JP2005298491A - Method for producing halogen-containing phthalocyanine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method capable of inexpensively producing a phthalocyanine compound in high yield by using a solvent capable of becoming a specific oxygen source involving a complex forming reaction of a metallic compound introduced into a phthalocyanine pigment. <P>SOLUTION: In the method for producing a halogen-containing phthalocyanine compound by carrying out cyclization reaction of a phthalonitrile compound alone or the phthalonitrile with a metallic compound, the cyclization reaction is carried out in an organic compound having a hydroxyl group and/or a carboxyl group in an amount of 0.01-10 pts. mass based on 1 pt. mass phthalocyanine while introducing an inert gas. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel method for producing a halogen-containing phthalocyanine compound. In particular, the present invention relates to a method for producing a halogen-containing phthalocyanine compound having heat ray absorption and / or absorption in the near infrared region, excellent solubility in a solvent, and high light resistance.

  Since the phthalocyanine compound obtained by the production method of the present invention is excellent in heat ray absorbing ability, it is useful as a heat ray absorbing dye. Further, since the phthalocyanine compound obtained by the production method of the present invention has absorption in the near infrared region of 600 to 1000 nm, writing or recording in an optical recording medium using a semiconductor laser, a liquid crystal display device, an optical character reader or the like. Near-infrared absorption dyes for reading, near-infrared sensitizers, thermal transfer, photothermal conversion agents such as thermal paper and thermal stencil, near-infrared absorption filters for plasma display panels (PDP), anti-eye strain agents Color separation filter used as a near-infrared absorbing material used as a photoconductive material, or a color separation filter used in an image pickup tube, a color filter for liquid crystal display, a color cathode ray tube selective absorption filter, a color toner, a toner dye for flash fixing, an ink jet ink, falsification Bar code ink for prevention, microbial deactivator, photosensitive color for tumor treatment Further automobiles or building materials of the heat ray shielding agent, and further is intended to exhibit an excellent effect when used as a resin segmentation determination agent.

  The need for near-infrared absorbing dyes is increasing as the field of use expands, and near-infrared for writing or reading in optical recording media, liquid crystal display devices, optical character readers, etc. using semiconductor lasers. Nearly used as absorption dyes, near-infrared sensitizers, thermal transfer, photothermal conversion agents such as thermal paper and thermal stencil, near-infrared absorption filters for plasma display (PDP), eye strain prevention agents, photoconductive materials, etc. Infrared absorbing materials or color separation filters used for image pickup tubes, color filters for liquid crystal displays, color cathode ray tube selective absorption filters, color toners, flash fixing toner dyes, inkjet inks, barcode inks for preventing falsification, and microorganisms Deactivator, photosensitive dye for tumor treatment, and heat ray shielding for automobiles or building materials In addition, in the near-infrared absorbing dye used as a resin classification discriminating agent, a method for producing a material satisfying all the characteristics such as light resistance, heat resistance, solubility (or compatibility with resin) has been studied. However, an industrially advantageous method has not been developed.

  As methods for producing these phthalocyanine compounds, for example, Patent Documents 1 to 4 are known.

  In Patent Document 1, tetrafluorophthalonitrile and vanadium trichloride are used alone with α-methylnaphthalene or benzonitrile, and a gas containing oxygen such as a gas diluted with air is introduced into the reaction solution. A method of reacting is described. The solvent α-methylnaphthalene used in this method is very expensive, or is a reaction method in which a gas containing oxygen is introduced at a high temperature. In addition to the problem of scattering outside, there is a risk of explosion and it is difficult to say that this is an industrially preferable method. Patent Document 2 reacts tetrafluorophthalonitrile and vanadium trioxide at 150 ° C. in the presence of paratoluenesulfonic acid and calcium carbonate in a benzonitrile solvent. In this publication, as the organic solvent used in the reaction, an inert solvent that is not reactive with the starting materials and the reactor is recommended, and in order to prevent corrosion of the reactor, a metal oxide and Although the reaction is carried out at a relatively low temperature using paratoluenesulfonic acid, according to the study by the present inventors, the desired performance of the target phthalocyanine compound may not be expressed and is not appropriate. It was.

In Patent Document 3, as a novel phthalocyanine compound and a method for producing the same, a fluorine-containing phthalocyanine compound is produced by reacting a corresponding phthalonitrile compound and vanadium chloride in an inert solvent or an aprotic polar solvent. Ethylene glycol listed as a reaction solvent is exemplified as an inert solvent, and there is no description regarding other alcohols. Moreover, although the synthesis example under nitrogen stream is given in the Example, benzonitrile is only used as an inert solvent. In Patent Document 4, a phthalonitrile compound having a substituent and vanadium chloride are reacted under reflux using benzonitrile and octanol, but the reaction is performed without using an inert gas such as nitrogen. As a result, the yield is as low as 63.2 mol%.
JP 2000-63693 A JP 2000-169743 A Japanese Patent Publication No. 07-103318 JP 2004-18561 A

  In view of the above problems, the object of the present invention is to have a halogen-containing phthalocyanine compound, in particular, a heat ray absorbing dye, a near infrared absorbing dye or a precursor thereof, a higher dye, etc. in a wide range of fields, for example, excellent heat ray absorbing ability. Heat-absorbing dyes, optical recording media that absorb in the near infrared region and use semiconductor lasers, liquid crystal display devices, near-infrared absorbing dyes, near-infrared sensitizers, photothermal conversion agents such as thermal transfer, and near-infrared absorbing filters Useful halogens that can be used for near-infrared absorbing materials, color separation filters, color filters for liquid crystal displays, optical color filters, color filters for plasma display displays, color cathode ray tube selective absorption filters, color toners, inkjet inks, etc. The object is to provide a method for industrially producing a phthalocyanine compound to be contained.

  Another object of the present invention is to provide a method for producing a phthalocyanine compound at a low cost and in a high yield by using a solvent that can be a specific oxygen source involved in the complexation reaction of a metal compound introduced into a phthalocyanine dye. It is to be.

  In addition to the above object, the object of the present invention is to use an oxygen source having an explosion risk such as an oxygen-containing gas when an oxygen source is required for the purpose of activating the complexation reaction. In addition, the present invention is to provide a method capable of industrially and inexpensively producing a near-infrared absorbing dye or a precursor thereof and a useful phthalocyanine compound used in the above-described applications in a safer and preferable method.

  As a result of intensive studies to achieve the above object, the inventors of the present invention produced a phthalonitrile compound represented by the general formulas (1) to (4) in the method for producing a halogen-containing phthalocyanine compound represented by the formula (5). , Alone or in the cyclization reaction with a metal compound, the cyclization reaction is carried out in the presence of a specific organic compound or in the coexistence of the organic compound with an inert solvent and / or an aprotic organic solvent. At the start of the reaction, the inside of the reactor is replaced with an inert gas, and the phthalocyanine compound is produced in a high yield by conducting the reaction while introducing the inert gas and in the absence of oxygen. It has been found that the object of the present invention can be achieved. Based on the above findings, the present invention has been completed.

  That is, the object of the present invention is the following formula (1):

A phthalonitrile compound (1) represented by the following formula (2):

A phthalonitrile compound (2) represented by the following formula (3):

A phthalonitrile compound (3) represented by the following formula (4):

A phthalonitrile compound (4) represented by
In the above formulas (1) to (4), Z _{1 to} Z ₁₆ each independently represent a hydrogen atom, NHR ¹ , SR ² , OR ³ or a halogen atom, and at least one of Z _{1 to} Z ₁₆ Is a halogen atom, and R ¹ , R ² and R ³ each independently have a phenyl group which may have a substituent, an aralkyl group which may have a substituent or a substituent. Represents an optionally substituted alkyl group having 1 to 20 carbon atoms,
By cyclization reaction alone or with a metal compound, the following formula (5):

_However, Z 1 _{to Z 16} represents a hydrogen ^atom, NHR ^1, SR 2, OR ^3, or a halogen atom, and at least one is a halogen ^atom, R 1, ^{R 2} and ^{R 3} are each independently A phenyl group which may have a substituent, an aralkyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms which may have a substituent; Represents metal-free, metal, metal oxide or metal halide,
A method for producing a halogen-containing phthalocyanine compound represented by:
The cyclization reaction is carried out in an organic compound having a hydroxyl group and / or a carboxyl group in an amount of 0.01 to 10 parts by mass and introducing an inert gas with respect to 1 part by mass of the phthalonitrile compound. It is achieved by the method for producing a phthalocyanine compound of formula (5), which is characterized.

  In the method of the present invention, when the phthalonitrile compound represented by the general formulas (1) to (4) is cyclized by itself or with a metal compound, the cyclization reaction is performed in the presence of a specific organic compound. Alternatively, in the coexistence of the organic compound with an inert solvent and / or an aprotic organic solvent, and the inside of the reactor is replaced with an inert gas at the start of the reaction, while introducing the inert gas during the reaction, This is a method for producing a halogen-containing phthalocyanine compound represented by the formula (5) by carrying out in the absence of oxygen, but according to this method, a desired phthalocyanine compound can be produced in a high yield. .

  The present invention provides the following formula (1):

A phthalonitrile compound (1) represented by the following formula (2):

A phthalonitrile compound (2) represented by the following formula (3):

A phthalonitrile compound (3) represented by the following formula (4):

A phthalonitrile compound (4) represented by
In the above formulas (1) to (4), Z _{1 to} Z ₁₆ each independently represent a hydrogen atom, NHR ¹ , SR ² , OR ³ or a halogen atom, and at least one of Z _{1 to} Z ₁₆ Is a halogen atom, and R ¹ , R ² and R ³ each independently have a phenyl group which may have a substituent, an aralkyl group which may have a substituent or a substituent. Represents an optionally substituted alkyl group having 1 to 20 carbon atoms,
By cyclization reaction alone or with a metal compound, the following formula (5):

_However, Z 1 _{to Z 16} represents a hydrogen ^atom, NHR ^1, SR 2, OR ^3, or a halogen atom, and at least one is a halogen ^atom, R 1, ^{R 2} and ^{R 3} are each independently A phenyl group which may have a substituent, an aralkyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms which may have a substituent; Represents metal-free, metal, metal oxide or metal halide,
A method for producing a halogen-containing phthalocyanine compound represented by:
The cyclization reaction is carried out in an organic compound having a hydroxyl group and / or a carboxyl group in an amount of 0.01 to 10 parts by mass and introducing an inert gas with respect to 1 part by mass of the phthalonitrile compound. A feature of the present invention is to provide a method for producing a phthalocyanine compound of the formula (5).

  Hereinafter, the present invention will be described in detail.

  The first feature of the present invention is that the phthalonitrile compound represented by the formulas (1) to (4) (also referred to collectively as “phthalonitrile compound” in this specification) alone or a phthalonitrile compound and a metal compound Is carried out in an organic compound having a hydroxyl group and / or a carboxyl group in an amount of 0.01 to 10 parts by mass with respect to 1 part by mass of the phthalonitrile compound. As a result, the yield of the target halogen-containing phthalocyanine compound can be improved. The reason why the target halogen-containing phthalocyanine compound can be obtained in high yield by using an organic compound containing a hydroxyl group and / or a carboxyl group is not clear, but the organic compound is preferentially selected from a metal compound that is a central metal source. It is presumed that a complex of a metal compound and an organic compound is produced in response to the reaction, and that the presence of this complex promotes the cyclization reaction between the halogen-containing phthalonitrile compound and the metal compound. . In addition to the above-mentioned advantages, the presence of a certain amount of organic compound improves the solubility of the precursor of the phthalocyanine compound (complex) in the solvent and promotes the reaction, which is considered to increase the reaction yield. Further, for example, when a metal halide is used as the central metal source, a compound such as a hydrogen halide produced by the reaction between an organic compound and a metal halide acts on the phthalonitrile compound catalytically to cyclize. It is assumed that the reaction is further accelerated. Furthermore, even when a metal halide is not used, it is presumed that a compound such as a hydrogen halide produced by a reaction between an organic compound and a halogen present in the phthalonitrile compound exhibits the same action as described above.

The organic compound having a hydroxyl group and / or carboxyl group used in the present invention (simply referred to herein as “organic compound”) may be any compound having a hydroxyl group and / or a carboxyl group. What can melt | dissolve the phthalonitrile compound represented by (1)-(4) is preferable. Specifically, alkyl alcohols such as n-butyl alcohol, t-butyl alcohol, isobutyl alcohol, n-pentyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, decyl alcohol, tridecyl alcohol; Aromatic alcohols such as benzyl alcohol, methylbenzyl alcohol, phenethyl alcohol, benzenedimethanol, naphthol; glycol ethers such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether; acetic acid, propionic acid, butyric acid, etc. Aliphatic carboxylic acids such as benzoic acid and naphthoic acid. These organic compounds may be used alone or in the form of a mixture of two or more types, but are generally used alone. Among these organic compounds, those having 6 to 15 carbon atoms are preferable, and those having strong hydrophobicity are more preferable. In the present specification, “an organic compound having a hydroxyl group and / or a carboxyl group” means an organic compound having at least one of a hydroxyl group and a carboxyl group. That is, the organic compound according to the present invention may have both a hydroxyl group and a carboxyl group in one molecule such as glyoxylic acid or glycol ether having a carboxyl group. n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, benzyl alcohol, naphthol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, benzoic acid, butyric acid and the like are particularly preferably used. In particular, when the phthalonitrile compound is a phthalonitrile compound in which all of tetrafluorophthalonitrile and the like are halogen atoms, it is preferable to use an organic compound such as n-octyl alcohol alone, and other substituents (NHR ¹ , SR ² , OR ³ ) as a raw material, the cyclization reaction may be carried out in the presence of an inert solvent and / or an aprotic organic solvent as described in detail below. preferable.

  The amount of the organic compound used is 0.01 to 10 parts by mass, preferably 0.02 to 7.5 parts by mass, and more preferably 0.05 to 1 part by mass with respect to 1 part by mass of the phthalonitrile compound that is the starting material. It is 5 mass parts, Most preferably, it is the range of 0.1-3 mass parts. In this case, if the amount of the organic compound used is less than the lower limit, the cyclization reaction does not proceed efficiently, and the solubility of the produced phthalocyanine compound (complex) precursor in the solvent is not sufficient. The yield of the halogen-containing phthalocyanine compound may be reduced. In addition to the above, when the amount of the organic compound is small, the slurry concentration becomes high, so that stirring becomes difficult during the reaction, a special stirrer is required, and the stirring efficiency is poor and a uniform reaction cannot be performed. There is a risk. On the other hand, if the organic compound is used excessively beyond the upper limit, the organic compound is used more than necessary, which may not be economical because not only the productivity decreases but also the reaction rate decreases. In the present invention, the organic compound may be charged at the time of charging, or may be added continuously or divided during the reaction as necessary. The organic compound may be used alone as an organic solvent.

