invention is to provide (1) a phthalocyanine compound characterized by reacting in the presence of an alkaline earth metal compound when producing a phthalocyanine compound from a halogen-containing phthalonitrile compound and a metal oxide. Can be achieved.

Another object of the present invention is to provide (2) a dissociation index pKa (reciprocal of the dissociation constant of an acid or conjugate acid) of an acid or a conjugate acid in an aqueous solution at 25 ° C. from a halogen-containing phthalonitrile compound and a metal oxide. When a phthalocyanine compound is produced in the presence of a compound having a logarithmic value of 7.0 or less, the phthalocyanine compound can be produced by a method for producing a phthalocyanine compound, which comprises reacting in the presence of an alkaline earth metal compound. .

Further, the object of the present invention is to provide (3) a method for producing a phthalocyanine compound as described in the above (1) or (2), wherein stirring is carried out with a stirring power of 0.03 kW / m ³ or more during the reaction. Can also be achieved.

Still another object of the present invention is to provide (4) the above (1), wherein the reaction is carried out in an organic solvent.
It can also be achieved by the method for producing a phthalocyanine compound according to any one of (1) to (3).

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a phthalocyanine compound according to the present invention is characterized in that when producing a phthalocyanine compound from a halogen-containing phthalonitrile compound and a metal oxide, an alkaline earth metal compound is allowed to coexist and react. Things. Thereby, in the industrial production of useful phthalocyanine compounds that can be used for various applications, reactor corrosion by hydrohalic acid such as hydrofluoric acid by-produced during the phthalocyanine reaction is prevented or extremely reduced. Thus, the corrosion of the reactor can be suppressed.

Further, in the method for producing a phthalocyanine compound of the present invention, a metal oxide is used as a metal source, but a conventional production method using a metal oxide (JP-A-6-2566)
No. 80, JP-A-7-36205, JP-A-63
JP-A-210166, JP-A-3-269063, and JP-B-7-17851) are not only insufficient for practical use, but there is no production example in which a bulky substituent is introduced on a phthalocyanine skeleton. It has been found and a new manufacturing method has been found.

That is, the method for producing a phthalocyanine compound of the present invention comprises the steps of: producing a dissociation index pKa (reciprocal of the dissociation constant of an acid or conjugate acid) of an acid or conjugate acid in an aqueous solution at 25 ° C. from a halogen-containing phthalonitrile compound and a metal oxide; When a phthalocyanine compound is produced in the presence of a compound having a logarithmic value of 7.0 or less, the reaction is carried out in the presence of an alkaline earth metal compound.

In the present production method, a compound having a dissociation index pKa (logarithm of the reciprocal of the dissociation constant of an acid or conjugate acid) of an acid or conjugate acid in an aqueous solution at 25 ° C. of 7.0 or less acts as a catalyst, By generating an active species between the oxide and the oxide, the reactivity with the halogen-containing phthalonitrile compound can be increased, which is not only practically sufficient as compared with the conventional method but also bulky on the phthalocyanine skeleton. This can be said to be extremely excellent in that a substituent can be introduced.

In the present invention, when a phthalocyanine compound is produced, an alkaline earth metal compound such as an oxide, hydroxide or carbonate of an alkaline earth metal is added to the reaction system in order to prevent corrosion of the reactor and the like. It has the characteristic of reacting. As a result, a reactive hydrohalic acid such as hydrofluoric acid generated by nucleophilic substitution is promptly reacted with an alkaline earth metal compound, thereby trapping as a noncorrosive halide such as fluoride. It can be removed from the system.

Further, when an alkaline earth metal compound is added and reacted, hydrohalic acid such as hydrofluoric acid generated by a side reaction is quickly trapped, so that by-products are formed and decomposition of the target product is performed. In addition to suppressing the side reaction, the yield and selectivity are improved, and purification steps such as washing can be simplified.

Although an alkali metal compound is also effective in trapping hydrohalic acid such as hydrofluoric acid, the alkali metal is too basic and causes a side reaction such as hydroxylation. It is not appropriate to do so.

The alkaline earth metal compound is not particularly limited as long as it can effectively trap hydrohalic acid such as hydrofluoric acid in a reaction solvent.
Alkaline earth metal compounds such as oxides, hydroxides, organic salts and inorganic salts of alkaline earth metals, and specifically,
Calcium acetate, calcium acetylacetonate, calcium carbonate, calcium phosphate, calcium silicate,
Calcium compounds such as calcium citrate, calcium formate, calcium hydroxide, calcium oxalate, calcium oxide and calcium stearate, magnesium acetate, magnesium acetylacetonate, magnesium carbonate, magnesium phosphate, magnesium silicate, magnesium citrate, and magnesium Magnesium compounds such as magnesium oxalate, magnesium hydroxide, magnesium oxalate, magnesium oxide and magnesium stearate;
Barium compounds such as barium acetate, barium acetylacetonate, barium carbonate, barium phosphate, barium silicate, barium citrate, barium formate, barium hydroxide, barium oxalate, barium oxide and barium stearate, strontium acetate, strontium Acetylacetonate, strontium carbonate, strontium phosphate, strontium silicate, strontium citrate, strontium formate, strontium hydroxide,
Examples include strontium compounds such as strontium oxalate, strontium oxide and strontium stearate. These may be used alone or in a combination of two or more as long as they do not affect each other.

