Method for producing phthalocyanine compound

Abstract

To provide a production method for a phthalocyanine compound that enables high-purity production of a phthalocyanine compound having an ester side chain.SOLUTION: A method for producing a phthalocyanine compound comprises a step of mixing a phthalonitrile compound represented by general formula (1), a metal compound, and a compound represented by general formula (5), wherein in general formula (1), Z1 to Z4 each independently represent a hydrogen atom, a halogen atom, an alkoxy group, or the like, and at least one of Z1 to Z4 is a substituent represented by general formula (2); in general formula (2), L represents an alkylene or arylene group, and R represents an alkyl group or an aryl group; and in general formula (5), R is the same as R in general formula (2).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a method for producing a phthalocyanine compound. [Background technology]

[0002] Conventionally, known methods for producing phthalocyanine compounds include the Wyler process, which uses a phthalic anhydride compound, urea, and a metal compound as raw materials, and the phthalonitrile process, which uses a phthalonitrile compound and a metal compound as raw materials. Phthalonitrile compounds have higher reactivity than phthalic anhydride compounds and the like. Therefore, when a phthalocyanine compound is synthesized using a metal compound with low reactivity, such as a zinc compound, a magnesium compound, or a vanadium oxide compound, or when it is necessary to synthesize a phthalocyanine compound with high purity, the phthalonitrile method is selected from the above methods. On the other hand, when a phthalonitrile compound having a highly electron-withdrawing substituent coexists with a metal compound that functions as a Lewis acid by coordinating with the phthalonitrile, for example, in the presence of a nucleophile such as water, an undesired side reaction may occur. In particular, when the phthalonitrile compound has an ester functional group as a substituent, an undesired hydrolysis reaction may occur in the presence of water.

[0003] A method for producing a phthalocyanine compound has been disclosed that aims to shorten the reaction time of a phthalocyanine compound, and includes a step of cyclizing a phthalonitrile compound with a metal compound, in which the water content is in the range of 0.05 to 0.40 mass % relative to 100 mass % of the reaction solution, and the metal compound is a metal iodide, and the cyclization reaction is carried out (see Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2022-133059 Summary of the Invention [Problem to be solved by the invention]

[0005] When a metal compound that is generally difficult to cyclize, such as zinc, magnesium, or vanadium, is used in the production of a phthalocyanine compound, the cyclization reaction is often subjected to severe reaction conditions, requiring high temperatures and a long reaction time, which results in a problem of a large energy load for industrial production. Furthermore, when the cyclization reaction is carried out under harsh reaction conditions, side reactions tend to proceed, making it difficult to obtain the target phthalocyanine compound with high purity and high yield. In particular, when the side chain has a weak functional group such as an ester, it is susceptible to decomposition reactions such as hydrolysis, making it particularly difficult to obtain the target product with high purity and high yield.

[0006] An object of one embodiment of the present disclosure is to provide a method for producing a phthalocyanine compound, which can provide a highly pure phthalocyanine compound having an ester side chain. [Means for solving the problem]

[0007] The present disclosure includes the following aspects. <1> A method for producing a phthalocyanine compound, comprising the step of mixing a phthalonitrile compound represented by the following general formula (1), a metal compound, and a compound represented by the following general formula (5): [ka]

[0008] In general formula (1), Z 1 , Z 2 , Z 3 , and Z 4 each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, or a substituent represented by general formula (2). 1 , Z 2 , Z 3, and Z 4 At least one of the groups is a substituent represented by the following general formula (2).

[0009] [ka]

[0010] In general formula (2), L represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

[0011] [ka]

[0012] In the general formula (5), R is the same as R in the general formula (2).

[0013] <2> The content of the compound represented by the general formula (5) is 0.01% by mass to 10% by mass relative to 100% by mass of a mixed liquid obtained by mixing the phthalonitrile compound represented by the general formula (1), the metal compound, and the compound represented by the general formula (5). <1> 1. A method for producing the phthalocyanine compound according to claim 1. <3> The content of the compound represented by the general formula (5) is 0.40% by mass to 5.00% by mass relative to 100% by mass of the mixed liquid. <2> 1. A method for producing the phthalocyanine compound according to claim 1.