  In the method of the present invention, the cyclization reaction is preferably carried out in the presence of an inert solvent and / or an aprotic organic solvent in addition to the organic compound having a hydroxyl group and / or a carboxyl group. By coexisting an inert solvent and / or an aprotic organic solvent in this way, the cyclization reaction can be carried out smoothly even with a relatively small amount of an organic compound, and the starting phthalonitrile compound or precursor can be changed. There is an advantage that the reaction can be promoted by dissolution. The inert solvent and the aprotic organic solvent may be used alone or in the form of a mixture of two or more, and an inert solvent and an aprotic organic solvent may be combined as appropriate. Although it may be used, it is preferable to use an inert solvent or an aprotic organic solvent alone in consideration of the ease of operation, ease of purification after the reaction and recovery of the solvent.

  In the present invention, the inert solvent or aprotic polar solvent that can be used with the organic compound having a hydroxyl group and / or a carboxyl group is not particularly limited as long as the above effect can be achieved, but the boiling point is 150 ° C. or higher. It is preferable that it is an aromatic compound. The inert solvent may be any inert solvent that has low reactivity with the phthalonitrile compound as a starting material, and preferably does not exhibit reactivity. For example, benzene, toluene, xylene, nitrobenzene, mono Chlorobenzene, dichlorobenzene, trichlorobenzene, chloronaphthalene, methylnaphthalene, benzonitrile and the like can be preferably used. In the present specification, “inactive” means inactive to the reaction according to the present invention. Also, as the aprotic polar solvent, any solvent may be used as long as it is an aprotic and polar solvent that has low reactivity with the phthalonitrile compound as a starting material, and preferably does not exhibit reactivity. Pyridine, N, N-dimethylformamide (DMF), N-methyl-2-pyrrolidinone, N, N-dimethylacetamide, triethylamine, tri-n-butylamine, dimethyl sulfoxide, sulfolane and the like can be preferably used. Of these, benzonitrile, nitrobenzene, dichlorobenzene, trichlorobenzene, chloronaphthalene, methylnaphthalene, and N, N-dimethylformamide are preferable. Nitrobenzene, dichlorobenzene, trichlorobenzene, chloronaphthalene, methylnaphthalene, benzonitrile, N , N-dimethylformamide is more preferable, and benzonitrile, N, N-dimethylformamide, and chloronaphthalene are particularly preferable. The inert solvent and the aprotic organic solvent may be used alone or in the form of a mixture of two or more, and an inert solvent and an aprotic organic solvent are appropriately combined. However, it is preferable to use an inert solvent or an aprotic organic solvent alone in view of ease of operation, ease of purification after the reaction and recovery of the solvent. The solvent used in combination with the organic compound may be an inert and aprotic organic solvent. Examples of such a solvent include benzonitrile.

  When an inert solvent and / or an aprotic organic solvent is used in combination with the organic compound having a hydroxyl group and / or carboxyl group described above, an organic compound having a hydroxyl group and / or a carboxyl group, an inert solvent and / or an aprotic compound The mixing ratio with the organic organic solvent is not particularly limited as long as it is a ratio that can sufficiently promote the cyclization reaction, and, as described above, varies depending on the type and number of substituents in the starting phthalonitrile compound. Preferably, the total amount of the inert solvent and the aprotic organic solvent is 0.01 to 50 parts by mass, more preferably 0.05 to 40 parts by mass, and particularly preferably 0.000 parts by mass with respect to 1 part by mass of the organic compound. The amount is 1 to 30 parts by mass. At this time, if the total amount of the inert solvent and the aprotic organic solvent is less than 0.01 parts by mass with respect to the organic compound, the effects of the inert solvent and the aprotic organic solvent are not sufficiently exhibited, There is a possibility that the cyclization reaction will not proceed sufficiently industrially. Conversely, even if it exceeds 50 parts by mass, the effect commensurate with the addition is not recognized, and the effect of the organic compound cannot be fully exhibited, and the cyclization reaction is efficient. It does not proceed, and the solubility of the precursor of the produced phthalocyanine compound (complex) in the solvent is not sufficient, and the yield of the target halogen-containing phthalocyanine compound may be reduced. Accordingly, the inert solvent and the aprotic organic solvent are compounds other than the organic compound having a hydroxyl group and the organic compound having a carboxyl group.

  The second feature of the present invention is that the inside of the reactor is preferably replaced with an inert gas in advance, and the cyclization reaction is carried out while introducing the inert gas. Thereby, the halogen-containing phthalocyanine compound which is the target product can be produced with high yield and excellent performance. The reason why the target product can be obtained in a high yield and excellent performance by cyclization reaction with the inside of the reactor substantially free of oxygen is not clear. When oxygen is present inside, the metal compound as the metal source is easily oxidized, and becomes a metal oxide and becomes a relatively stable state. As a result, the solubility of the metal compound in the organic compound decreases, Not only does the contact efficiency with the phthalonitrile compound decrease and the reaction rate of the normal reaction slows, but also side reactions occur, the selectivity of the reaction decreases and by-products are generated, yield decreases, etc. An unfavorable situation seems to occur. On the other hand, when the inside of the reactor is replaced with an inert gas, a reaction between the oxygen element in the organic compound structure having the hydroxyl group and / or carboxyl group and the metal compound occurs preferentially. The reaction product with the organic compound is relatively easy to dissolve in the reaction solvent, and as a result of being in an appropriate oxidized state and activated, it is assumed that the cyclization reaction is accelerated and a good reaction result is obtained. ing. Conversely, in an atmosphere where oxygen is present, such as in the presence of excess oxygen or in normal air, the activated state of the metal compound hardly occurs and the cyclization reaction efficiency is lowered. Further, by replacing the inside of the reactor with an inert gas, the risk of explosion of an oxygen-containing gas or the like can be avoided, so that the cyclization reaction can be performed more safely and efficiently. Therefore, as in the method of the present invention, the cyclization reaction is carried out while introducing an inert gas, and more preferably, the oxygen concentration in the gas phase portion in contact with the reaction solution during the reaction is 10 vol% as described in detail below. It is important to carry out while introducing the inert gas so that In addition, when the phthalocyanine compound is metal-free, it is presumed that the action of promoting the cyclization reaction is working between the organic compound having the hydroxyl group and / or carboxyl group and the starting phthalonitrile compound. ing. For example, when a metal halide is used as the central metal source, a compound produced by a reaction between an organic compound and a metal halide is considered to be an active species for the reaction. Further, it is assumed that the hydrogen halide generated at this time acts catalytically on the phthalonitrile compound to further promote the cyclization reaction.

  The inert gas that can be used in this case is not particularly limited as long as it is inert to the cyclization reaction of the present invention, and examples thereof include nitrogen gas, helium gas, argon gas, and carbon dioxide gas. Gas.

  The oxygen concentration inside the reactor when the inside of the reactor is replaced with an inert gas is such that the oxygen concentration in the gas phase portion in contact with the reaction liquid during the reaction is 10 vol% or less, preferably 0 to 7 vol%, more preferably The concentration is from 0 to 5 vol%, and most preferably from 0 to 3 vol%. At this time, when the oxygen concentration exceeds 10 vol%, the cyclization reaction rate is lowered, the yield of the target phthalocyanine compound is lowered, and it is within the explosion range of the organic solvent to be used. There is a possibility. Moreover, even when dissolved oxygen is present in the raw material solution, it is preferable to adjust the oxygen concentration in the solution to be within the above oxygen concentration range by using bubbling or the like together. The oxygen concentration of 0 vol% means a state in which the inside of the reactor is completely replaced with an inert gas.

  As a method of replacing the inside of the reactor with an inert gas, the inert gas is circulated until the oxygen concentration inside the reactor becomes sufficiently low as described above, or the inside of the reactor is added with an inert gas. There are methods such as reducing the pressure to the desired oxygen concentration by repeatedly releasing the pressure and returning it to the normal pressure after the pressure state, but the oxygen concentration inside the reactor (finally during the reaction) This can be achieved by measuring the oxygen concentration of the gas phase portion in contact with the reaction solution using an oxygen concentration meter or the like. There is no particular limitation on the flow rate of the inert gas, and the oxygen concentration in the reactor may be circulated so as to be 10 vol% or less. For example, when a cooling pipe is installed in the reactor, The linear velocity with respect to the cross-sectional area of the connecting portion between the reactor and the cooling pipe is 0.01 to 10 cm / sec, preferably 0.1 to 5 cm / sec, more preferably 0.2 to 3 cm / sec. When the linear velocity is 0.01 cm / sec or less, substitution with an inert gas becomes insufficient, and the reaction becomes disadvantageous. If it is higher than 10 cm / sec, the solvent used in the reaction may be scattered, which may be industrially unfavorable.

  The metal compound used in the method of the present invention is not particularly limited as long as it can produce a target phthalocyanine compound by cyclization reaction with a phthalonitrile compound, but metal, metal oxide, metal carbonyl, metal There are halides and organic acid metals. These metal compounds may be used alone or in the form of a mixture of two or more, and are appropriately selected depending on the structure of the target phthalocyanine compound. The metal compound has a metal corresponding to M of the phthalocyanine compound of the formula (5) obtained after the reaction. Specifically, metals such as iron, copper, zinc, vanadium, titanium, indium, magnesium, and tin; metal halides such as chloride, bromide, and iodide of the metal, such as vanadium chloride, titanium chloride, and chloride Copper, zinc chloride, cobalt chloride, nickel chloride, iron chloride, indium chloride, aluminum chloride, tin chloride, gallium chloride, germanium chloride, magnesium chloride, copper iodide, zinc iodide, cobalt iodide, indium iodide, iodide Aluminum, gallium iodide, copper bromide, zinc bromide, cobalt bromide, aluminum bromide, gallium bromide; vanadium monoxide, vanadium trioxide, vanadium tetroxide, vanadium pentoxide, titanium dioxide, iron monoxide, three Iron dioxide, iron trioxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt dioxide , Cobalt dioxide, cuprous oxide, cupric oxide, copper trioxide, barium oxide, zinc oxide, germanium monoxide, germanium dioxide and other metal oxides; copper acetate, zinc acetate, cobalt acetate, copper benzoate, And organic acid metals such as zinc benzoate; and complex compounds such as acetylacetonate; and metal carbonyls such as cobalt carbonyl, iron carbonyl and nickel carbonyl. Of these, metals, metal oxides and metal halides are preferred, and vanadium chloride and copper chloride are particularly preferably used. When vanadium chloride or copper chloride is used, the central metal is vanadium or copper, respectively.

  The cyclization reaction in the present invention is the same as a generally known method except that the cyclization reaction is carried out in the presence of an organic compound having a hydroxyl group and / or a carboxyl group while introducing an inert gas during the reaction. The reaction conditions of the phthalonitrile compound and the metal compound are not particularly limited as long as the reaction proceeds. For example, the organic compound is in the range of 0.01 to 10 parts by weight, preferably 0.02 to 7.5 parts by weight, and more preferably 0.05 to 5 parts by weight with respect to 1 part by weight of the phthalonitrile compound. It will be charged to become. Moreover, a metal compound is prepared so that it may become the range of 1-3 mol with respect to 4 mol of phthalonitrile compounds, Preferably it is 1.05-2 mol. The reaction temperature is 80 to 250 ° C, preferably 100 to 220 ° C, more preferably 120 to 200 ° C. At this time, if the reaction temperature is too low, the reaction rate becomes very slow and impractical, whereas if the reaction temperature is too high, side reactions are likely to occur and the yield of the target product is reduced. The reaction time is 0.1 to 24 hours, preferably 0.5 to 20 hours, more preferably 1 to 18 hours. In addition, after reaction, according to the synthesis method of a conventionally well-known phthalocyanine compound, it can obtain efficiently and with high purity by filtering, washing | cleaning, and drying.

  Hereinafter, the phthalonitrile compounds of the formulas (1) to (4) used as raw materials in the present invention and the phthalocyanine compound of the formula (5) produced therefrom will be described.

  The phthalonitrile compounds represented by the formulas (1) to (4) used in the present invention have at least one halogen atom in the benzene nucleus of phthalonitrile, or phenyl which may have a substituent. Group, an aralkyl group which may have a substituent, or an alkyl group having 1 to 20 carbon atoms which may have a substituent is a phthalonitrile in which a nitrogen, oxygen or sulfur atom is bonded. Reaction using one or different types of phthalonitrile, in which at least one halogen atom is contained in the phthalocyanine skeleton, the metal compound and the organic group having a hydroxyl group and / or a carboxyl group A halogen atom-containing phthalocyanine represented by the formula (5) can be produced by reacting in the presence of a compound while introducing an inert gas during the reaction. .

In the above formulas (1) to (4), Z _{1 to} Z ₄ , Z _{5 to} Z ₈ , Z _{9 to} Z ₁₂ , and Z _{13 to} Z ₁₆ are a hydrogen atom, NHR ¹ , SR ² , OR ^3. Or represents a halogen atom. In this case, Z _{1 to} Z ₄ , Z _{5 to} Z ₈ , Z _{9 to} Z ₁₂ , and Z _{13 to} Z ₁₆ may be the same or different. In addition, at least one of Z _{1 to} Z ₄ , Z _{5 to} Z ₈ , Z _{9 to} Z ₁₂ , and Z _{13 to} Z ₁₆ is a halogen atom. R ¹ , R ² and R ³ are each an optionally substituted phenyl group, an optionally substituted aralkyl group or an optionally substituted carbon atom having 1 to 20 carbon atoms. Represents an alkyl group. At this time, R ¹ , R ² and R ³ may be the same or different. In addition, when there are a plurality of R ¹ in the above formula (1), R ¹ may be the same or different from each other. R ² and R ³ in the formula (1) The same applies to the case where a plurality of these are present, and the same definition as in the above formula (1) is applied to the above formulas (2) to (4).

In the above formula (5), Z _{1 to} Z ₁₆ represent a hydrogen atom, NHR ¹ , SR ² , OR ³ or a halogen atom, and at least one is a halogen atom. In the above formula (5), Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ , Z ₁₆ (also referred to as substituents substituted at eight α-positions of the phthalocyanine nucleus) are all halogens. 0 to 8 of Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ , Z ₁₅ (also referred to as substituents substituted at 8 positions of the phthalocyanine nucleus) are atoms. A halogen atom is preferred. Alternatively, 1 to 7 of the substituents at the α-position are halogen atoms, and more preferably 1 to 4 of the substituents at the α-position are halogen atoms and 4 are OR ^3. preferable. In this case, at least one substituent at the β-position preferably represents SR ² , more preferably 4 or more represent SR ² , and particularly preferably all 8 represent SR ² . Thus, by introducing an electron donating group such as SR ² , a phthalocyanine compound that has a long absorption wavelength, is particularly excellent in visible light transmittance, and obtains near-infrared selective absorption ability, and Become. R ¹ , R ² and R ³ are the same as defined in the above formulas (1) to (4).

  In the above formula (5), M represents a metal-free, metal, metal oxide or metal halide. Here, the term “metal-free” means that there is no metal at the center, that is, there are two hydrogen atoms instead of the central metal. Examples of the metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl, vanadyl, cobalt carbonyl, iron carbonyl and the like. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, silicon chloride, gallium chloride, dichlorogermanium, indium iodide, aluminum iodide, and gallium iodide. It is done. Preferably, it is a metal, metal oxide or metal halide, specifically, copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, tin (II) chloride, more preferably copper, Zinc, cobalt, vanadyl, and tin (II) chloride.