Among the above alkaline earth metal compounds,
(1) A calcium salt in a calcium compound is useful because it traps a hydrohalic acid such as HF and becomes a stable calcium halide such as CaF ₂ . Also,
(2) Use of an alkaline earth metal carbonate is advantageous because no acid remains. In this case, since the by-produced water may have an adverse effect, it is desirable to azeotropically distill the water with the reaction solvent.
Therefore, the reaction solvent that can be used in the present invention is desirably azeotropic with water or has a boiling point higher than that of water. From the viewpoints of the above (1) and (2), calcium carbonate is particularly preferable among the alkaline earth metal compounds.

The amount of the alkaline earth metal compound added to the reaction system is such that hydrohalic acid such as hydrofluoric acid generated by a side reaction is promptly reacted with the alkaline earth metal compound and trapped. It may be added as much as possible, but in order to stably trap hydrohalic acid such as hydrofluoric acid industrially stably, it is usually added in an amount of 0.1 to 1 mol of a halogen atom contained in the compound in the reaction system. 05-5
It is desirably 0 mol times, preferably 0.1 mol times to 10 mol times, particularly preferably 1.1 mol times to 1.5 mol times. If it is less than 0.05 mole times 1 mole of the halogen atom in the reaction system, H
The trapping of hydrohalic acid such as F is not sufficient, and the corrosion of the reactor and the like cannot be sufficiently prevented. Also,
If it exceeds 50 moles per mole of the halogen atom in the reaction system, no further effect corresponding to the excessive addition can be obtained, which is uneconomical from an industrial point of view. Alkaline earth metal compounds such as calcium are not preferred because they inhibit the nucleophilic substitution reaction.

In the production method of the present invention, any of a phthalonitrile compound having only a halogen atom and a phthalonitrile compound having both a halogen atom and another substituent can be used. Here, "halogen-containing"
The term refers to any of those having a halogen atom on the benzene ring of phthalonitrile and those having a halogen atom in a part of the substituent substituted on the benzene ring of phthalonitrile.

In the above-mentioned halogen-containing phthalonitrile compound, the substituents that can be substituted on the benzene ring of phthalonitrile (halogen atoms and other substituents (including those partially substituted by halogen atoms)) are not particularly limited. Are not, for example, a halogen atom, an 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, sulfonylamino, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocyclic oxy, azo, acyloxy, carbamoyloxy, silyloxy, aryloxycarbonyl, imide, heterocyclic thio Groups, sulfinyl groups, phosphoryl groups, acyl groups, and the like. The kind of the substituent may be one kind or two or more kinds, and the number of the substituents may be any integer in the range of 1 to 4, provided that at least one has no halogen atom. No. Hereinafter, representative ones of the above substituents will be described in more detail, but it goes without saying that the present invention is not limited to these.

First, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a chlorine atom or a fluorine atom is preferable, and a fluorine atom is particularly preferable. That is, by using a phthalonitrile compound in which a chlorine atom or a fluorine atom, particularly a fluorine atom is substituted, a part of the fluorine atoms in the raw material generates more corrosive hydrofluoric acid, but the present invention is particularly applicable. It works effectively and can prevent the corrosion of the reactor. In addition, phthalocyanine compounds containing chlorine or fluorine, especially fluorine, satisfy all the properties such as light resistance, heat resistance and solubility (or compatibility with resin). This is advantageous in obtaining the material.

Examples of the alkyl group include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a halogen atom, an alkoxy group, a nitro group, an amino group, an alkoxycarbonyl group, a halogenated alkoxy group, and a halogenated alkyl group. Group, a halogenated alkoxycarbonyl group, an alkyl group 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. And alkyl groups having a substituent such as a group, a nitro group, an amino group, an alkoxycarbonyl group, a halogenated alkoxycarbonyl group, and an aryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, and an n- Octyl group, 2-ethylhexyl group, n-decyl group, lauryl group, stearyl group, and halogen atom, alkyl group, alkoxy group, halogenated alkyl group, halogenated alkoxy group, nitro group, amino group, alkylamino group, alkoxy Examples thereof include an alkyl group having a substituent such as a carbonyl group, a halogenated alkoxycarbonyl group, and an aryl group.

Specific examples of the aryl group include an aryl group such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a biphenylyl group, a naphthyl group, an anthryl group and a phenanthryl group, a halogen atom, an alkyl group, And aryl groups having a substituent such as an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, a nitro group, an amino group, an alkylamino group, an alkoxycarbonyl group, a halogenated alkoxycarbonyl group, and an aryl group. Preferably, the aryl group having a substituent such as a halogen atom, a halogenated alkyl group, a halogenated alkoxycarbonyl group and the aryl group having a substituent such as an alkoxycarbonyl group and an aryl group. is there.

Here, the halogen atom which can be substituted for the above-mentioned alkyl group or aryl group includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Similarly, the alkyl group which can be substituted for 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.

The alkoxy group which can be substituted on the above-mentioned alkyl group or aryl group is a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, preferably a linear alkoxy group having 1 to 8 carbon atoms. , A branched or cyclic alkoxy group.