[0014] <4> The compound represented by the general formula (5) is contained in an amount of 0.05 to 2.0 equivalents relative to 1 equivalent of the phthalonitrile compound represented by the general formula (1), <1> ~ <3> 10. A method for producing the phthalocyanine compound according to claim 9, wherein the phthalocyanine compound is a phthalocyanine compound. <5> In the mixing step, benzonitrile is further mixed as a reaction solvent. <1> ~ <4> 10. A method for producing the phthalocyanine compound according to claim 9, wherein the phthalocyanine compound is a phthalocyanine compound. <6> the content of water is less than 0.05% by mass relative to 100% by mass of a mixed liquid obtained by mixing the phthalonitrile compound represented by the general formula (1), the metal compound, and the compound represented by the general formula (5); <1> ~ <5> 10. A method for producing the phthalocyanine compound according to claim 9, wherein the phthalocyanine compound is a phthalocyanine compound.

[0015] <7> Further comprising a step of heating to 130°C or higher and 170°C or lower; <1> ~ <6> 10. A method for producing the phthalocyanine compound according to claim 9, wherein the phthalocyanine compound is a phthalocyanine compound. <8> The phthalocyanine compound is a phthalocyanine compound represented by the following general formula (3): <1> ~ <7> 10. A method for producing the phthalocyanine compound according to claim 9, wherein the phthalocyanine compound is a phthalocyanine compound.

[0016] [ka]

[0017] In the general formula (3), M represents a metal atom or an oxide of a metal atom. Z 11 , Z 12 , Z 13 , Z 14 , Z 15 , Z 16 , Z 17 , Z 18 , Z 19 , Z 20 , Z 21 , Z 22 , Z 23 , Z 24 , Z 25 , and Z 26 each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, or a substituent represented by general formula (4). However, Z 11 , Z 12 , Z 13 , Z 14 , Z 15 , Z 16 , Z 17 , Z 18, Z 19 , Z 20 , Z 21 , Z 22 , Z 23 , Z 24 , Z 25 , and Z 26 At least one of these is a substituent represented by the following general formula (4).

[0018] [ka]

[0019] In general formula (4), L represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. <9> M in the general formula (3) is zinc, magnesium, or oxyvanadium (V=O). <8> 1. A method for producing the phthalocyanine compound according to claim 1. [Effects of the Invention]

[0020] According to one embodiment of the present disclosure, it is possible to provide a method for producing a phthalocyanine compound, which can obtain a highly pure phthalocyanine compound having an ester side chain. DETAILED DESCRIPTION OF THE INVENTION

[0021] Hereinafter, an embodiment that is an example of the method for producing the phthalocyanine compound of the present disclosure will be described. These descriptions and examples are intended to illustrate the embodiment and are not intended to limit the scope of the invention. In the present disclosure, the use of "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower limit and upper limit. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In the present disclosure, the "mixed liquid" obtained in the step of mixing the phthalonitrile compound represented by general formula (1), a metal compound, and a compound represented by the following general formula (5) refers to a liquid obtained by mixing the phthalonitrile compound represented by the general formula (1), the metal compound, and the compound represented by the general formula (5) and before the cyclization reaction occurs. The term "reaction liquid" refers to a liquid containing the phthalonitrile compound represented by general formula (1) or the like in which a cyclization reaction is progressing over time or by applying energy such as heating.

[0022] Each component may contain multiple types of the corresponding substance. When referring to the amount of each component in a composition, if there are multiple substances corresponding to each component in the composition, the amount refers to the total amount of those multiple substances present in the composition, unless otherwise specified. In the present disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0023] [Method of producing phthalocyanine compounds] The method for producing a phthalocyanine compound of the present disclosure (hereinafter also referred to as the production method of the present disclosure) includes a step of mixing a phthalonitrile compound represented by the following general formula (1), a metal compound, and a compound represented by the following general formula (5) (hereinafter also referred to as the mixing step). [ka]

[0024] In general formula (1), Z 1 , Z 2 , Z 3 , and Z 4 each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, or a substituent represented by general formula (2). 1 , Z 2 , Z 3 , and Z 4 At least one of the groups is a substituent represented by the following general formula (2).

[0025] [ka]

[0026] In general formula (2), L represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

[0027] [ka]

[0028] In the general formula (5), R is the same as R in the general formula (2).

[0029] The mechanism by which a highly pure phthalocyanine compound can be obtained by the production method of the present disclosure is not clear, but is presumed to be as follows. In the phthalocyaninization reaction using phthalonitrile as a raw material, the coexistence of a nucleophilic component causes addition to the nitrile group of phthalonitrile, resulting in the generation of an active iminoester, which is thought to accelerate the reaction, i.e., accelerate the reaction via an active intermediate. However, if the target phthalocyanine compound has an ester group, the coexisting nucleophilic component may also undergo an addition reaction to the ester group, resulting in the generation of unintended by-products. In the production method of the present disclosure, a phthalonitrile compound represented by general formula (1) (also referred to as specific compound (1)), a metal compound, and a compound represented by general formula (5) (also referred to as specific alcohol (5)) are mixed. It is presumed that the coexistence of specific alcohol (5) as a nucleophilic component, which has the same substituent R as the substituent R of the ester side chain bonded to specific compound (1), results in the same structure even if a transesterification reaction of the ester side chain occurs, and therefore no by-products are generated, compared to the case where nucleophilic components of different structures are coexisted. It is believed that this makes it possible to produce a phthalocyanine compound with high purity in a short period of time.