Here, examples of the aralkyl group in R ¹ , R ² and R ³ include, but are not limited to, a benzyl group, a phenethyl group, and a diphenylmethyl group.

  Examples of the substituent that may be present in the phenyl group or aralkyl group include a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxyl group, a halogenated alkyl group, a halogenated alkoxyl group, a nitro group, and an amino group. Group, alkylamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, oxyalkyl ether group, cyano Examples include groups, but are not limited thereto. These substituents can be substituted with 1 to 5 phenyl groups or aralkyl groups, and the types of these substituents may be the same or different when a plurality of substituents are substituted. Some of the above substituents are shown below with more specific examples.

  In the present specification, the “halogen atom” is a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom.

  In addition, the phenyl group or aralkyl group may or may not have a substituent. However, among the substituents that can be present when the phenyl group or aralkyl group has a substituent, acyl Examples of the group include an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, a pentylcarbonyl group, a hexylcarbonyl group, a benzoyl group, and a pt-butylbenzoyl group. Among these, the ethylcarbonyl group is preferable.

  Of the substituents optionally present in the phenyl group or aralkyl group, the alkyl group is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably 1 carbon atom. ~ 8 linear, branched or cyclic alkyl groups. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1, 2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2 -Methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group and the like can be mentioned. Of these, a methyl group and an ethyl group are preferred.

  Of the substituents optionally present in the phenyl group or aralkyl group, the alkoxyl group is a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. Straight, branched or cyclic alkoxyl groups. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, neo Examples include pentyloxy group, 1,2-dimethyl-propoxy group, n-hexyloxy group, cyclohexyloxy group, 1,3-dimethylbutoxy group, 1-isopropylpropoxy group and the like. Of these, methoxy and ethoxy groups are preferred.

  Among the substituents optionally present in the phenyl group or aralkyl group, the halogenated alkyl group is a halogenated part of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Preferably, a part of a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is halogenated. Specific examples include chloromethyl group, bromomethyl group, trifluoromethyl group, chloroethyl group, 2,2,2-trichloroethyl group, bromoethyl group, chloropropyl group, bromopropyl group and the like.

  Among the substituents optionally present in the phenyl group or aralkyl group, the halogenated alkoxyl group is a halogenated part of a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms. Preferably, a part of a linear, branched or cyclic alkoxyl group having 1 to 8 carbon atoms is halogenated. Specific examples include chloromethoxy group, bromomethoxy group, trifluoromethoxy group, chloroethoxy group, 2,2,2-trichloroethoxy group, bromoethoxy group, chloropropoxy group, bromopropoxy group and the like.

  Of the substituents optionally present in the phenyl group or aralkyl group, the alkylamino group is an alkylamino group having an alkyl moiety having 1 to 20 carbon atoms, preferably an alkyl having 1 to 8 carbon atoms. An alkylamino group having a moiety. Specifically, methylamino group, ethylamino group, n-propylamino group, n-butylamino group, sec-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n -An octylamino group, 2-ethylhexylamino group, etc. are mentioned. Of these, a methylamino group, an ethylamino group, an n-propylamino group, and an n-butylamino group are preferable.

  Of the substituents optionally present in the phenyl group or aralkyl group, the alkylcarbonylamino group is an alkylcarbonylamino group having an alkyl moiety having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. An alkylcarbonylamino group having the following alkyl moiety. Specifically, methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, n-butylcarbonylamino group, sec-butylcarbonylamino group, n-pentylcarbonylamino group, n-hexylcarbonylamino group, Examples include n-heptylcarbonylamino group, n-octylcarbonylamino group, 2-ethylhexylcarbonylamino group and the like. Of these, a methylcarbonylamino group, an ethylcarbonylamino group, an n-propylcarbonylamino group, and an n-butylcarbonylamino group are preferable.

  Of the substituents optionally present in the phenyl group or aralkyl group, the alkylaminocarbonyl group is an alkylaminocarbonyl group having the same alkyl group as the alkylcarbonylamino group.

  Among the substituents optionally present in the above phenyl group or aralkyl group, the alkoxycarbonyl group is a C 1-8, preferably 1-5 carbon atom which may contain a hetero atom in the alkyl group part of the alkoxyl group. Or a cyclic alkoxycarbonyl group having 3 to 8, preferably 5 to 8 carbon atoms which may contain a hetero atom. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, and a tert-butoxycarbonyl group. . Of these, a methoxycarbonyl group and an ethoxycarbonyl group are preferred.

  Of the substituents optionally present in the phenyl group or aralkyl group, the alkoxysulfonyl group is an alkoxysulfonyl group having an alkyl moiety having 1 to 20 carbon atoms, preferably an alkyl having 1 to 8 carbon atoms. An alkoxysulfonyl group having a moiety.

  Of the substituents optionally present in the phenyl group or aralkyl group, the alkylthio group is an alkylthio group having an alkyl moiety having 1 to 20 carbon atoms, preferably an alkyl moiety having 1 to 8 carbon atoms. It has an alkylthio group.

  Of the substituents optionally present in the phenyl group or aralkyl group, the oxyalkyl ether group is an oxyalkyl ether group having an alkyl moiety having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. It is an oxyalkyl ether group having an alkyl moiety.

On the other hand, the unsubstituted alkyl group having 1 to 20 carbon atoms in R ¹ , R ² and R ³ may be any one of linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. , Preferably a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1, 2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2 -Methyl 1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group and the like can be mentioned. Of these, methyl, ethyl, n-propyl, isopropyl and n-butyl groups are preferred.

  Examples of the substituent optionally present in the alkyl group having 1 to 20 carbon atoms include a halogen atom, an alkoxyl group, a hydroxyalkoxyl group, an alkoxyalkoxyl group, a halogenated alkoxyl group, a nitro group, and an amino group. An alkylamino group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkoxysulfonyl group, and the like can be exemplified, but are not limited thereto. These types of substituents may be the same or different when a plurality of substituents are substituted. More specific examples of a part of these substituents may be those listed above as more specific examples of a part of the substituents optionally present in the phenyl group or aralkyl group. This is omitted here.

As described above, the halogen-containing phthalocyanine compound produced by the method of the present invention has various uses including a heat ray absorbing dye, and exhibits its function by selecting an optimal one from the above substituents. Can be made. For example, when used for heat ray absorbing dyes, Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ , Z ₁₆ (substitution substituted at eight α positions of the phthalocyanine nucleus) Are all halogen atoms and are also Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ , Z ₁₅ (substituents substituted at eight β positions of the phthalocyanine nucleus). It is particularly preferred to use as a raw material a phthalonitrile compound that produces a phthalocyanine compound of the formula (5) (claim 8) wherein 0-8 of the halogen atoms are halogen atoms.

  As a phthalonitrile compound preferably used as a raw material for producing such a phthalocyanine compound, there is one represented by the following formula (6).

  In the above formula (6), -CN is a nitrile group, X is a halogen atom, F is a fluorine atom, and Y is the following substituents (a), (b), (c), (d) , (E), (f) or (g), m is 0, 1 or 2, and n is 0, 1 or 2. However, at this time, 0 ≦ m + n ≦ 2.

  In the above formula (6), the substituent (a) is a substituted or unsubstituted phenoxy group having the following formula.

  In the above formula, R is an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, preferably a fluorine atom or a chlorine atom, and a and b are each independently 0 It is an integer of ~ 5. At this time, 0 ≦ a + b ≦ 5. Examples of such substituent (a) include o-methoxycarbonylphenoxy group, m-methoxycarbonylphenoxy group, p-methoxycarbonylphenoxy group, o-ethoxycarbonylphenoxy group, m-ethoxycarbonylphenoxy group, p- Ethoxycarbonylphenoxy group, o-butoxycarbonylphenoxy group, m-butoxycarbonylphenoxy group, p-butoxycarbonylphenoxy group, o-methyl-p-methoxycarbonylphenoxy group, o-methoxy-p-ethoxycarbonylphenoxy group, o- Fluoro-p-methoxycarbonylphenoxy group, tetrafluoro-p-ethoxycarbonylphenoxy group, o-ethoxycarbonyl-p-methylphenoxy group, o-butoxycarbonyl-p-methylphenoxy group, o-butoxy Carbonyl -p- fluorophenoxy group, p- methyl -m- butoxycarbonyl phenoxy group, 2,5-dichlorophenoxy group.

  In the above formula (6), the substituent (b) is a substituted or unsubstituted phenylthio group having the following formula.

  In the above formula, R is an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, preferably a fluorine atom or a chlorine atom, and a and b are each independently And it is an integer of 0-5. At this time, 0 ≦ a + b ≦ 5. Examples of such substituent (b) include o-methoxycarbonylphenylthio group, m-methoxycarbonylphenylthio group, p-methoxycarbonylphenylthio group, o-ethoxycarbonylphenylthio group, m-ethoxycarbonylphenyl. Thio group, p-ethoxycarbonylphenylthio group, o-butoxycarbonylphenylthio group, m-butoxycarbonylphenylthio group, p-butoxycarbonylphenylthio group, o-methyl-p-methoxycarbonylphenylthio group, o-methoxy -P-methoxycarbonylphenylthio group, o-fluoro-p-methoxycarbonylphenylthio group, tetrafluoro-p-ethoxycarbonylphenylthio group, o-ethoxycarbonyl-p-methylphenylthio group, o-butoxycarbonyl-p −Me Rufeniruchio group, o- butoxycarbonyl -p- fluorophenylthio group, such as p- methyl -m- butoxycarbonyl phenylthio group.

  In the above formula (6), the substituent (c) is a substituted or unsubstituted anilino group having the following formula.

  In the above formula, Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, or an alkoxycarbonyl group having 1 to 4 carbon atoms, and c is 0, 1 or 2 is there. Examples of such substituent (c) include anilino group, o-toluidino group, m-toluidino group, p-toluidino group, 2,4-xylidino group, 2,6-xylidino group, o-methoxyanilino. Group, m-methoxyanilino group, p-methoxyanilino group, o-fluoroanilino group, m-fluoroanilino group, p-fluoroanilino group, tetrafluoroanilino group, p-ethoxycarbonylanilino group Etc.

  In the above formula (6), the substituent (d) is an alkoxy group substituted with an alkylamino group having the following formula.

  In the above formula, R ′ and R ″ are each independently an alkyl group having 1 to 8 carbon atoms, and d is an integer of 1 to 8. Examples of such substituent (d) include Dimethylaminoethoxy group, diethylaminoethoxy group, diethylaminobutoxy group and the like.

  In the above formula (6), the substituent (e) is an alkylthio group substituted with an alkylamino group having the following formula.

  In the above formula, R ′ and R ″ are each independently an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and d is an integer of 1 to 8. Such a substituent ( Examples of e) include dimethylaminoethylthio group, diethylaminoethylthio group, dibutylaminobutylthio group and the like.

  In the above formula (6), the substituent (f) is a substituted or unsubstituted alkylamino group having the following formula.

  In the above formula, e is an integer of 0 to 7, preferably 0 to 4, and the alkylene group and / or the alkyl group are each independently an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms. It may be substituted with at least one selected from the group consisting of an alkoxy group and an alkoxycarbonyl group having 1 to 4 carbon atoms. Examples of such substituent (f) include a methylamino group, an ethylamino group, and a butylamino group.

  In the above formula (6), the substituent (g) is a substituted alkoxy group having the following formula.

  In said formula, W is a C1-C4, Preferably it is 1-2 alkoxy group or an acyl group, f is an integer of 1-6, Preferably it is 1-4. Examples of such a substituent (g) include a methoxyethoxy group, 3 ′, 6 ′, 9′-oxadecyloxy group, 3 ′, 6 ′, 9 ′, 12′-oxatridecyloxy group, acetyl An ethoxy group, 5'-acetyl-3'-oxapentyloxy group, 8'-acetyl-3 ', 6'-oxaoctyloxy group, etc. are mentioned.

  Among these phthalonitrile compounds of the formulas (1) to (4), a phthalonitrile compound having at least one fluorine atom, specifically, tetrafluorophthalonitrile, 3,5,6-trifluoro-4 -Methoxycarbonylphenoxyphthalonitrile, 3,5,6-trifluoro-4-ethoxycarbonylphenoxyphthalonitrile, 3,5,6-trifluoro-4-butoxycarbonylphenoxyphthalonitrile, 3,5,6-trifluoro- 4- (o-methyl-p-methoxycarbonylphenoxy) phthalonitrile, 3,5,6-trifluoro-4- (o-fluoro-p-methoxycarbonylphenoxy) phthalonitrile, 3,5,6-trifluoro- 4- (o-methoxy-p-ethoxycarbonylphenoxy) phthalonitrile, 3 5,6-trifluoro-4- (tetrafluoro-p-ethoxycarbonylphenoxy) phthalonitrile, 3,5,6-trifluoro-4- (p-methyl-o-ethoxycarbonylphenoxy) phthalonitrile, 3,6 -Difluoro-4,5-bis (methoxycarbonylphenoxy) phthalonitrile, 3,6-difluoro-4,5-bis (ethoxycarbonylphenoxy) phthalonitrile, 3,6-difluoro-4,5-bis (butoxycarbonylphenoxy) ) Phthalonitrile, 3,6-difluoro-4,5-bis (o-methyl-p-methoxycarbonylphenoxy) phthalonitrile, 3,6-difluoro-4,5-bis (o-fluoro-p-methoxycarbonylphenoxy) ) Phthalonitrile, 3,6-difluoro-4,5-bis (o-meth) Cis-p-ethoxycarbonylphenoxy) phthalonitrile, 3,6-difluoro-4,5-bis (tetrafluoro-p-ethoxycarbonylphenoxy) phthalonitrile, 3,6-difluoro-4,5-bis (2,5 -Dichlorophenoxy) phthalonitrile, 3,6-difluoro-4,5-bis (methoxycarbonylphenylthio) phthalonitrile, 3,6-difluoro-4,5-bis (ethoxycarbonylphenylthio) phthalonitrile, 3,6 -Difluoro-4,5-bis (butoxycarbonylphenylthio) phthalonitrile, 3,6-difluoro-4,5-bis (o-methyl-p-methoxycarbonylphenylthio) phthalonitrile, 3,6-difluoro-4 , 5-Bis (o-fluoro-p-methoxycarbonylphenylthio) phthalo Nitrile, 3,6-difluoro-4,5-bis (o-methoxy-p-ethoxycarbonylphenylthio) phthalonitrile, 3,5,6-trifluoro-4-anilinophthalonitrile, 3,5,6- Trifluoro-4-toluidinophthalonitrile, 3,5,6-trifluoro-4-xylidinophthalonitrile, 3,5,6-trifluoro-4-methoxyanilinophthalonitrile, 3,5,6- Trifluoro-4-fluoroanilinophthalonitrile, 3,5,6-trifluoro-4-methylaminophthalonitrile, 3,5,6-trifluoro-4-ethylaminophthalonitrile, 3,5,6-tri Fluoro-4-butylaminophthalonitrile, 3,5,6-trifluoro-4-octylaminophthalonitrile, 3,6-difluoro-4,5-bis Nilinophthalonitrile, 3,6-difluoro-4,5-bistoluidinophthalonitrile, 3,6-difluoro-4,5-bis (methoxyanilino) phthalonitrile, 3,6-difluoro-4,5- Bis (ethoxycarbonylanilino) phthalonitrile, 3,5,6-trifluoro-4-dimethylaminoethoxyphthalonitrile, 3,5,6-trifluoro-4-diethylaminoethoxyphthalonitrile, 3,5,6-tri Fluoro-4-diethylaminoethylthiophthalonitrile, 3,5,6-trifluoro-4-diethylaminobutylthiophthalonitrile and the like are preferably used.