Further, the halogenated alkyl group or halogenated alkoxy group which can be substituted for the above-mentioned alkyl group or aryl group includes straight-chain, branched-chain or cyclic alkyl groups having 1 to 20 carbon atoms or part of alkoxy groups. Is halogenated, and preferably has 1 to 8 carbon atoms.
Are partially halogenated linear, branched or cyclic alkyl groups or alkoxy groups.

The alkylamino group which can be substituted for 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.

The alkoxycarbonyl group or the halogenated alkoxycarbonyl group which can be substituted on the alkyl group or the aryl group has 1 to 8 carbon atoms which may contain a hetero atom in the alkyl group of the alkoxy group, and preferably has 1 to 8 carbon atoms. It is an alkoxycarbonyl group or a halogenated alkoxycarbonyl group having 1 to 5 carbon atoms, or a cyclic alkoxycarbonyl group or a halogenated alkoxycarbonyl group having 3 to 8 carbon atoms, preferably 5 to 8 carbon atoms which may contain a hetero atom.

The aryl group which can be substituted for the above-mentioned alkyl group or aryl group is an aryl group which may have a substituent.

The above-mentioned alkyl or aryl group may have one or more substituents.

Further, regarding the alkoxy group, halogenated alkyl group, halogenated alkoxy group, alkylamino group, alkoxycarbonyl group and halogenated alkoxycarbonyl group which can be substituted on the benzene ring of the halogen-containing phthalonitrile compound, Or an alkoxy group which can be substituted with an aryl group, a halogenated alkyl group, a halogenated alkoxy group, an alkylamino group, an alkoxycarbonyl group and a halogenated alkoxycarbonyl group, as long as they are the same as those described above;
Here, the description is omitted.

Further, the benzene ring of the halogen-containing phthalonitrile compound may have a substituent other than the above-mentioned halogen atom substituted (for example, an alkyl group, an amino group (including an alkylamino group which is a substituted amino group), an alkoxy group). And when substituted with 1 to 3 substituents represented by an alkylthio group, etc., it is preferable that all residues are halogen atoms, more preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom or a chlorine atom. Is an atom.

Examples of the halogen-containing phthalonitrile compound of the present invention include, for example, 3-trifluoromethylphthalonitrile, tetrafluorophthalonitrile,
3,4,5-trifluorophthalonitrile, 3,4,6
-Trifluorophthalonitrile, 3,5-difluorophthalonitrile, 3,6-difluorophthalonitrile,
4,5-difluorophthalonitrile, 3-fluorophthalonitrile, 4-fluorophthalonitrile, tetrachlorophthalonitrile, 3,4,5-trichlorophthalonitrile, 3-chloro-4-fluorophthalonitrile, 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-xyridino) phthalonitrile, 4- (o-chloroanilino) -3,5,6-trifluorophthalonitrile,
4- (2,4-dichloroanilino) -3,5,6-trifluorophthalonitrile, 4- (2,6-dichloroanilino) -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-butoxy-3,5,6-trifluorophthalonitrile, 3,5,6-trifluoro-4-phenoxyphthalonitrile, 3,5,6-triphenyl Fluoro-4-
(O-methylphenoxy) phthalonitrile, 3,5,6
-Trichloro-4- (p-methylphenoxy) phthalonitrile, 3,5,6-trifluoro-4- (2,4-dimethylphenoxy) phthalonitrile, 3,5,6-trifluoro-4- (2, 6-dimethylphenoxy) phthalonitrile, 4- (o-chlorophenoxy) -3,5,6
-Trifluorophthalonitrile, 4- (2,6-dichlorophenoxy) -3,5,6-trifluorophthalonitrile, 4- (o-fluorophenoxy) -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-ethoxy-6-methoxyethoxycarbonylphenoxy) phthalonitrile, 3,5,6-trifluoro-4- (2- Methyl-6-tetrahydrofurfuryloxycarbonylphenoxy) phthalonitrile, 3,5,6-trifluoro-4- (2-methoxyethoxycarbonyl-6-phenylphenoxy) phthalonitrile, 3,5,6-trifluoro-4 -(2-tetrahydrofurfuryloxycarbonyl-6-phenylphenoxy) phthalonitrile, 3,
5,6-trifluoro-4- (2- (2-propoxycarbonyl) -6-phenylphenoxy) phthalonitrile, 3,5,6-trifluoro-4- (2- (2,4-
Dimethyl-3-pentoxycarbonyl) -6-phenylphenoxy) phthalonitrile, 4- (2- (1,3-dibromo-2-propoxycarbonyl) -6-phenyl)
Phenoxy-3,5,6-trifluorophthalonitrile, 4- (2- (1,4-dibromo-2-butoxycarbonyl) -6-phenyl) phenoxy-3,5,6-trifluorophthalonitrile, 3, 6-difluoro-4,
5-bisbutylthiophthalonitrile, 3,6-difluoro-4,5-bis (tert-butylthio) phthalonitrile, 3,6-difluoro-4,5-bisphenylthiophthalonitrile, 4,5-bisethylphenyl Thio-
3,6-difluorophthalonitrile, 3,6-difluoro-4,5-bispropylphenylthiophthalonitrile, 4,5-bisbutylphenylthio-3,6-difluorophthalonitrile, 3,6-difluoro-4, 5-bis (p-tolylthio) phthalonitrile, 3,6-difluoro-4,5-bis (m-tolylthio) phthalonitrile, 3,6-difluoro-4,5-bis (2,4-xylylthio) phthalonitrile 4,4-bis (o-chlorophenylthio) -3,6-difluorophthalonitrile,
4,5-bis (2,6-dichlorophenylthio) -3,
6-difluorophthalonitrile, 3,6-difluoro-
4,5-bis (o-fluorophenylthio) 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, 4-phenylthio-3,5,6-trifluorophthalonitrile,
4- (2-ethoxycarbonyl-6-methyl) phenoxy-3,5,6-trifluorophthalonitrile, 4-
(2-phenyl) phenoxy-3,5,6-trifluorophthalonitrile, 4,5-diphenoxy-3,6-difluorophthalonitrile and the like.