  The phthalonitrile compounds of formulas (1) to (4) according to the present invention are all known and can be produced by various methods. For example, in the case of tetrafluorophthalonitrile, it can be easily obtained by a halogen exchange reaction between tetrachlorophthalonitrile obtained by chlorination reaction of phthalonitrile and a fluorinating agent. The phthalonitrile compound having the substituents (a) to (g) includes, for example, tetrafluorophthalonitrile and a compound in which a hydrogen atom or an alkali metal atom is linked to each substituent (for example, the substituent (a) In the case of the following formula:

Where M ′ is a hydrogen atom or an alkali metal atom). Under the present circumstances, the phthalonitrile compound of Formula (1)-(4) is suitably selected by the structure of the phthalocyanine compound manufactured, and may be the same or different.

  As the halogen-containing phthalocyanine compound suitably used for the heat ray absorbing dye produced in this way, the following formula:

There is a compound represented by

  In the above, F is a fluorine atom, Me is two hydrogen atoms, or a metal atom or a metal compound, which corresponds to M in the above formula (5), and Y is the substituents (a) to (g ).

  A halogen-containing phthalocyanine compound having Me as a hydrogen atom can be obtained by subjecting a halogen-containing phthalonitrile compound as a starting material to a cyclization reaction alone. The type and position of the substituent of the halogen-containing phthalocyanine compound of the above formula are determined by the type and position of the substituent of the halogen-containing phthalonitrile compound of the formulas (1) to (4) used as a starting material. The

Preferable examples of the halogen-containing phthalocyanine compound (wherein M in formula (5) is metal-free) obtained by the method of the present invention include the following. The phthalocyanine compound according to the present invention is not limited to this, and it goes without saying that the phthalocyanine compound exemplified below may be an appropriate metal other than a metal, a metal oxide, or a metal halide. . Further, in the following compounds, the 3rd and 6th positions are substituted with the α position of the phthalocyanine nucleus (substitution positions of Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ , Z ₁₆ ). The 4th and 5th positions are substituted at the β position of the phthalocyanine nucleus (substitution positions of Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ , Z ₁₅ ).

  Hexadecafluorophthalocyanine, 3,5,6-dodecafluoro-4-tetrakis (methoxycarbonylphenoxy) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis (ethoxycarbonylphenoxy) phthalocyanine, 3,5,6-dodeca Fluoro-4-tetrakis (butoxycarbonylphenoxy) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis (o-methyl-p-methoxycarbonylphenoxy) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis ( o-fluoro-p-methoxycarbonylphenoxy) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis (o-methoxy-p-ethoxycarbonylphenoxy) phthalocyanine, 3,5,6-dodecafluoro-4-tetraki (Tetrafluoro-p-ethoxycarbonylphenoxy) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis (p-methyl-o-ethoxycarbonylphenoxy) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis ( Methoxycarbonylphenoxy) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis (ethoxycarbonylphenoxy) phthalocyanine, 3,6-octafluoro-4,5-octakis (methoxycarbonylphenoxy) phthalocyanine, 3,6-octafluoro -4,5-octakis (ethoxycarbonylphenoxy) phthalocyanine, 3,6-octafluoro-4,5-octakis (butoxycarbonylphenoxy) phthalocyanine, 3,6-octafluoro-4,5-octaki (O-methyl-p-methoxycarbonylphenoxy) phthalocyanine, 3,6-octafluoro-4,5-octakis (o-fluoro-p-methoxycarbonylphenoxy) phthalocyanine, 3,6-octafluoro-4,5-octakis (O-methoxy-p-ethoxycarbonylphenoxy) phthalocyanine, 3,6-octafluoro-4,5-octakis (2,5-dichlorophenoxy) phthalocyanine, 3,6-octafluoro-4,5-octakis (methoxycarbonyl) Phenylthio) phthalocyanine, 3,6-octafluoro-4,5-octakis (ethoxycarbonylphenylthio) phthalocyanine, 3,6-octafluoro-4,5-octakis (butoxycarbonylphenylthio) phthalocyanine, 3,6-octa Fluoro -4,5-octakis (o-methyl-p-methoxycarbonylphenylthio) phthalocyanine, 3,6-octafluoro-4,5-octakis (o-fluoro-p-methoxycarbonylphenylthio) phthalocyanine, 3,6 Octafluoro-4,5-octakis (o-methoxy-p-ethoxycarbonylphenylthio) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis (anilino) phthalocyanine, 3,5,6-dodecafluoro-4 Tetrakis (toluidino) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis (xylidino) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis (methoxyanilino) phthalocyanine, 3,5,6-dodeca Fluoro-4-tetrakis (fluoroanilino) lid Cyanine, 3,5,6-dodecafluoro-4-tetrakis (methylamino) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis (ethylamino) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis (Butylamino) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis (octylamino) phthalocyanine, 3,6-octafluoro-4,5-octakis (anilino) phthalocyanine, 3,6-octafluoro-4, 5-octakis (toluidino) phthalocyanine, 3,6-octafluoro-4,5-octakis (methoxyanilino) phthalocyanine, 3,6-octafluoro-4,5-octakis (ethoxycarbonylanilino) phthalocyanine, 3,5 , 6-Dodecafluoro-4-tetrakis Ruaminoethoxy) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis (diethylaminoethoxy) phthalocyanine, 3,5,6-dodecafluoro-4-tetrakis (diethylaminoethylthio) phthalocyanine, and 3,5,6- Examples include dodecafluoro-4-tetrakis (diethylaminobutylthio) phthalocyanine.

  Of the above phthalocyanine compounds, hexadecafluorophthalocyanine, 3,6-octafluoro-4,5-octakis (anilino) phthalocyanine, 3,6-octafluoro-4,5-octakis (methoxycarbonylphenoxy) phthalocyanine, 3,6 -Octafluoro-4,5-octakis (2,5-dichlorophenoxy) phthalocyanine is preferably used, and these halogen-containing phthalocyanine compounds are obtained using the above-mentioned suitable halogen-containing phthalonitrile compounds as starting materials.

Alternatively, the halogen-containing phthalocyanine compound produced by the method of the present invention is used for applications such as a heat ray shielding material, a filter for plasma display, a non-infrared fixing toner such as flash fixing, or a near-infrared absorber for heat-retaining heat storage fibers. In some cases, 1 to 7 of the substituents at the α-position are halogen atoms, more preferably 1 to 4 of the substituents at the α-position are halogen atoms and 4 are OR ³ . It is preferable to use as a raw material a phthalonitrile compound from which the phthalocyanine compound of the formula (5) (claims 9 and 10) is produced. Even more preferably, a phthalocyanine compound in which the substituent at the β-position represents SR ² or a halogen atom is preferably used. Such a phthalocyanine compound is characterized by excellent near infrared selective absorption ability. Furthermore, it is because it is excellent in compatibility with resin and is excellent in characteristics such as heat resistance, light resistance, and weather resistance.

Examples of the phthalonitrile compound preferably used as a raw material for producing such a phthalocyanine compound include 4,5-bis (phenylthio) -3-fluoro-6-anilinophthalonitrile, 4,5-bis ( Phenylthio) -3-fluoro-6-anisidinophthalonitrile, 4,5-bis (phenylthio) -3-fluoro-6-benzylaminophthalonitrile, 4,5-bis (phenylthio) -3-fluoro-6-butyl Aminophthalonitrile, 4,5-bis (phenylthio) -3-fluoro-6-ethoxyethanol aminophthalonitrile, 4,5-bis (2-chlorophenylthio) -3-fluoro-6-anilinophthalonitrile, 4, 5-Bis (2-chlorophenylthio) -3-fluoro-6-benzylaminophthalonitrile 4,5-bis (4-methoxyphenylthio) -3-fluoro-6-anilinophthalonitrile, 4,5-bis (4-methoxyphenylthio) -3-fluoro-6-benzylaminophthalonitrile, 4, , 5-bis (4-methoxyphenylthio) -3-fluoro-6-butylaminophthalonitrile, 4,5-bis (2,5-dichlorophenylthio) -3-fluoro-6-anilinophthalonitrile, 4, 5-bis (2,5-dichlorophenylthio) -3-fluoro-6-benzylaminophthalonitrile, 4,5-bis (2,5-dichlorophenylthio) -3-fluoro-6-butylaminophthalonitrile, 4, 5-bis (phenylthio) -3-fluoro-6-phenoxyphthalonitrile, 4,5-bis (phenylthio) -3-fluoro-6- (di Tilphenoxy) phthalonitrile, 4,5-bis (phenylthio) -3-fluoro-6- (dichlorophenoxy) phthalonitrile, 4,5-bis (butylthio) -3-fluoro-6-anilinophthalonitrile, 4, 5-bis (butylthio) -3-fluoro-6- (phenoxy) phthalonitrile, 4,5-bis (butylthio) -3-fluoro-6- (hexyloxy) phthalonitrile, 4,5-bis (phenylthio)- 3-chloro-6-anilinophthalonitrile, 4,5-bis (phenylthio) -3-chloro-6-anisidinophthalonitrile, 4,5-bis (phenylthio) -3-chloro-6-benzylaminophthalonitrile 4,5-bis (phenylthio) -3-chloro-6-butylaminophthalonitrile, 4,5-bis (phenylthio)- 3-chloro-6-ethoxyethanolaminophthalonitrile, 4,5-bis (2-chlorophenylthio) -3-chloro-6-anilinophthalonitrile, 4,5-bis (2-chlorophenylthio) -3-chloro -6-benzylaminophthalonitrile, 4,5-bis (2-chlorophenylthio) -3-chloro-6-butylaminophthalonitrile, 4,5-bis (2-chlorophenylthio) -3-chloro-6-ethoxy Ethanolaminophthalonitrile, 4,5-bis (4-methoxyphenylthio) -3-chloro-6-anilinophthalonitrile, 4,5-bis (4-methoxyphenylthio) -3-chloro-6-benzylamino Phthalonitrile, 4,5-bis (4-methoxyphenylthio) -3-chloro-6-butylaminophthalonitrile, 4,5- (2,5-dichlorophenylthio) -3-chloro-6-anilinophthalonitrile, 4,5-bis (2,5-dichlorophenylthio) -3-chloro-6-benzylaminophthalonitrile, 4,5- Bis (2,5-dichlorophenylthio) -3-chloro-6-butylaminophthalonitrile, 4,5-bis (phenylthio) -3-chloro-6-phenoxyphthalonitrile, 4,5-bis (phenylthio) -3 -Chloro-6- (dimethylphenoxy) phthalonitrile, 4,5-bis (phenylthio) -3-chloro-6- (dichlorophenoxy) phthalonitrile, 4,5-bis (2-chlorophenylthio) -3-chloro -6-phenoxyphthalonitrile, 4,5-bis (2-chlorophenylthio) -3-chloro-6- (dimethylphenoxy) phthalo Tolyl, 4,5-bis (2-chlorophenylthio) -3-chloro-6- (dichlorophenoxy) phthalonitrile, 4,5-bis (4-methoxyphenylthio) -3-chloro-6-phenoxyphthalonitrile 4,5-bis (4-phenylthio) -3-chloro-6- (dimethylphenoxy) phthalonitrile, 4,5-bis (4-phenylthio) -3-chloro-6- (dichlorophenoxy) phthalonitrile,
4,5-bis (butylthio) -3-chloro-6-anilinophthalonitrile, 4,5-bis (butylthio) -3-chloro-6- (phenoxy) phthalonitrile, 4,5-bis (butylthio)- 3-chloro-6- (hexyloxy) phthalonitrile, 3,4-difluoro-5-phenylthio-6-anilinophthalonitrile, 3,4-difluoro-5- (2-chlorophenylthio) -6-anilino Phthalonitrile, 3,4-difluoro-5- (2-chlorophenylthio) -6-benzylaminophthalonitrile, 3-fluoro-4-chloro-5-phenylthio-6-anilinophthalonitrile, 3,4-difluoro -5-phenylthio-6-phenoxyphthalonitrile, 3,4-difluoro-5- (4-methoxyphenylthio) -6-anilinophthaloni Lil, etc. 3,4-difluoro-5- (4-methoxyphenyl-thio) -6- phenoxy shifter nitrile and the like.

Preferable examples of such phthalocyanine compounds (wherein M in formula (5) is metal-free) include the following. The phthalocyanine compound according to the present invention is not limited to this, and it goes without saying that the phthalocyanine compound exemplified below may be an appropriate metal other than a metal, a metal oxide, or a metal halide. . Further, in the following compounds, the 3rd and 6th positions are substituted with the α position of the phthalocyanine nucleus (substitution positions of Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ , Z ₁₆ ). The 4th and 5th positions are substituted at the β position of the phthalocyanine nucleus (substitution positions of Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ , Z ₁₅ ).