Next, the metal oxide used in the present invention is not particularly limited, and may be vanadium, titanium, iron, magnesium, nickel, cobalt, copper, silver,
Examples include oxides of palladium, zinc, germanium, tin, niobium, molybdenum, tungsten, silicon, lithium, and the like. Specifically, vanadium monoxide, vanadium trioxide, vanadium tetroxide, vanadium pentoxide, titanium dioxide, iron monoxide, iron sesquioxide, iron sesquioxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt sesquioxide Cobalt, cobalt dioxide, cuprous oxide, cupric oxide, copper trioxide, palladium oxide, zinc oxide, germanium monoxide, germanium dioxide, stannous oxide, stannic oxide, silicon monoxide, silicon dioxide, oxide Oxides such as lithium, molybdenum trioxide, niobium oxide, and niobium pentoxide are given. Preferred are oxides of iron, zinc, copper, cobalt, vanadium, molybdenum and titanium, more preferred are oxides of trivalent or higher metals such as oxides of titanium, motibdenum and vanadium, and particularly preferred are vanadium oxides. Examples of the vanadium oxide include vanadium trioxide, vanadium tetroxide, and vanadium pentoxide. Of these, lower oxides are preferred, and vanadium trioxide is particularly preferred. By using a metal oxide, there is an advantage that a chlorine atom is not mixed into a phthalocyanine skeleton as compared with a conventional phthalocyanine production method using chloride as a metal salt.

The compounding amount of the metal oxide with respect to the halogen-containing phthalonitrile compound may be a stoichiometric amount or more, but the metal oxide is added in an amount of 1 to 2 equivalents to 4 equivalents of the halogen-containing phthalonitrile compound. , Preferably in the range of 1.0 to 1.5 equivalents. When the amount of the metal oxide is less than 1 equivalent relative to 4 equivalents of the halogen-containing phthalonitrile compound, the amount of the metal oxide is insufficient in terms of stoichiometry, which is not preferable because a metal-free phthalocyanine compound is by-produced. When the metal oxide exceeds 2 equivalents relative to 4 equivalents of the halogen-containing phthalonitrile compound, a large amount of unreacted metal oxide remains,
It is uneconomical, and it is not preferable because it takes time to recover or remove these in the purification stage.

In the production method of the present invention, the dissociation index pKa (logarithm of the reciprocal of the dissociation constant of an acid or conjugate acid) of an acid or conjugate acid in an aqueous solution at 25 ° C. is 7.0 or less. , But pKa 7.0.
In the case of the following, multi-stage dissociation is performed, and a compound in which the pKa of the first dissociation stage is 7.0 or less even when the pKa exceeds 7.0 in the second and subsequent dissociation stages is also included. Preferably, the compound has a pKa of 7.0 or less in all dissociation stages. More preferably, it is carried out in the presence of a compound having a pKa in the range of -5.0 to 5.0. That is, when a phthalocyanine compound is synthesized by reacting a halogen-containing phthalonitrile compound with a metal oxide, the dissociation index pKa of an acid or conjugate acid in an aqueous solution at 25 ° C. is 7.
It has been found that the presence of 0 or less compound acts as a very useful catalyst. When the pKa of the compound exceeds 7.0, the activity as a catalyst is insufficient, so that the phthalocyanine-forming reaction does not easily proceed, which is not preferable.

The compound having a dissociation index pKa of an acid or a conjugate acid in an aqueous solution at 25 ° C. of not more than 7.0 used in the present invention is not particularly limited, as long as it has a pKa of not more than 7.0. Any of organic compounds and inorganic compounds may be used, for example, adipic acid, N-acetylalanine, N-acetylglycine, azelaic acid, 5 ′
-Adenosine triphosphate, 2'-adenosine phosphate, 3 '
-Adenosine phosphate, 5'-adenosine phosphate, o-anisic acid, m-anisic acid, p-anisic acid, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, benzoic acid, isokichi Valeric acid, isonicotinic acid, methyl isonicotinate, isobutyric acid, 5'-inosine phosphoric acid, oxaloacetic acid, octanoic acid, formic acid, valeric acid, quinaldic acid, citric acid, glyoxylic acid, glycolic acid, 2-glycerin phosphate, D -Glucose 1-phosphate, glutaric acid, crotonic acid, o-chloroaniline, m-chloroaniline, p-
Chloroaniline, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, chloroacetic acid, 2-chloropropionic acid, 3-chloropropionic acid, cis-cinnamic acid, trans-cinnamic acid, succinic acid Acetic acid, m-cyanobenzoic acid, p-cyanobenzoic acid, cyanoacetic acid, o-cyanophenol, cyclohexanecarboxylic acid, dichloroacetic acid, 2,6-dimethylpyridine, oxalic acid, d-tartaric acid, (R, R)- Tartaric acid, thenoyltrifluoroacetylacetone, trichloroacetic acid, trifluoroacetylacetone, p-toluenesulfonic acid, 1-naphthoic acid, 2
-Naphthoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, nitroacetic acid, p-nitrophenol, lactic acid, uric acid, barbituric acid, picric acid, picolinic acid, 2,2'-bipyridine, 4,4'-bipyridine, pimelic acid, 2,6-pyridinedicarboxylic acid, pyruvic acid, phenylacetic acid, phenoxyacetic acid, fumaric acid, o
-Fluorobenzoic acid, m-fluorobenzoic acid, p-fluorobenzoic acid, fluoroacetic acid, propionic acid, o-bromobenzoic acid, m-bromobenzoic acid, p-bromobenzoic acid, bromoacetic acid, hexafluoroacetylacetone, hexanoic acid , Heptanoic acid, o-benzenedicarboxylic acid, m
-Benzenedicarboxylic acid, p-benzenedicarboxylic acid,
Maleic acid, malonic acid, mandelic acid, o-iodobenzoic acid, m-iodobenzoic acid, p-iodobenzoic acid, iodoacetic acid, butyric acid, malic acid, levulinic acid, L-ascorbic acid, aspartic acid, adenine, adenosine, 5'-adenosine diphosphate, m-hydroxybenzoic acid, p-hydroxybenzoic acid, methanesulfonic acid, ethanesulfonic acid, 1,2-ethanedisulfonic acid, trifluoromethanesulfonic acid, 3-hydroxypropanesulfonic acid, 1,
3-propanedisulfonic acid, heptadecafluorooctanesulfonic acid, benzenesulfonic acid, p-phenolsulfonic 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, pyridine- Use 3-sulfonic acid, 2,5-dichlorosulfanilic acid, 4-chloroaniline-3-sulfonic acid, 3-nitroaniline-4-sulfonic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphinic acid, phosphonic acid, and the like. However, an organic compound is preferable. When an organic compound is used as the reaction solvent in producing the phthalocyanine compound, the organic compound is preferably used because the solubility in the used organic solvent is higher than that of the inorganic compound and the effect of promoting the reaction is improved. Among the organic compounds, organic acids are preferable, and 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,
3-propanedisulfonic acid, heptadecafluorooctanesulfonic acid, benzenesulfonic acid, p-phenolsulfonic acid, p-toluenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-nitrobenzenesulfonic acid, 4-nitrobenzenesulfonic acid, 4-chlorobenzene Sulfonic 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, and p-toluenesulfone is particularly easy to obtain when industrialized. Acids are preferred.

The amount of the compound having a pKa of 7.0 or less is not included in the stoichiometric reaction formula of the reaction system because it is used as a catalyst, so that the amount does not change before and after the reaction. For example, when the reaction is carried out in a batch system, the amount of the halogen-containing phthalonitrile compound is 0.0
A sufficient catalytic action can be obtained by charging 5 to 5 mol%, preferably 0.05 to 2 mol%. If the amount of the compound having a pKa of 7.0 or less is less than 0.05 mol% with respect to the amount of the halogen-containing phthalonitrile compound, active species cannot be generated with the metal oxide. This is not preferable because the reactivity with the halogen-containing phthalonitrile compound cannot be sufficiently increased, and it becomes difficult to introduce a bulky substituent on the phthalocyanine skeleton. On the other hand, when the use amount of the compound having a pKa of 7.0 or less exceeds 5 mol% with respect to the use amount of the halogen-containing phthalonitrile compound, an excess compound having a pKa of 7.0 or less is contained in the reaction system. In addition to the possibility of causing a side reaction to reduce the yield, a sufficient catalytic effect has already been obtained, and a more remarkable effect corresponding to further addition cannot be obtained, which is not preferable.

In the method for producing a phthalocyanine compound of the present invention, it is desirable to react the halogen-containing phthalonitrile compound with the metal oxide in the presence of the compound having a pKa of 7.0 or less. The reaction conditions are as follows: a reaction temperature of 30 to 250 ° C., preferably 80 ° C.
~ 200 ° C. When the reaction temperature is lower than 30 ° C., the reaction rate is remarkably reduced due to a decrease in the catalytic activity and the time required for the synthesis is significantly increased, so that it is not economical. In
This is not preferable because the amount of by-products increases.

Further, in the method for producing a phthalocyanine compound of the present invention, a stirring power of 0.03 kW / m
³ or more, preferably 0.05 kW / m ³ or more, more preferably it is desirable to carry out stirring at 0.1 kW / m ³ or more. When the stirring power is less than 0.03 kW / m ³ , it is difficult to uniformly disperse the coexisting alkaline earth metal in the reaction system, and a part of the reaction system may have a disadvantage in the phthalocyanine conversion reaction. The time and amount of the generated hydrofluoric acid or the like staying without reacting with the alkaline earth metal compound increases, and the corrosion of the reactor proceeds, which is not preferable.

The stirring device for providing such stirring power is not particularly limited, and a conventionally known stirring device may be appropriately selected and used.