4,5-octakis (phenoxy) -3,6- {tetrakis (phenoxy) -tris (anilino) -fluoro} phthalocyanine, 4,5-octakis (2,6-dichlorophenoxy) -3,6- {tetrakis (2 , 6-Dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} phthalocyanine, 4,5-octakis (2,6-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -Tris (benzylamino) -fluoro} phthalocyanine, 4,5-octakis (2,6-dichlorophenoxy) -3,6- {tetrakis (2,6-dibromo-4-methylphenoxy) -tris (DL-1- Phenylethylamino) -fluoro} phthalocyanine, 4,5-octakis (2,5-dichlorophenoxy) ) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} phthalocyanine, 4,5-octakis (2,5-dichlorophenoxy) -3,6- {Tetrakis (2,6-dimethylphenoxy) -tris (benzylamino) -fluoro} phthalocyanine, 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dibromo-4- Methylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} phthalocyanine, 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dibromo-4-methylphenoxy) ) -Bis (DL-1-phenylethylamino) -difluoro} phthalocyanine, 4,5-octakis (4 Cyanophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} phthalocyanine, 4,5-octakis (4-cyanophenoxy) -3,6- {Tetrakis (2,6-dimethylphenoxy) -tris (benzylamino) -fluoro} phthalocyanine, 4,5-octakis (4-cyanophenoxy) -3,6- {tetrakis (2,6-dibromo-4-methylphenoxy) ) -Tris (DL-1-phenylethylamino) -fluoro} phthalocyanine, 4,5- {tetrakis (butoxy) -tetrakis (2,6-dimethylphenoxy)}-3,6- {tetrakis (2,6-dimethyl) Phenoxy) -tris (benzylamino) -fluoro} phthalocyanine, 4,5-octakis ( Phenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (benzylamino) -fluoro} phthalocyanine, 4,5-octakis (phenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) ) -Tris (anilino) -fluoro} phthalocyanine, 4,5-octakis (butylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (benzylamino) -fluoro} phthalocyanine, 4,5- { Tetrakis (butoxy) -tetrakis (phenylthio)}-3,6- {tetrakis (2,6-dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} phthalocyanine, 4,5-octakis (phenoxy)- 3,6- {tetrakis (phenoxy) -tris (benzylamido ) - chloro} phthalocyanine,
4,5-octakis (phenylthio) -3,6- (heptakisphenylethylamino-fluoro) phthalocyanine, 4,5-octakis (phenylthio) -3,6- (pentakisphenylethylamino-trifluoro) phthalocyanine, 4 , 5-octakis (phenylthio) -3,6- {heptakis (DL-1-phenylethylamino) -fluoro} phthalocyanine, 4,5-octakis (phenylthio) -3,6- {pentakis (DL-1-phenylethyl) Amino) -trifluoro} phthalocyanine, 4,5-octakis (phenylthio) -3,6- (heptakisbenzhydrylamino-fluoro) phthalocyanine, 4,5-octakis (phenylthio) -3,6- (pentakisbenz Hydrylamino-trifluoro) phthalocyanine, 4 5-octakis (p-cyanophenoxy) -3,6- (heptakisphenylethylamino-fluoro) phthalocyanine, 4,5-octakis (p-cyanophenoxy) -3,6- (pentakisphenylethylamino-trifluoro) ) Phthalocyanine, 4,5-octakis (p-cyanophenoxy) -3,6- {heptakis (DL-1-phenylethylamino) -fluoro} phthalocyanine, 4,5-octakis (p-cyanophenoxy) -3,6 -{Pentakis (DL-1-phenylethylamino) -trifluoro} phthalocyanine, 4,5-octakis (p-cyanophenoxy) -3,6- (heptakisbenzhydrylamino-fluoro) phthalocyanine, 4,5- Octakis (p-cyanophenoxy) -3,6- (pentakisbenzhi Riruamino - trifluoromethyl) phthalocyanine,
4,5-octakis (phenoxy) -3,6- (pentakisanilino-trifluoro) phthalocyanine, 4,5-octakis (phenoxy) -3,6- (tetrakisanilino-tetrafluoro) phthalocyanine, 4,5 -Octakis (phenoxy) -3,6- (trisanilino-pentafluoro) phthalocyanine, 4,5-octakis (phenoxy) -3,6- (pentakisanisidino-trifluoro) phthalocyanine, 4,5-octakis (phenoxy) -3,6- (trisanisidino-pentafluoro) phthalocyanine, 4,5-octakis (phenoxy) -3,6- (heptakisbenzylamino-monofluoro) phthalocyanine, 4,5-octakis (phenoxy) -3,6- (Hexakisbenzylamino-difluoro) phthalocyanine 4,5-octakis (phenoxy) -3,6- (hexakisbenzylamino-difluoro) phthalocyanine, 4,5-octakis (phenoxy) -3,6- (pentakisbenzylamino-trifluoro) phthalocyanine, 4, 5-octakis (phenoxy) -3,6- (tetrakisbenzylamino-tetrafluoro) phthalocyanine, 4,5-octakis (phenoxy) -3,6- (heptakisbutylamino-monofluoro) phthalocyanine, 4,5-octakis (Phenoxy) -3,6- (pentakisbutylamino-trifluoro) phthalocyanine, 4,5-octakis (phenoxy) -3,6- (hexakisethoxyethanolamino-difluoro) phthalocyanine, 4,5-octakis (phenoxy) ) -3,6- (pentakisuchi) Carbonylphenylamino-trifluoro) phthalocyanine, 4,5-octakis (butoxy) -3,6- (pentakisanilino-trifluoro) phthalocyanine, 4,5-octakis (butoxy) -3,6- (trisanilino-penta Fluoro) phthalocyanine, 4,5-octakis (butoxy) -3,6- (heptakisbenzylamino-monofluoro) phthalocyanine,
4,5-octakis (butoxy) -3,6- (pentakisbenzylamino-trifluoro) phthalocyanine, 4,5- (trisbutoxy-pentafluoro) -3,6- (heptakisbutylamino-monofluoro) phthalocyanine 4,5- (tetrakisbutoxy-tetrafluoro) -3,6- (pentakisbutylamino-trifluoro) phthalocyanine, 4,5- (tetrakisphenoxy-tetrafluoro) -3,6- (hexakisbenzylamino- Difluoro) phthalocyanine, 4,5-octakis (p-cyanophenoxy) -3,6- (heptakisphenylethylamino-fluoro) phthalocyanine, 4,5-octakis (p-cyanophenoxy) -3,6- (pentakis) Phenylethylamino-trifluoro) phthalocyanine, 4,5 Octakis (p-cyanophenoxy) -3,6- {heptakis (DL-1-phenylethylamino) -fluoro} phthalocyanine, 4,5-octakis (p-cyanophenoxy) -3,6- {pentakis (DL-1 -Phenylethylamino) -trifluoro} phthalocyanine, 4,5-octakis (p-cyanophenoxy) -3,6- (heptakisbenzhydrylamino-fluoro) phthalocyanine, 4,5-octakis (p-cyanophenoxy) -3,6- (pentakisbenzhydrylamino-trifluoro) phthalocyanine, 4,5-octakis (2,5-dichlorophenoxy) -3,6- {pentakis (DL-1-phenylethylamino) -trifluoro } Phthalocyanine, 4,5-octakis (2,5-dichlorophenoxy) -3 6- {hexakis (DL-1-phenyl-ethylamino) - difluoro} phthalocyanine and the like.

According to the present invention, the starting material, the phthalonitrile compound represented by the formulas (1) to (4) is introduced in the presence of an organic compound having a hydroxyl group and / or a carboxyl group, while introducing an inert gas during the reaction, The corresponding halogen-containing phthalocyanine compound can be produced in a high yield by reacting alone or with a metal compound, but according to the study by the present inventors, the above substituents of NHR ¹ , SR ² or OR ³ Depending on the type or the number of substituents, even if the cyclization reaction described above is carried out, the substituents of NHR ¹ , SR ² or OR ³ are not substituted at an advantageous reaction rate, and the desired halogen-containing phthalocyanine compound is obtained. It turns out that there are cases where it is not possible.

For this reason, such a phthalocyanine compound having 12 or more substituents of NHR ¹ , SR ² or OR ³ may be obtained by the above production method, but the halogen-containing phthalocyanine compound is represented by the formula: M′-NHR An amino compound represented by formula ⁴ , a sulfur-containing compound represented by formula M′-SR ⁵ , and an alcohol compound represented by formula M′-OR ⁶ (in the above formula, M ′ represents a hydrogen atom or an alkali metal atom) Each of R ⁴ , R ⁵ and R ⁶ may independently have a phenyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. A desired NHR ¹ , SR ² or OR ³ by further substitution reaction with at least one compound selected from the group consisting of an alkyl group having 1 to 20 carbon atoms. Can efficiently introduce the desired number of substituents, for example, containing halogen having a desired function such as selective absorption of light of near-infrared wavelength, compatibility with resin, high transmittance in the visible region, etc. It has been found that phthalocyanine compounds can be produced in high yield (claim 2). In this case, the halogen-containing phthalocyanine compound is preferably a compound of the formula (5) in which at least two of Z _{1 to} Z ₁₆ are halogen atoms, particularly fluorine atoms. As the phthalonitrile compounds of the above formulas (1) to (4) used as starting materials, preferred compounds for producing such phthalocyanine compounds are also selected.

  That is, the following formula (1):

A phthalonitrile compound (1) represented by the following formula (2):

A phthalonitrile compound (2) represented by the following formula (3):

A phthalonitrile compound (3) represented by the following formula (4):

A phthalonitrile compound (4) represented by
In the above formulas (1) to (4), Z _{1 to} Z ₁₆ each independently represent a hydrogen atom, NHR ¹ , SR ² , OR ³ or a halogen atom, and at least two of Z _{1 to} Z ₁₆ Is a halogen atom, and R ¹ , R ² and R ³ each independently have a phenyl group which may have a substituent, an aralkyl group which may have a substituent or a substituent. Represents an optionally substituted alkyl group having 1 to 20 carbon atoms,
Cyclization alone or in an organic compound having a hydroxyl group and / or carboxyl group in an amount of 0.01 to 10 parts by mass with respect to 1 part by mass of a metal compound and a phthalonitrile compound, and introducing an inert gas By reacting, the following formula (5):

_However, Z 1 _{to Z 16} represents a hydrogen ^atom, NHR ^1, SR 2, OR ^3, or a halogen atom, and at least two are halogen ^atoms, R 1, ^{R 2} and ^{R 3} are each independently A phenyl group which may have a substituent, an aralkyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms which may have a substituent; Represents metal-free, metal, metal oxide or metal halide,
After obtaining the halogen-containing phthalocyanine compound (a) represented by the formula (7): an amino compound represented by the formula (7): M′-NHR ⁴ , the formula (8): M′- A sulfur-containing compound represented by SR ⁵ and an alcohol compound represented by formula (9): M′-OR ⁶ (in the above formula, M ′ represents a hydrogen atom or an alkali metal atom, and R ⁴ , R ⁵ and R ⁶ are each independently a phenyl group which may have a substituent, an aralkyl group which may have a substituent or a carbon atom which may have a substituent 1 -Represents -20 alkyl groups) and is substituted with at least one compound selected from the following formula (5):

However, Z < ₁ > -Z < ₁₆ > represents a hydrogen atom, NHR < ¹ >, SR < ² >, OR < ³ > or a halogen atom, and at least 1 is a halogen atom and at least 1 is NHR < ¹ >, SR < ² > or OR < ³ >. Each of R ¹ , R ² and R ³ may independently have a phenyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. Represents an alkyl group having 1 to 20 carbon atoms, and M represents a metal-free, metal, metal oxide or metal halide,
In which the halogen-containing phthalocyanine compound (b) is produced. In the above formula, definitions of R ¹ , R ² , R ³ , M, and a halogen atom are the same as described above, and thus description thereof is omitted here. Similarly, in the method for producing the halogen-containing phthalocyanine compound (a), at least two of Z _{1 to} Z ₁₆ in the formulas (1) to (4), which are starting materials, are used. Since the method is the same as that described above except that is selected to be a halogen atom, description thereof is omitted here.

Therefore, hereinafter, the halogen-containing phthalocyanine compound (a) and the amino compound represented by the formula (7): M′-NHR ⁴ (hereinafter referred to as “amino compound (7)”), the formula (8): M ′ A sulfur-containing compound represented by —SR ⁵ (hereinafter referred to as “sulfur-containing compound (8)”), and an alcohol compound represented by formula (9): M′-OR ⁶ (hereinafter referred to as “alcohol compound (9)”). Will be described in detail.

In the above formulas (7) to (9), M ′ is a hydrogen atom or an alkali metal atom. In this case, examples of the alkali metal atom include lithium, sodium, and potassium. Of these, M ′ is preferably a hydrogen atom or a sodium atom. R ⁴ , R ⁵ and R ⁶ each independently have a phenyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. Represents an optionally substituted alkyl group having 1 to 20 carbon atoms, and their definitions and examples are the same as those of R ¹ , R ² and R ^{3 in} the above formulas (1) to (4).

In the present invention, the amino compound (7) is not particularly limited as long as it is represented by M′-NHR ⁴ , but specifically, those represented by the following formula are preferably used.

  In the above formula, M ′ has the same definition as in the above formulas (7) to (9), Z and c have the same definition as the above substituent (c), and e represents the above substituent. It is the same definition as (f). Examples of such amino compounds (7) include benzylamine, aniline, o-, m-, p-toluidine, 2,4-, 2,6-xylidine, o-, m-, p-methoxyaniline, o-, m-, p-fluoroaniline, tetrafluoroaniline, p-ethoxycarbonylaniline; methylamine, ethylamine, butylamine and the like. The amino compound (7) may be used alone or in the form of a mixture of two or more.

Further, the sulfur-containing compound (8) is not particularly limited as long as it is represented by the formula: M′-SR ⁵ , but specifically, those represented by the following formula are preferably used.

  In the above formula, M ′ has the same definition as in the above formulas (7) to (9), and R, X, a, and b have the same definition as the substituent (b). ', R "and d have the same definition as in the substituent (e). Examples of such a sulfur-containing compound (8) include benzenethiol, o-, m-, p-methoxycarbonylbenzenethiol. O-, m-, p-ethoxycarbonylbenzenethiol, o-, m-, p-butoxycarbonylbenzenethiol, o-methyl-p-methoxycarbonylbenzenethiol, o-methoxy-p-methoxycarbonylbenzenethiol, o -Fluoro-p-methoxycarbonylbenzenethiol, tetrafluoro-p-ethoxycarbonylbenzenethiol, o-ethoxycarbonyl-p-methylbenzene All, o-butoxycarbonyl-p-methylbenzenethiol, o-butoxycarbonyl-p-fluorobenzenethiol, p-methyl-m-butoxycarbonylbenzenethiol; dimethylaminoethylthiol, diethylaminoethylthiol, dibutylaminobutylthiol; The sulfur-containing compound (8) may be used alone or in the form of a mixture of two or more.

Furthermore, the alcohol compound (9) is not particularly limited as long as it is represented by the formula: M′-OR ⁶ , but specifically, those represented by the following formula are preferably used.

  In the above formula, M ′ has the same definition as in the above formulas (7) to (9), and R, X, a, and b have the same definition as the substituent (a). ', R "and d have the same definitions as in the above substituent (d), and W and f have the same definitions as in the above substituent (g). Examples of such alcohol compounds (9) O-, m-, p-methoxycarbonylphenol, o-, m-, p-ethoxycarbonylphenol, o-, m-, p-butoxycarbonylphenol, o-methyl-p-methoxycarbonylphenol, o- Methoxy-p-ethoxycarbonylphenol, o-fluoro-p-methoxycarbonylphenol, tetrafluoro-p-ethoxycarbonylphenol, o-ethoxycarbonyl-p-methylphenol, o-butyl Xycarbonyl-p-methylphenol, o-butoxycarbonyl-p-fluorophenol, p-methyl-m-butoxycarbonylphenol, 2,5-dichlorophenol; dimethylaminoethanol, diethylaminoethanol, diethylaminobutanol; methoxyethanol, 3 ′ , 6 ′, 9′-oxadecanol, 3 ′, 6 ′, 9 ′, 12′-oxatridecanol, acetylethanol, 5′-acetyl-3′-oxapentanol, 8′-acetyl-3 ′ These alkali metal salts, etc. The alcohol compound (9) may be used alone or in the form of a mixture of two or more.

  In the present invention, the amino compound (7), the sulfur-containing compound (8), and the alcohol compound (9) may be used alone or in combination of two or more.