Further, in the production method of the present invention, there is provided a method in which the above-mentioned metal oxide and a compound having a pKa of 7.0 or less are mixed in advance, and after a certain period of time, the above-mentioned halogen-containing phthalonitrile compound is added to start the reaction. May be used. When this method is used, an active species of the reaction is generated before the addition of the halogen-containing phthalonitrile compound, so that the progress of the reaction may be accelerated.

In the method for producing a phthalocyanine compound of the present invention, the reaction between the halogen-containing phthalonitrile compound and the metal oxide in the presence or absence of the compound having a pKa of 7.0 or less is not affected. Although the reaction can be performed in a solvent (that is, the halogen-containing phthalonitrile compound itself, which is a reaction raw material (substituting reagent), can be used as a solvent), the reaction is preferably performed using an organic solvent.
The organic solvent is not particularly limited as long as it is an inert solvent having no reactivity with the materials of the reactor and the like in addition to the starting materials and synthetic products, but as described above, one of the preferable alkaline earth metal compounds is used. When a certain carbonate is used, water produced as a by-product may have an adverse effect. Therefore, it is preferable to azeotropically distill off such water. Alternatively, those having a boiling point higher than that of water are more desirable. Such organic solvents include, for example, nitromethane, nitroethane, nitrobenzene, triethylamine, tri-n-butylamine, tri-n-
Octylamine, N, N-dimethylaniline, N, N-
Diethylaniline, N, N-dimethylacetamide,
Nitrogen compound solvents such as N, N-dimethylformamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, acetonitrile, benzonitrile, benzene, ethylbenzene, toluene, xylene, naphthalene, 1-methylnaphthalene, 1- Hydrocarbon solvents such as ethylnaphthalene and dimethylnaphthalene, tetrachloroethane, monochlorobenzene, o-dichlorobenzene,
Halogenated hydrocarbon solvents such as m-dichlorobenzene, 1,2,4-trichlorobenzene and 1-chloronaphthalene; alcohol solvents such as n-octanol and ethylene glycol; sulfur compound solvents such as dimethyl sulfoxide and sulfolane; And preferably a nitrogen compound-based solvent, a hydrocarbon-based solvent, or a halogenated hydrocarbon-based solvent. Particularly, the compound having a pKa of 7.0 or less enhances the catalytic ability and accelerates the generation of active species. A nitrogen compound-based solvent is preferred because it has an effect, and benzonitrile is particularly preferred. These may be used alone or in a combination of two or more as long as they do not affect each other.

The amount of the organic solvent used is 100
Halogen-containing phthalonitrile compound 10 to 10 parts by weight
75 parts by weight, preferably 20 to 60 parts by weight. If the content of the halogen-containing phthalonitrile compound is less than 10 parts by weight with respect to 100 parts by weight of the organic solvent, the productivity is low, and the reaction rate is slow, requiring extra time, which is not economically preferable. On the other hand, when the halogen-containing phthalonitrile compound exceeds 75 parts by weight with respect to 100 parts by weight of the organic solvent, stirring becomes difficult because the slurry concentration becomes high, and a large stirrer is required, and the stirring efficiency becomes poor. It is not preferable because a uniform reaction cannot be performed.

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

Such phthalocyanine compounds include:
For example, 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-tert-butoxycarbonyl-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-isopropoxycarbonylphenoxy) dodecafluorovanadyl phthalocyanine, tetrakis (bromo-2-isopropoxycarbonyl-6- Phenylphenoxy) dodecafluorovanadyl phthalocyanine, tetrakis (6- (4
-Bromomethylphenyl) -2- (2-tetrahydrofurfuryloxy) carbonylphenoxy) dodecafluorotitanyl phthalocyanine, tetrakis (6- (4-bromomethoxyphenyl) -2- (2-isopropoxycarbonylphenoxy) dodecafluorovanadyl phthalocyanine , Tetrakis (2- (1,3-dibromo-2-propoxycarbonyl) -6-phenylphenoxy) dodecafluorovanadyl 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-phenylphenoxy) 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) dodecafluoro Iron phthalocyanine, tetrakis (2,6-dichloroanilino) titanyl phthalocyanine, octaphenoxyoctafluorovanadyl phthalocyanine, Fine tetrakis (4-(p-methylphenoxy)) - such as dodeca-chloro vanadyl phthalocyanine and the like.

[0055]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1 A 300 ml glass separable flask was stirred with a stirrer (Three One Motor 600G, Haydon) and a diameter of 50 mm.
And four baffles having a width of 8 mm were set. The reactor was charged with 125.8 g of tetrafluorophthalonitrile (TFPN) and 12.0 g of vanadium trioxide.
2 g, p-toluenesulfonic acid 8.37 g, calcium carbonate 1.42 g and benzonitrile 251.6 as a solvent
g, and reacted at 150 ° C. for 20 hours. During the reaction, the stirring blade was rotated at a speed of 502 rpm (corresponding to a stirring power of 1.0 kW / m ³ in this case). After completion of the reaction, the produced solid content was filtered, washed once with benzonitrile, and then dried to obtain the desired purple cake 114.1.
5 g were obtained. When the purity of the obtained target product was analyzed, it was 9
Since it was 3.5%, the yield was 7 based on this value.
8.3 mol% (vs. TFPN).

After the completion of the reaction, the annual corrosion rate was calculated from the weight loss of the reactor and found to be 0.33 mm / year.

Example 2 The same operation as in Example 1 was carried out except that the amount of calcium carbonate was changed to 8.00 g, to obtain 116.88 g of a target purple cake. When the purity of the obtained target product was analyzed, it was 92.6%. When converted from this value, the yield was 79.4 mol% (vs. TFPN).

After completion of the reaction, the weight of the reactor was not reduced, and the annual corrosion rate was 0.00 mm / year.

Example 3 The same operation as in Example 2 was carried out except that the reaction temperature was changed to 180 ° C.
2.06 g were obtained. When the purity of the obtained target product was analyzed, it was 91.8%. When converted from this value, the yield was 82.2 mol% (vs. TFPN).

After completion of the reaction, the annual corrosion rate was 0.39 mm / year due to the weight loss of the reactor.

Comparative Example 1 The same operation as in Example 1 was carried out except that calcium carbonate was not added, to obtain 102.20 g of a target purple cake. When the purity of the obtained target product was analyzed, it was 88.7%. When converted from this value, the yield was 66.5 mol% (vs. TFPN).

After the completion of the reaction, the annual corrosion rate was 3.12 mm / year due to the weight loss of the reactor.

Example 4 In Example 2, the stirring speed was changed to 400 rpm (in this case,
Example 2 except that the stirring power became 0.5 kW / m ³ )
When the same operation as described above was performed, the target purple cake 11 was obtained.
3.42 g were obtained. When the purity of the obtained target product was analyzed, it was 91.1%. When converted from this value, the yield was 75.8 mol% (based on TFPN).

After the completion of the reaction, the annual corrosion rate was 0.08 mm / year due to the weight loss of the reactor.

Example 5 In Example 2, the stirring speed was set to 200 rpm, and the stirring blade was changed to a two-blade blade having a diameter of 68 mm (in this case, a stirring power of 0.0
(Equivalent to 4 kW / m ³ ), and the same operation was carried out except that the baffle was not used, to obtain 103.14 g of a purple cake as a target. When the purity of the obtained target product was analyzed, it was 90.4%. When converted from this value, the yield was 68.4 mol% (vs. TFPN).

After completion of the reaction, the annual corrosion rate was 1.39 mm / year due to the decrease in the weight of the reactor.

Example 6 Example 2 was repeated except that 172.39 g of 4-phenoxy-3,5,6-trifluorophthalonitrile was used in place of tetrafluorophthalonitrile and isopropyl alcohol was used as a washing solvent. By performing the same operation as described above, 97.08 g of the target purple cake
I got The purity of the obtained target product was analyzed.
Since it was 9%, the yield was calculated to be 63.2 based on this value.
Mol% (vs. 4-phenoxy-3,5,6-trifluorophthalonitrile).

After the completion of the reaction, the annual corrosion rate was 0.21 mm / year due to the weight loss of the reactor.

Example 7 The same procedure as in Example 2 was carried out except that 13.05 g of zinc oxide was used instead of vanadium trioxide, to obtain 125.15 g of the desired purple cake.
When the purity of the obtained target product was analyzed, it was 89.7%. When converted from this value, the yield was 82.5 mol%.
(Vs. TFPN).

After completion of the reaction, the annual corrosion rate was 0.18 mm / year due to the decrease in the weight of the reactor.

Example 8 The procedure of Example 7 was repeated, except that 239.18 g of 4,5-bisphenylthio-3,6-difluorophthalonitrile was used instead of tetrafluorophthalonitrile. The desired purple cake 111.
05 g were obtained. When the purity of the obtained target product was analyzed, it was 93.1%.
8.8 mol% (vs. 4,5-bisphenylthio-3,6-
Difluorophthalonitrile).

After completion of the reaction, the annual corrosion rate was 0.26 mm / year due to the weight loss of the reactor.

Example 9 Example 7 was repeated except that 172.39 g of 4-anilino-3,5,6-trifluorophthalonitrile was used in place of tetrafluorophthalonitrile and isopropyl alcohol was used as a washing solvent. By performing the same operation as described above, 95.91 g of the desired purple cake was obtained. When the purity of the obtained target product was analyzed, it was 92.7.
%, The yield was 67.3 mol% (based on 4-anilino-3,5,6-trifluorophthalonitrile).

After completion of the reaction, the annual corrosion rate was 0.24 mm / year due to the weight loss of the reactor.

Example 10 In Example 8, niobium oxide was used instead of zinc oxide.
By operating in the same manner as in Example 8 except that 46 g was used, 118.84 g of the target purple cake was obtained. When the purity of the obtained target product was analyzed, it was 83.8%. When converted from this value, the yield was 75.9 mol% (vs. 4,
5-bisphenylthio-3,6-difluorophthalonitrile).

After the completion of the reaction, the annual corrosion rate was 0.30 mm / year due to the weight loss of the reactor.

Example 11 In Example 8, tin oxide 21.60 was used instead of zinc oxide.
By operating in the same manner as in Example 8 except that g was used,
120.72 g of the desired purple cake was obtained. When the purity of the obtained target product was analyzed, it was 83.8%.
When converted from this value, the yield was 79.4 mol% (vs. 4,5-
Bisphenylthio-3,6-difluorophthalonitrile).

After completion of the reaction, the annual corrosion rate was 0.06 mm / year due to the weight loss of the reactor.