  The amount of the amino compound (7), sulfur-containing compound (8), and alcohol compound (9) used is appropriately selected depending on the structure of the target phthalonitrile compound (b), and these compounds The total amount used is not particularly limited as long as these reactions can proceed to produce a desired phthalonitrile compound, but is usually 1 to 50 mol, preferably 1 mol, per 1 mol of the phthalocyanine compound (a). 2 to 40 moles.

In the present invention, the substitution reaction conditions of the phthalocyanine compound (a) with the amino compound (7), the sulfur-containing compound (8), and the alcohol compound (9) are Z ₁ of the phthalocyanine compound (b) of the formula (5). as can be the substitution position of the to Z ₁₆ is introduced as designed desired substituent is not particularly limited by selecting the most suitable range. For example, if necessary, the substitution reaction can be carried out by mixing with a compound used in the reaction in the presence of an inert liquid having no reactivity and heating to a certain temperature, but preferably the reaction is carried out. This is carried out by heating to a certain temperature in the amino compound (7), the sulfur-containing compound (8) and the alcohol compound (9). As the inert liquid, for example, in the reaction of the phthalocyanine compound (b) with the amino compound of the formula (7), a nitrile such as benzonitrile or acetonitrile, or an amide such as N-methylpyrrolidone or dimethylformamide alone is used. Or it can use with the form of 2 or more types of liquid mixture. In addition, the amino compound (7), the sulfur-containing compound (8), and the alcohol compound (9) can also be used as a solvent for the substitution reaction.

The reaction conditions in the substitution reaction according to the present invention are suitably in an optimal range so that a desired substituent can be introduced as designed at the substitution positions of Z _{1 to} Z ₁₆ of the phthalocyanine compound (b) of the formula (5). For example, the following conditions can be preferably used. That is, amino compound (7) / sulfur-containing compound (8) / alcohol compound (9) is charged in the amount as described above. In the above step, the phthalocyanine compound (a) is once separated and purified, and then reacted with the amino compound (7) / sulfur-containing compound (8) / alcohol compound (9), whereby the phthalocyanine skeleton is subjected to desired substitution. Group may be introduced to produce the phthalocyanine compound (b), or the amino compound (7) / sulfur-containing compound (in the same reaction vessel without separation and purification of the phthalocyanine compound (a). 8) / By reacting with the alcohol compound (9), a desired substituent may be introduced into the phthalocyanine skeleton to produce the phthalocyanine compound (b). Industrially, it is desirable to produce a target phthalocyanine compound (b) by introducing a substituent into the phthalocyanine skeleton in the same reaction vessel without separating and purifying the obtained phthalocyanine compound. In addition, the reaction temperature and time of the substitution reaction according to the present invention are not particularly limited as long as the substitution reaction can proceed sufficiently, but the reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 190 ° C. In addition, the reaction time is preferably 1 to 30 hours, more preferably 2 to 20 hours. In addition, after the reaction, according to a conventionally known synthesis method by substitution reaction of phthalocyanine compounds, inorganic components are filtered and the amino compound is distilled off (washed), whereby the desired phthalocyanine compound of the present invention is produced in a complicated production process. It can be obtained efficiently and with high purity without going through.

  In the substitution reaction according to the present invention, since the raw material phthalonitrile compound has a halogen atom such as a fluorine atom, a small amount of hydrogen halide such as hydrogen fluoride is generated during the reaction. May corrode stainless steel reactors. Therefore, for the purpose of capturing the generated hydrogen halide and preventing corrosion of the reactor, for example, a hydrogen fluoride scavenger may be added and reacted. Such scavengers include alkaline earth metal compounds such as calcium carbonate, calcium hydroxide, calcium oxide, calcium silicate, calcium acetate, or tri-n-butylamine, tri-n-octylamine, N, N, -dimethyl. Examples thereof include alkylamines such as aniline and N, N, -diethylaniline. These scavengers may be used alone or in combination of two or more as long as they are one kind or a combination that does not affect each other. At this time, the amount of the scavenger used is not particularly limited as long as it can sufficiently trap the generated hydrogen halide. For example, it is preferably 1 to 20 moles per mole of the phthalocyanine compound (a), More preferably, it is the range of 2-10 mol.

  In the cyclization reaction according to the present invention, the metal compound used as the central metal source may contain moisture as so-called crystal water, and in this case, generation of moisture is observed during the cyclization reaction. Sometimes. In addition, as described above, in order to prevent corrosion of the reactor due to hydrogen fluoride generated during the reaction, water is generated according to the following reaction formula even when calcium carbonate or the like is used as a hydrogen fluoride scavenger. To do.

  When such moisture is generated, water separation is appropriately performed in order to perform safe and stable production from the viewpoint of industrially stable operation management such as corrosion prevention of the reactor and temperature stability of the reaction solution. It is desirable to perform a cyclization reaction by installing a tube or the like in the reactor and separating moisture generated inside the reactor to the outside of the reactor.

  Hereinafter, specific examples will be described with reference to examples.

Example 1: Synthesis of hexadecafluorovanadyl phthalocyanine Nitrogen gas was introduced into a 300-ml glass separable flask equipped with a stirrer, a thermometer, a water separation tube and a cooling tube for 10 minutes at 500 ml / min. Replaced with nitrogen gas. Next, tetrafluorophthalonitrile 30gr (0.15mol) n-octanol 58.6gr (0.45mol) and vanadium trichloride 6.9gr (manufactured by Shinsei Chemical Co., Ltd., 0.0438mol) were charged again, Nitrogen gas was introduced at 500 ml / min for 10 minutes, and the inside of the reactor was replaced with nitrogen gas. When the oxygen concentration inside the reactor was measured with an oxygen concentration meter, it was 1.8 vol%.

  While stirring, nitrogen gas was circulated at 30 ml / min, and the temperature was raised. The linear velocity at the inlet of the cooling pipe (connection portion between the reactor and the cooling pipe) was 0.6 cm / sec. The oxygen concentration inside the reactor was measured by an oxygen concentration meter and found to be 1.8 vol%. .

  The temperature was raised to 150 ° C. over 2 hours, and the reaction was further continued for 3 hours, followed by cooling to room temperature. During this time, the nitrogen gas was kept flowing. The conversion of the tetrafluorophthalonitrile measured by liquid chromatography was 99.2%. After the cyclization reaction, the reaction slurry was filtered to separate a solid content. This solid content was washed with 300 gr of benzonitrile, then washed with 100 gr of methanol, and dried under reduced pressure at 150 ° C. for 12 hours.

  The weight of the target product, hexadecafluorovanadyl phthalocyanine, calculated from the weight after drying was 28.1 gr (yield: 86.4 mol%).

Example 2
In Example 1, the reaction was carried out in the same manner except that 60 gr (0.50 mol) of diethylene glycol monomethyl ether was used in place of n-octanol as the solvent for the cyclization reaction, and the target product, hexadecafluorovanadyl phthalocyanine. Was 23.1 gr (yield: 71.1 mol%).

Example 3
In Example 1, the reaction was carried out in the same manner except that 48.7 gr (0.45 mol) of benzyl alcohol was used in place of n-octanol as the solvent for the cyclization reaction. As a result, the target product hexadecafluorovanadyl phthalocyanine was obtained. Was 25.5 gr (yield: 78.3 mol%).

Example 4
In Example 1, instead of n-octanol 58.6gr (0.45mol), a mixed solvent of n-octanol 28.6gr (0.22mol) and benzonitrile 30gr (0.29mol) was used. The reaction was performed in the same manner except for the above.

  The conversion ratio of tetrafluorophthalonitrile measured by liquid chromatography was 99.5%. After the cyclization reaction, the reaction slurry was filtered to separate a solid content. This solid content was washed with 300 gr of benzonitrile, then washed with 100 gr of methanol, and dried under reduced pressure at 150 ° C. for 12 hours.

  The weight of the target product, hexadecafluorovanadyl phthalocyanine, calculated from the weight after drying was 29.6 gr (yield: 91.0 mol%).

Example 5
In Example 4, the reaction was carried out in the same manner except that 30 gr (0.18 mol) of 1-chloronaphthalene was added instead of 30 gr of benzonitrile. The conversion of the tetrafluorophthalonitrile measured by liquid chromatography was 99.2%. After the cyclization reaction, 100 g of benzonitrile was added to the reaction solution and stirred at room temperature for 1 hour, and then the reaction slurry was filtered to separate a solid content. This solid content was washed with 300 gr of benzonitrile, then washed with 100 gr of methanol, and dried under reduced pressure at 150 ° C. for 12 hours.

  The weight of the target product, hexadecafluorovanadyl phthalocyanine, calculated from the weight after drying was 28.8 gr (yield: 88.6 mol%).

Example 6
In Example 4, the reaction was performed in the same manner except that 11.6 gr (0.0438 mol) of vanadyl acetylacetonate was added instead of vanadium trichloride. The conversion rate of the tetrafluorophthalonitrile measured by liquid chromatography was 98.8%. After the cyclization reaction, the reaction slurry was filtered to separate the solid content. This solid content was washed with 300 gr of benzonitrile, then washed with 100 gr of methanol, and dried under reduced pressure at 150 ° C. for 12 hours.

  The weight of the target product, hexadecafluorovanadyl phthalocyanine, calculated from the weight after drying was 28.4 gr (yield: 87.5 mol%).

Example 7 Synthesis of Octafluorooctakisanilinovanadyl Phthalocyanine Nitrogen gas was introduced into a 300 ml glass separable flask equipped with a stirrer, a thermometer, a water separation tube and a cooling tube for 10 minutes at 500 ml / min. The inside of the vessel was replaced with nitrogen gas. Next, 30 gr (0.15 mol) of tetrafluorophthalonitrile, 58.6 gr (0.45 mol) of n-octanol, 6.9 gr of vanadium trichloride (manufactured by Shinsei Chemical Co., Ltd., 0.0438 mol), calcium carbonate 4 0.5 gr (0.045 mol) was charged, nitrogen gas was introduced again at 500 ml / min for 10 minutes, and the inside of the reactor was replaced with nitrogen gas. When the oxygen concentration inside the reactor was measured with an oxygen concentration meter, it was 1.6 vol%.

  Under stirring, the temperature was raised to 150 ° C. over 2 hours and reacted for 3 hours. At this time, the nitrogen gas was kept flowing, and the oxygen concentration inside the reactor was measured by an oxygen concentration meter and found to be 1.6 vol%. The conversion of the tetrafluorophthalonitrile measured by liquid chromatography was 99.2%. After the cyclization reaction, 112 gr (1.204 mol) of aniline and 15 gr (0.15 mol) of calcium carbonate were added to the reaction slurry, reacted at 150 ° C. for 2 hours, then heated to 170 ° C. and heated to 9 ° C. Reacted for hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 60 gr of acetone was added with stirring. The reaction solution was filtered to separate a solid content, and the solid content was washed with 30 gr of acetone. The reaction filtrate was transferred to a 2 L glass separable flask equipped with a stirrer and a thermometer, and 540 g of isopropyl alcohol was added with stirring for about 10 minutes, and stirring was continued for 1 hour after the addition was completed. After stirring, the reaction slurry was filtered, and the cake was washed again with a mixed solution of isopropyl alcohol and acetone. The cake was filtered and dried under reduced pressure at 80 ° C. for 15 hours.

  The solid content after drying was 37.4 gr, and the yield of the target product, octafluorooctakisanilinovanadyl phthalocyanine, was 68.7 mol%.

Reference Example 1: Synthesis of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile To a 300 ml glass separable flask equipped with a stirrer, thermometer, water separation tube and cooling tube, Acetone 42.5 gr and tetrafluorophthalonitrile 19.1 gr (0.0955 mol) were charged and dissolved uniformly. Next, 13.4 gr (0.2306 mol) of potassium fluoride was charged, and the reaction slurry was kept at -5 ° C. To this reaction slurry, 34.1 g (0.2092 mol) of 2,5-dichlorophenol uniformly dissolved in 30.5 g of acetone was added dropwise over 1 hour. The reaction proceeded while cooling from the outside so that the internal temperature of the reaction product during dropping was -5 ° C to 0 ° C. After completion of dropping, the mixture was further maintained for 2 hours. After completion of the reaction, the temperature of the contents was set to 20 ° C., and the solid matter was separated by filtration.

  The solid was washed with 10 gr of acetone and mixed with the filtrate, and the acetone was distilled off by evaporation under reduced pressure. The weight of the obtained dried product was 45.8 gr (crude yield 98.7 mol%), and the desired 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile was obtained. Contained 42.9 gr (yield 92.4 mol%).

Example 8: Synthesis of octafluorooctakis (2,5-dichlorophenoxy) copper phthalocyanine A 300 ml glass separable flask equipped with a stirrer, thermometer, water separation tube and cooling tube was charged with nitrogen gas at 500 ml / min. It was introduced for 10 minutes, and the inside of the reactor was replaced with nitrogen gas. Next, a solid content of 34.4 gr [4,5-bis (2,5-dichloro) containing 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile synthesized in Reference Example 1 was used. Phenoxy) -3,6-difluorophthalonitrile, 0.0663 mol], n-octanol 51.6 gr (0.3962 mol), cuprous chloride 1.72 gr (0.0174 mol) and calcium carbonate 6. 7 gr (0.067 mol) was charged, nitrogen gas was introduced again at 500 ml / min for 10 minutes, and the inside of the reactor was replaced with nitrogen gas. It was 1.5 vol% when the oxygen concentration inside a reactor was measured with the oxygen concentration meter.

  Under stirring, while flowing nitrogen at 30 ml / min, the temperature was raised to 150 ° C. over 1 hour, the reaction was performed for 3 hours, and then cooled to room temperature. The linear velocity at the inlet of the cooling pipe (connection portion between the reactor and the cooling pipe) was 0.6 cm / sec. At this time, the oxygen concentration inside the reactor was measured by an oxygen concentration meter and found to be 1.5 vol%. When the conversion rate of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile was measured by liquid chromatography, it was 99.6%. 150 g of benzonitrile was added to the reaction slurry, followed by filtration to separate the solid content. After this solid content was washed with 30 gr of benzonitrile, the filtrate was put into 1000 ml of stirred acetonitrile and left for 1 hour. The precipitate was filtered, washed with 100 ml of acetonitrile, and then dried under reduced pressure at 100 ° C. for 8 hours. The weight of octafluorooctakis (2,5-dichlorophenoxy) copper phthalocyanine, which was the target product calculated from the weight after drying, was 26.3 gr (yield 79.0 mol%).

Example 9
In Example 8, after completion of the cyclization reaction, the same octafluorooctakis (2,5-dichlorophenoxy) copper phthalocyanine was used without purification for the purpose of further replacing the fluorine of phthalocyanine with a benzylamino group. The following reaction was continued in the reaction vessel.

  The reaction liquid after completion of the cyclization reaction is cooled to 90 ° C., 25.1 gr (0.23 mol) of benzylamine and 3.5 gr of calcium carbonate as a corrosion inhibitor are added, and the reaction is performed at 90 ° C. for 8 hours. went. After completion of the reaction, 27.5 gr of benzonitrile was added, cooled to room temperature, and solid content was separated by filtration.

  2200 gr of acetonitrile was added to the filtrate, the target product was precipitated, the precipitate was separated by filtration, washed with acetonitrile, and then dried under reduced pressure at 60 ° C. for 12 hours. The weight of 4,5-octakis (2,5-dichlorophenoxy) -3,6- (tetrakisbenzylamino-tetrafluoro) copper phthalocyanine, which is the target product calculated from the weight after drying, was 29.3 gr (yield 72). 0.6 mol%).

Example 10
In Example 8, a cyclization reaction was performed in the same manner except that 23 g (0.177 mol) of n-octanol and 30 gr (0.291 mol) of benzonitrile were used instead of 51.6 gr of n-octanol. . The conversion of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile measured by liquid chromatography was 99.8%. After the reaction, the same purification operation was performed, and the weight of octafluorooctakis (2,5-dichlorophenoxy) copper phthalocyanine, which was the target product calculated from the weight after drying under reduced pressure at 100 ° C. for 8 hours, was 28.9 gr. (Yield: 86.8 mol%).

Reference Example 2: Synthesis of 4- (2-chlorophenylthio) -3,5,6-trifluorophthalonitrile Into a 100 ml glass four-necked flask equipped with a stirrer, thermometer, water separation tube and cooling tube, 2 -30 g of butanone, 10 g (0.05 mol) of tetrafluorophthalonitrile, 3.63 g (0.062 mol) of potassium fluoride, charged in a water bath, and stirred at room temperature, 7.6 g of 2-chlorobenzenethiol (0 .053 mol) was added in about 20 minutes. The reaction temperature rose to a maximum of 30 ° C. When the reaction was further continued for 1 hour after the addition was completed, the conversion of tetrafluorophthalonitrile was 99.0%. After completion of the reaction, the solid content was filtered and evaporated at 50 ° C. under reduced pressure to distill about 15 g of 2-butanone. To the residue, 100 ml of methanol was added and the precipitated crystals were filtered, and 11.4 gr of 4- (2-chlorophenylthio) -3,5,6-trifluorophthalonitrile (0.035 mol, yield 70.). 2 mol%) was obtained.

Example 11: Synthesis of dodecafluorotetrakis (2-chlorophenylthio) vanadyl phthalocyanine A 100 ml glass four-necked flask equipped with a stirrer, thermometer, water separation tube and cooling tube was charged with nitrogen gas at 100 ml / min for 10 minutes. Then, the inside of the reactor was replaced with nitrogen gas. Next, 4- (2-chlorophenylthio) -3,5,6-trifluorophthalonitrile synthesized in Reference Example 1 (11.4 gr, 0.035 mol), n-octanol (10 gr) (0.077 mol), benzo 30 g (0.29 mol) of nitrile and 2.07 g (0.013 mol) of vanadium trichloride were charged, nitrogen gas was again introduced at 100 ml / min for 10 minutes, and the inside of the reactor was replaced with nitrogen gas. When the oxygen concentration inside the reactor was measured with an oxygen concentration meter, it was 1.1 vol%. Under stirring, while flowing nitrogen at 30 ml / min, the temperature was raised to 190 ° C. over 1 hour, reacted for 3 hours, and then cooled to room temperature. The linear velocity at the inlet of the cooling pipe (connection portion between the reactor and the cooling pipe) was 0.6 cm / sec. The oxygen concentration inside the reactor at this time was measured by an oxygen concentration meter and found to be 1.1 vol%. The conversion rate of 4- (2-chlorophenylthio) -3,5,6-trifluorophthalonitrile measured by liquid chromatography was 99.3%. Benzonitrile (20 gr) was added to the reaction slurry, and the solid content was separated by filtration. After this solid content was washed with 30 gr of benzonitrile, the filtrate was put into 300 ml of stirred methanol and left for 1 hour. The precipitate was filtered, and the precipitate was washed with 50 ml of acetonitrile and dried under reduced pressure at 60 ° C. for 12 hours. The weight of dodecafluorotetrakis (2-chlorophenylthio) vanadyl phthalocyanine, which was the target product calculated from the weight after drying, was 9.8 gr (yield 82.2 mol%).

Reference Example 3: Synthesis of 4,5-bis (2-chlorophenylthio) -3-fluoro-6- (2,6-dimethylphenoxy) phthalonitrile 100 ml equipped with stirrer, thermometer, water separation tube and cooling tube A glass four-necked flask was charged with 30 gr of 2-butanone, 10 gr of tetrafluorophthalonitrile (0.05 mol) and 7.26 gr of potassium fluoride (0.125 mol), placed in a water bath and stirred at room temperature with 2 -15.2 g (0.105 mol) of chlorobenzenethiol was added in about 40 minutes. The reaction temperature rose to a maximum of 35 ° C. When the reaction was further continued for 1 hour after the addition was completed, the conversion of tetrafluorophthalonitrile in the liquid chromatography analysis was 99.2%. The content of 4,5-bis (2-chlorophenylthio) -3,6-difluorophthalonitrile, which is a bisthiol body, in liquid chromatography was 92.5%. Next, 7.33 gr (0.06 mol) of 2,6-xylenol, 4.35 gr (0.075 mol) of potassium fluoride and 6 gr of 2-butanone were added to the reactor, and the temperature was raised to 83 to 86 ° C. After warming, the reaction was carried out for 30 hours while refluxing. The conversion of 4,5-bis (2-chlorophenylthio) -3,6-difluorophthalonitrile in the liquid chromatographic analysis after completion of the reaction was 99.8%, and the desired product, 4,5-bis The content of (2-chlorophenylthio) -3-fluoro-6- (2,6-dimethylphenoxy) phthalonitrile in liquid chromatography was 70%. After cooling the reaction slurry to room temperature and filtering the solids, separating the filtrate, the cake was washed with about 200 ml of chloroform, and the washing was evaporated at 50 ° C. under reduced pressure to give 4,5-bis ( 2-chlorophenylthio) -3- (2,6-dimethylphenoxy) -6-fluorophthalonitrile (18.0 g, 0.0326 mol, based on tetrafluoronitrile yield of 65.2 mol%) was obtained.

Example 12: Synthesis of 4,5-octakis (2-chlorophenylthio) -3,6- (tetrakis (2,6-dimethylphenoxy) -tetrafluoro) vanadyl phthalocyanine Stirrer, thermometer, water separator tube and condenser tube Nitrogen gas was introduced into a 100 ml glass four-necked flask equipped at 100 ml / min for 10 minutes, and the inside of the reactor was replaced with nitrogen gas. Next, 18-gr (0.0326 mol) of 4,5-bis (2-chlorophenylthio) -3- (2,6-dimethylphenoxy) -6-fluorophthalonitrile synthesized in Reference Example 3 and 10 gr of n-octanol ( 0.077 mol), 30 gr (0.29 mol) of benzonitrile, 1.92 gr (0.012 mol) of vanadium trichloride, and again introducing nitrogen gas at 100 ml / min for 10 minutes. Replaced with gas. When the oxygen concentration inside the reactor was measured with an oxygen concentration meter, it was 1.1 vol%.

  Under stirring, while flowing nitrogen at 30 ml / min, the temperature was raised to 190 ° C. over 1 hour, reacted for 3 hours, and then cooled to room temperature. The linear velocity at the inlet of the cooling pipe (connection portion between the reactor and the cooling pipe) was 0.6 cm / sec. The oxygen concentration inside the reactor at this time was measured by an oxygen concentration meter and found to be 1.1 vol%. The conversion rate of 4,5-bis (2-chlorophenylthio) -3- (2,6-dimethylphenoxy) -6-fluorophthalonitrile measured by liquid chromatography was 98.4%. Benzonitrile (20 gr) was added to the reaction slurry, and the solid content was separated by filtration. After this solid content was washed with 30 gr of benzonitrile, the filtrate was put into 300 ml of stirred methanol and left for 1 hour. The precipitate was filtered, and the precipitate was washed with 50 ml of acetonitrile and dried under reduced pressure at 60 ° C. for 12 hours. The weight of 4,5-octakis (2-chlorophenylthio) -3,6-tetrakis ((2,6-dimethylphenoxy) -fluoro) vanadyl phthalocyanine, which is the target product calculated from the weight after drying, was 15.5 gr ( The yield was 83.4 mol%.

Example 13
In Example 12, reaction and purification were performed in the same manner except that cyclization reaction was performed using 10 gr (0.069 mol) of 2-naphthol instead of n-octanol. As a result, the weight of 4,5-octakis (2-chlorophenylthio) -3,6-tetrakis ((2,6-dimethylphenoxy) -fluoro) vanadyl phthalocyanine, which is the target product calculated from the weight after drying, was 14 0.5 gr (yield 77.8 mol%).

Example 14
In Example 12, the reaction and purification were performed in the same manner except that 1.2 g (0.006 mol) of cuprous chloride was used instead of 1.92 gr of vanadium trichloride. . As a result, the weight of 4,5-octakis (2-chlorophenylthio) -3,6-tetrakis ((2,6-dimethylphenoxy) -fluoro) copper phthalocyanine, which is the target product calculated from the weight after drying, was 15 0.7 gr (yield 84.9 mol%).

Example 15
In Example 4, a cyclization reaction was performed in the same manner except that 28.6 gr (0.39 mol) of N, N-dimethylformamide was used instead of benzonitrile. In addition, when the oxygen concentration inside the reactor at this time was measured with an oxygen concentration meter, it was 1.3 vol%. As a result, the conversion rate of the tetrafluorophthalonitrile measured by liquid chromatography was 98.7%. After the cyclization reaction, the reaction slurry was filtered to separate a solid content. The solid was washed with 300 gr of dimethylformamide, washed with 100 gr of methanol, and dried under reduced pressure at 150 ° C. for 12 hours.

The weight of the target product, hexadecafluorovanadyl phthalocyanine, calculated from the weight after drying was 27.2 gr (yield: 83.7 mol%). Example 16
In Example 4, the cyclization reaction was carried out in the same manner except that the flow rate of nitrogen introduced during the reaction was 1 ml / min (linear speed 0.02 cm / sec at the lower part of the cooling pipe at the outlet of the reactor). The conversion rate of the fluorophthalonitrile measured by liquid chromatography was 98.1%. At this time, the oxygen concentration inside the reactor was measured by an oxygen concentration meter and found to be 2.6 vol%. After the cyclization reaction, the reaction slurry was filtered to separate a solid content. This solid content was washed with benzonitrile, then with 100 g of methanol, and dried under reduced pressure at 150 ° C. for 12 hours.

  The weight of the target product, hexadecafluorovanadyl phthalocyanine, calculated from the weight after drying was 28.8 gr (yield: 88.5 mol%).

Example 17
In Example 4, the cyclization reaction was carried out in the same manner except that the nitrogen flow rate introduced during the reaction was changed to 60 ml / min (linear velocity 1.2 cm / sec at the lower part of the cooling pipe at the outlet of the reactor). The conversion rate of the fluorophthalonitrile measured by liquid chromatography was 99.7%. At this time, the oxygen concentration inside the reactor was measured by an oxygen concentration meter and found to be 0.9 vol%. After the cyclization reaction, the reaction slurry was filtered to separate a solid content. This solid content was washed with benzonitrile, then with 100 g of methanol, and dried under reduced pressure at 150 ° C. for 12 hours. The weight of the target product, hexadecafluorovanadyl phthalocyanine, calculated from the weight after drying was 29.3 gr (yield: 90.2 mol%).

Example 18
Nitrogen gas was introduced at 100 ml / min for 10 minutes into a 100 ml glass four-necked flask equipped with a stirrer, thermometer, water separation tube and cooling tube, and the inside of the reactor was replaced with nitrogen gas. Next, 9 g (0.0163 mol) of 4,5-bis (2-chlorophenylthio) -3- (2,6-dimethylphenoxy) -6-fluorophthalonitrile synthesized in Reference Example 3 and tetrafluorophthalonitrile 3 were used. .3 gr (0.0163 mol), n-octanol 10 gr (0.077 mol), benzonitrile 30 gr (0.29 mol), vanadium trichloride 1.92 gr (0.012 mol) were charged, and nitrogen gas was supplied again. It was introduced at 100 ml / min for 10 minutes, and the inside of the reactor was replaced with nitrogen gas. When the oxygen concentration inside the reactor was measured with an oxygen concentration meter, it was 1.1 vol%. Under stirring, while flowing nitrogen at 30 ml / min, the temperature was raised to 190 ° C. over 1 hour, reacted for 3 hours, and then cooled to room temperature. The linear velocity at the inlet of the cooling pipe (connection portion between the reactor and the cooling pipe) was 0.6 cm / sec. The oxygen concentration inside the reactor at this time was measured with an oxygen concentration meter, and found to be 1.4 vol%. The conversion of 4,5-bis (2-chlorophenylthio) -3- (2,6-dimethylphenoxy) -6-fluorophthalonitrile as measured by liquid chromatography was 98.4%. Conversion of tetrafluorophthalonitrile The rate was 99.8%. Benzonitrile (20 gr) was added to the reaction slurry, and the solid content was separated by filtration. After this solid content was washed with 30 gr of benzonitrile, the filtrate was added to 500 ml of stirred methanol and left for 1 hour. The precipitate was filtered, and the precipitate was washed with 50 ml of acetonitrile and dried under reduced pressure at 60 ° C. for 12 hours. The weight of 4,5-tetrakis (2-chlorophenylthio) -3-bis (2,6-dimethylphenoxy) -6-decafluoro) vanadyl phthalocyanine calculated from the weight after drying was 10.9 gr ( The yield was 85.1 mol%.

Example 19
In Example 18, after completion of the cyclization reaction, 4,5-tetrakis (2-chlorophenylthio) -3-bis (2,6-dimethylphenoxy)-for the purpose of further substituting the fluorine of the produced phthalocyanine with an anilino group. The following reaction was continued in the same reaction vessel without purifying (decafluoro) vanadyl phthalocyanine.

  The reaction liquid after completion of the cyclization reaction was cooled to 150 ° C., 26.9 gr (0.29 mol) of aniline and 3.5 gr (0.035 mol) of calcium carbonate as a corrosion inhibitor were added, and 90 ° C. The reaction was carried out for 8 hours. After completion of the reaction, 27.5 gr of benzonitrile was added, cooled to room temperature, and solid content was separated by filtration. The filtrate was added to 1 L of methanol to precipitate the target product, and the precipitate was separated by filtration, washed with acetonitrile, and then dried under reduced pressure at 60 ° C. for 12 hours. The weight of 4,5-tetrakis ((2-chlorophenylthio) -anilino) -3-bis (2,6-dimethylphenoxy) -6-tetrafluoro) vanadyl phthalocyanine, which seems to be the target product calculated from the weight after drying, is It was 10.2 gr (yield 67.5 mol%).