[0080]

According to the present invention, optical recording using a semiconductor laser having absorption in the near-infrared region, for example, a semiconductor laser, is used as a soluble phthalocyanine compound, particularly a near-infrared absorbing dye or its precursor, a high-grade dye, and the like. Medium, liquid crystal display,
Near-infrared absorbing dyes, near-infrared sensitizers, photothermal conversion agents such as thermal transfer, near-infrared absorbing materials such as near-infrared absorbing filters,
Color separation filter, color filter for liquid crystal display, color filter for optics, color filter for plasma display, color CRT selective absorption filter,
In the industrial production of useful soluble phthalocyanine compounds that can be used for color toners, ink-jet inks, etc., by-products are produced during the phthalocyanine conversion reaction by adding an alkaline earth metal compound to the reaction system. Since hydrohalic acid such as hydrofluoric acid can be quickly trapped, reactor corrosion caused by hydrohalic acid such as hydrofluoric acid can be extremely effectively prevented or reduced to a very low level. Halides such as hydrofluoric acid are also advantageous in that they can be removed by filtration and the purification step can be simplified.

Further, according to the present invention, in the industrial production of a soluble phthalocyanine compound, a conventionally known production method whose usefulness has been confirmed at the laboratory level except that an alkaline earth metal compound is added to the reaction system. Can be applied as it is, it can be used in a wide range of fields as near-infrared absorbing dyes or precursors thereof, higher dyes, etc. Infrared absorbing dye, near infrared sensitizer, photothermal conversion agent such as thermal transfer, near infrared absorbing material such as near infrared absorbing filter, color separation filter, liquid crystal display color filter, optical color filter, plasma display color Can be used for filters, color CRT selective absorption filters, color toners, inkjet inks, etc. A useful soluble phthalocyanine compound can be produced on an industrial scale with the same yield as that of a laboratory scale, and the reaction rate can be increased by easily progressing the trapping of hydrohalic acid such as HF. It is possible to achieve a further action and effect that is to be improved,
It also has the advantage of increasing production efficiency in industrial production.

Further, according to the present invention, the method for producing a phthalocyanine compound of the present invention comprises the step of dissociation index pKa (acid or conjugate acid) of an acid or a conjugate acid in an aqueous solution at 25 ° C. from a halogen-containing phthalonitrile compound and a metal oxide. When producing a phthalocyanine compound in the presence of a compound having a logarithm of the reciprocal of the dissociation constant of 7.0 or less, the pKa is reduced by coexisting and reacting with an alkaline earth metal compound.
Can act as a catalyst to generate an active species with the metal oxide, thereby increasing the reactivity with the halogen-containing phthalonitrile compound. It is not only sufficient, but also extremely excellent in that a bulky substituent can be introduced onto the phthalocyanine skeleton.

Further, in the present invention, the stirring power is set to 0.1 at the time of the reaction.
By performing the stirring at 03 kW / m ³ or more, the effects of the invention described above can be more remarkably obtained.

Further, in the present invention, by using a calcium compound as the alkaline earth metal compound, a hydrohalic acid such as hydrofluoric acid is trapped to form a calcium halide such as CaF ₂ which is extremely stable and non-corrosive. Since it is produced, it can be easily separated and removed by filtration or the like in the purification process.

Further, in the present invention, a carbonate such as calcium carbonate, which is suitable as an alkaline earth metal compound, is used, and water produced during the reaction is reacted while azeotropically distilling off with an organic solvent. Even if hydrohalic acid such as hydrofluoric acid is trapped, there is an advantage that no acid component remains in the reaction system and the reaction can proceed smoothly without any adverse effect due to by-produced water.

Further, in the present invention, since the phthalocyanine conversion reaction is carried out in an organic solvent, the slurry concentration in the reactor can be optimally maintained, so that the productivity is excellent and the reaction rate can be maintained without lowering the reaction rate. It is economical without extra time, is easy to stir, is excellent in stirring efficiency even with a small stirrer, and can perform a uniform reaction.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Seiji Masuda 1-25-12 Kannondai, Tsukuba, Ibaraki Pref. Nippon Shokubai Co., Ltd. (72) Inventor Koichi Hirota Nippon Shokubai Co., Ltd. (72) Inventor Hisawa Shindo 992, Nishioki, Okahama-ku, Abashiri-ku, Himeji-shi, Hyogo Japan Nippon Shokubai Co., Ltd. In the catalyst

Claims (4)

[Claims] 1. A method for producing a phthalocyanine compound, comprising reacting a phthalocyanine compound from a halogen-containing phthalonitrile compound and a metal oxide in the presence of an alkaline earth metal compound. 2. A dissociation index pKa of an acid or a conjugate acid in an aqueous solution at 25 ° C. (logarithm of a reciprocal of a dissociation constant of an acid or a conjugate acid) of 7.0 or less from a halogen-containing phthalonitrile compound and a metal oxide. A method for producing a phthalocyanine compound, comprising reacting a phthalocyanine compound in the presence of the compound in the presence of an alkaline earth metal compound. 3. The method for producing a phthalocyanine compound according to claim 1, wherein the stirring is performed with a stirring power of 0.03 kW / m ³ or more during the reaction. 4. The method for producing a phthalocyanine compound according to claim 1, wherein the reaction is performed in an organic solvent.