Example 20
In Example 8, the reaction was carried out in the same manner except that 51.6 gr (0.43 mol) of diethylene glycol monomethyl ether was used instead of n-octanol as the solvent for the cyclization reaction. 2,4.7 g of 2,5-dichlorophenoxy) copper phthalocyanine (yield 74.2 mol%) was obtained.

Example 21
In Example 8, the reaction was carried out in the same manner except that 51.6 gr (0.48 mol) of benzyl alcohol was used in place of n-octanol as the solvent for the cyclization reaction. As a result, octafluorooctakis (2 , 5-dichlorophenoxy) copper phthalocyanine (25.6 g, yield 76.9 mol%) was obtained.

Example 22
In Example 12, the reaction was carried out in the same manner except that the amount of n-octanol used as a solvent for the cyclization reaction was changed from 10 gr to 2 gr (0.015 mol). As a result, 4,5-octakis (2 As for -chlorophenylthio) -3,6-tetrakis ((2,6-dimethylphenoxy) -fluoro) vanadyl phthalocyanine, 15.2 gr (yield: 81.8 mol%) was obtained.

Example 23
In Example 4, 10 g (0.058 mol) of 1-naphthoic acid was used instead of 28.6 gr (0.22 mol) of n-octanol, and the amount of benzonitrile was changed to 50 gr. The reaction was performed. The conversion rate of the tetrafluorophthalonitrile measured by liquid chromatography was 98.8%. After the cyclization reaction, the reaction slurry was filtered, the same treatment as in Example 4 was performed, and the weight of hexadecafluorovanadyl phthalocyanine, which was the target product calculated from the weight after drying, was 25.0 gr (yield was 76.9 mol%).

Example 24
In Example 11, the reaction was conducted in the same manner except that 5 gr (0.041 mol) of benzoic acid was used instead of 10 gr (0.77 mol) of n-octanol and the amount of benzonitrile was changed to 50 gr. It was. The conversion rate of 4- (2-chlorophenylthio) -3,5,6-trifluorophthalonitrile measured by liquid chromatography was 98.7%. After the cyclization reaction, the reaction slurry was filtered, the same treatment as in Example 11 was performed, and the weight of dodecafluorotetrakis (2-chlorophenylthio) vanadyl phthalocyanine, which was the target product calculated from the weight after drying, was 8. It was 9gr (a yield is 74.7 mol%).

Example 25
In Example 12, the reaction was performed in the same manner except that 5 gr (0.041 mol) of benzoic acid was used instead of 10 gr (0.77 mol) of n-octanol and the amount of benzonitrile was changed to 50 gr. It was. The conversion rate of 4,5-bis (2-chlorophenylthio) -3- (2,6-dimethylphenoxy) -6-fluorophthalonitrile measured by liquid chromatography was 98.5%. After the cyclization reaction, the reaction slurry was filtered, treated in the same manner as in Example 12, and then 4,5-octakis (2-chlorophenylthio) -3,6-tetrakis, which was the target product calculated from the weight after drying. The weight of ((2,6-dimethylphenoxy) -fluoro) vanadyl phthalocyanine was 14.0 gr (yield: 75.3 mol%).

Example 26
Nitrogen gas was introduced into a 300-ml glass separable flask equipped with a stirrer, thermometer, water separation tube and cooling tube for 10 minutes at 500 ml / min, and the inside of the reactor was replaced with nitrogen gas. Next, 3- (2,6-dimethylphenoxy) -4,5-bis (phenylthio) -6-fluorophthalonitrile 30 gr (0.0621 mol), vanadium trichloride 2.93 gr (manufactured by Shinsei Chemical Co., Ltd., 0 0.187 mol), 2.43 gr (0.0187 mol) of n-octanol and 42.6 gr of benzonitrile, nitrogen gas was introduced again at 500 ml / min for 10 minutes, and the inside of the reactor was replaced with nitrogen gas. When the oxygen concentration inside the reactor was measured with an oxygen concentration meter, it was 1.6 vol%.

  While stirring, nitrogen was passed at a rate of 30 ml / min, and heating was started. The linear velocity at the inlet of the cooling pipe (connection portion between the reactor and the cooling pipe) was 0.7 cm / sec. The oxygen concentration inside the reactor at this time was measured by an oxygen concentration meter, and it was 1.6 vol%.

  The temperature was raised to 180 ° C. over 2 hours and then maintained for 4 hours with stirring under reflux. During this time, the nitrogen gas was kept flowing. The conversion rate measured by liquid chromatography of 3- (2,6-dimethylphenoxy) -4,5-bis (phenylthio) -6-fluorophthalonitrile measured after 4 hours was 99.0%. Thereafter, 90 gr of benzonitrile was added, and after cooling to 60 ° C., 43.4 gr (0.372 mol) of N, N-diethylethylenediamine was added, and the mixture was kept at 60 ° C. with stirring for about 6 hours. After cooling, the reaction solution was filtered, and the filtrate was dropped into a mixed solution of acetonitrile and water for crystallization, and further washed with a mixed solution of acetonitrile and water. By vacuum drying, the target product 4,5-octakis (phenylthio) -3,6-tetrakis ((2,6-dimethylphenoxy) -N, N-diethylethylenediamino) baanthyl phthalocyanine was converted to 28.6 gr (77. 3 mol%).

Example 27
In Example 1, the reaction was performed in the same manner except that 29.55 gr (0.15 mol) of 4,5-dichlorophthalonitrile was used instead of 30 gr of tetrafluorophthalonitrile (0.15 mol). Certain octachlorovanadyl phthalocyanine was 27.25 gr (yield: 85.0 mol%).

Example 28
In Example 27, after completion of the cyclization reaction, in order to further replace the chlorine of octachlorovanadyl phthalocyanine with 4-methylbenzenethiol group, the target product, octachlorovanadyl phthalocyanine, was purified in the same reaction vessel without purification. The following reactions were continued. That is, the reaction solution after completion of the cyclization reaction is cooled to 80 ° C., and 8.58 gr (0.153 mol) of potassium hydroxide is added and dissolved. After dissolution, the reaction solution temperature was cooled to 60 ° C., 19.00 gr (0.153 mol) of 4-methylbenzenethiol was added, and the reaction was performed at 60 ° C. for 2 hours.

  After completion of the reaction, the reaction mixture was cooled to room temperature, 2200 gr of acetonitrile was added to the reaction solution to precipitate the target product, the precipitate was separated by filtration, washed with water until the pH of the filtrate became neutral, and further methanol. And dried under reduced pressure at 60 ° C. for 12 hours. The weight of tetrachlorotetrakis (4-methylphenylthio) vanadyl phthalocyanine, which was the target product calculated from the weight after drying, was 32.57 gr (yield 71.8 mol%).

  The results of Examples 1-28 are summarized in Table 1 below.

Comparative Example 1
In Example 1, except that n-octanol used in the cyclization reaction was changed to 58.6 gr (0.41 mol) of methylnaphthalene, the reaction was conducted in the same manner as in Example 1, and hexadecafluorovanadyl was obtained. The mass of phthalocyanine was 17.2 gr (yield 52.9 mol%).

Comparative Example 2
In Example 1, n-octanol used in the cyclization reaction was changed to 58.6 gr (0.41 mol) of methylnaphthalene, and nitrogen substitution performed before the reaction and nitrogen introduced during the reaction were not introduced. Further, when the reaction was carried out while supplying air to the reactor at 5 ml / min, the mass of hexadecafluorovanadyl phthalocyanine was 13.5 gr (yield: 41.5 mol%). The oxygen concentration inside the reactor at this time was measured with an oxygen concentration meter, and it was 20.5 vol%.

Comparative Example 3
In Example 7, the reaction was carried out in the same manner as in Example 7 except that n-octanol used in the cyclization reaction was changed to 58.6 gr (0.75 mol) of dimethyl sulfoxide. The mass of the fluorooctakisililino vanadyl phthalocyanine was 23.7 gr (yield 43.5 mol%).

Comparative Example 4
In Example 1, when the reaction was performed while supplying air at 30 ml / min without introducing the nitrogen substitution performed before the reaction and the nitrogen introduced during the reaction, the mass of hexadecafluorovanadyl phthalocyanine was 12.5 gr (yield 38.5 mol%). When the oxygen concentration inside the reactor at this time was measured with an oxygen concentration meter, it was 20.3 vol%.

Comparative Example 5
In Example 8, the reaction was performed in the same manner as in the cyclization reaction except that nitrogen was not introduced and air was supplied at 30 ml / min. As a result, octafluorooctakis (2,5- The mass of (dichlorophenoxy) copper phthalocyanine was 16.2 gr (yield 48.6 mol%). When the oxygen concentration inside the reactor at this time was measured with an oxygen concentration meter, it was 20.8 vol%.

  Further, the phthalocyanine compound thus obtained was subjected to benzyl amination in the same manner as in Example 9. As a result, 4,5-octakis (2,5-dichlorophenoxy) -3-tetrakis (benzylamino) copper was obtained. The weight of phthalocyanine was 17.0 gr (yield 42.1 mol%).

Comparative Example 6
In Example 12, 40 g (0.28 mol) of methylnaphthalene was used without using n-octanol and benzonitrile used in the cyclization reaction, and the reaction was performed while supplying air to the reactor at 30 ml / min. As a result, the weight of 4,5-octakis (2-chlorophenylthio) -3,6-tetrakis ((2,6-dimethylphenoxy) -fluoro) vanadyl phthalocyanine was 8.53 gr (yield 45.9 mol%). )Met. When the oxygen concentration inside the reactor at this time was measured with an oxygen concentration meter, it was 20.7 vol%.

Comparative Example 7
In Example 4, the same reaction as in Example 4 was performed except that the amount of n-octanol was changed to 0.1 gr (0.003 parts by mass with respect to 1 part by mass of the raw material phthalonitrile compound). The conversion rate of phthalonitrile measured by liquid chromatography was 25.7%, and the cyclization reaction hardly proceeded.

Comparative Example 8
In Example 12, the amount of raw material 4,5-bis (2-chlorophenylthio) -3- (2,6-dimethylphenoxy) -6-fluorophthalonitrile was 1.8 gr (0.033 mol), and A reaction similar to Example 12 was carried out except that only 36 gr of n-octanol (20 parts by mass relative to 1 part by mass of the starting phthalonitrile compound) was used instead of n-octanol and benzonitrile. The conversion rate of 4,5-bis (2-chlorophenylthio) -3- (2,6-dimethylphenoxy) -6-fluorophthalonitrile after the cyclization reaction measured by liquid chromatography was 45.8%. The cyclization reaction did not proceed sufficiently, and the absorption spectrum obtained by UV measurement was significantly different from the spectrum obtained in Example 12, so that the cyclization reaction was normal in this comparative example. It was speculated that it was not progressing.

Comparative Example 9
In Example 12, the cyclization reaction was carried out without replacing the inside of the reactor with nitrogen gas and introducing nitrogen gas into the reactor from the preparation to the end of the reaction. As a result, the conversion rate measured by liquid chromatography of 4,5-bis (2-chlorophenylthio) -3- (2,6-dimethylphenoxy) -6-fluorophthalonitrile after the cyclization reaction was 68.1. %Met. Further, after adding benzonitrile to the reaction slurry, and further purifying after the reaction in the same manner as in Example 12 using methanol and acetonitrile, 4,5-octakis (2-chlorophenylthio) which is the target product was obtained. ) -3,6- (tetrakis (2,6-dimethylphenoxy) -tetrafluoro) vanadyl phthalocyanine weighed 7.2 gr (yield 38.7 mol%).

Claims (12)

Following formula (1):

A phthalonitrile compound (1) represented by the following formula (2):

A phthalonitrile compound (2) represented by the following formula (3):

A phthalonitrile compound (3) represented by the following formula (4):

A phthalonitrile compound (4) represented by
In the above formulas (1) to (4), Z _{1 to} Z ₁₆ each independently represent a hydrogen atom, NHR ¹ , SR ² , OR ³ or a halogen atom, and at least one of Z _{1 to} Z ₁₆ Is a halogen atom, and R ¹ , R ² and R ³ each independently have a phenyl group which may have a substituent, an aralkyl group which may have a substituent or a substituent. Represents an optionally substituted alkyl group having 1 to 20 carbon atoms,
By cyclization reaction alone or with a metal compound, the following formula (5):

_However, Z 1 _{to Z 16} represents a hydrogen ^atom, NHR ^1, SR 2, OR ^3, or a halogen atom, and at least one is a halogen ^atom, R 1, ^{R 2} and ^{R 3} are each independently A phenyl group which may have a substituent, an aralkyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms which may have a substituent; Represents metal-free, metal, metal oxide or metal halide,
A method for producing a halogen-containing phthalocyanine compound represented by:
The cyclization reaction is carried out in an organic compound having a hydroxyl group and / or a carboxyl group in an amount of 0.01 to 10 parts by mass and introducing an inert gas with respect to 1 part by mass of the phthalonitrile compound. A method for producing a phthalocyanine compound of formula (5), characterized in that After the cyclization reaction, the obtained phthalocyanine compound is further represented by the amino compound represented by the formula: M′-NHR ⁴ , the sulfur-containing compound represented by the formula: M′-SR ⁵ , and the formula: M′-OR ⁶ . Alcohol compound (in the above formula, M ′ is a hydrogen atom or an alkali metal atom, and R ⁴ , R ⁵ and R ⁶ may each independently have a substituent. A phenyl group, an aralkyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms which may have a substituent.) And a substitution reaction with at least one compound selected from The method of claim 1, comprising steps.   The method according to claim 1 or 2, wherein the metal compound is at least one selected from the group consisting of metals, metal oxides, metal carbonyls, metal halides, and organic acid metals.   The method according to any one of claims 1 to 3, wherein the cyclization reaction is carried out in a mixed solvent of an organic compound having a hydroxyl group and / or a carboxyl group and an inert solvent and / or an aprotic organic solvent. .   The method according to any one of claims 1 to 4, wherein the organic compound having a hydroxyl group and / or a carboxyl group is an organic compound having 6 to 15 carbon atoms.   The method according to claim 4 or 5, wherein the inert solvent and / or aprotic organic solvent is an aromatic compound having a boiling point of 150 ° C or higher.   The method according to any one of claims 4 to 6, wherein the inert solvent and / or the aprotic organic solvent are mixed in an amount of 0.01 to 50 parts by mass with respect to the organic compound.   The cyclization reaction is carried out while introducing an inert gas so that the oxygen concentration in a gas phase portion in contact with the reaction solution during the reaction is 10 vol% or less. the method of. In formula (5), Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ , Z ₁₆ are halogen atoms, and Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z _10. of the _{Z 11, Z 14, Z 15} , 0~8 pieces is a halogen atom the method according to any one of claims 1-8. In the formula _{(5), Z 1, Z} 4, Z 5, Z 8, Z 9, Z 12, of Z _{13, Z 16,} is a one to seven halogen atoms, any one of claims 1 to 8 2. The method according to item 1. In the formula (5), _{1-4 of} Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ , Z ₁₆ are halogen atoms and 4 are OR ³ . The method of claim 10. The method according to any one of claims 1 to 11, wherein, in the formula (5), the halogen atom is a fluorine atom or a chlorine atom.