[0030] (Specific Compound (1): Phthalonitrile Compound Represented by General Formula (1)) Z in general formula (1) 1 , Z 2 , Z 3 , and Z 4 each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, or a substituent represented by general formula (2). 1 , Z 2 , Z 3 , and Z 4 At least one of the groups is a substituent represented by the following general formula (2).

[0031] Examples of the halogen atom include a fluorine atom, an iodine atom, a bromine atom, and a chlorine atom, with a fluorine atom being preferred. The alkoxy group is preferably an alkoxy group having 1 to 12 carbon atoms. The aryloxy group is preferably an aryloxy group having 6 to 18 carbon atoms. The alkylthio group is preferably an alkylthio group having 1 to 12 carbon atoms. The arylthio group is preferably an arylthio group having 6 to 18 carbon atoms. When the alkoxy group, aryloxy group, alkylthio group, and arylthio group have a substituent, examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (which may be linear, branched, or cyclic), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a silyl group, a hydroxy group, a nitro group, an amino group, an alkylamino group, an alkoxy group, an aryloxy group, an acylamino group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonylamino group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an alkoxycarbonylamino group, a hydroxyl group, a nitro group, an arylamino group, an alkoxycarbonylamino group, a hydroxyl group, a nitro group, an arylamino group, an alkoxycarbonylamino group, a hydroxyl group, a nitro group, an arylamino group, an alkoxycarbonylamino group, a hydroxyl group, a nitro group, an arylamino group, an alkoxycarbonylamino group, a hydroxyl group, a nitro group, an arylamino group, an alkoxycarbonylamino group, a hydroxyl group, a nitro group, an alkoxycarbonylamino ... Examples of the alkyl group include a carbonyl group, a heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imido group, a heterocyclic thio group, a phosphoryl group, an acyl group, a carboxy group, and a sulfo group. From the viewpoint of easy availability of raw materials, an alkyl group, a phenoxycarbonyl group, a halogen atom, an alkoxycarbonyl group, a phenyl group, an alkenyl group, or an alkoxy group is preferred, an alkyl group, a phenoxycarbonyl group, or an alkoxy group is more preferred, an alkyl group or an alkoxy group is even more preferred, and an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms is particularly preferred.

[0032] Below, Z 1 , Z 2 , Z 3 , and Z 4 , Z 1 , ~Z 4 It is sometimes abbreviated as. Z 1 ~Z 4 are each independently preferably a hydrogen atom, a halogen atom, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, or the like. 1 ~Z 4 At least one of the groups is a substituent represented by the following formula (2), and Z 1 ~Z 4 Among them, Z 1 ~Z 4 may all be substituents represented by formula (2), 1 ~Z 4Among them, it is preferable that any three of them are substituents represented by formula (2), and it is more preferable that any two of them are substituents represented by formula (2). It is also preferable that any one of them is a substituent represented by formula (2). Z 1 ~Z 4 are each independently preferably a hydrogen atom, a halogen atom or a substituent represented by general formula (2).

[0033] More specifically, Z in general formula (1) 1 and Z 4 is a hydrogen atom or a halogen atom, preferably a fluorine atom, and Z 2 and Z 3 is a structure represented by formula (2), Z 1 , Z 3 and Z 4 is a hydrogen atom or a halogen atom, preferably a fluorine atom, and Z 2 A preferred example is a structure represented by formula (2). Preferred examples of the phthalonitrile compound represented by general formula (1) include a compound represented by the following general formula (1A) or a compound represented by general formula (1B).

[0034] [ka]

[0035] In the above general formula (1A) or general formula (1B), each X independently represents a hydrogen atom or a halogen atom, and L and R are the same as L and R in the above general formula (2), respectively.

[0036] In general formula (2), L represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and is preferably an unsubstituted alkylene group or an unsubstituted arylene group. R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group, an allyl group, or a phenyl group, and still more preferably a phenyl group.

[0037] (Specific alcohol (5): Compound represented by general formula (5)) The compound represented by general formula (5) (specific alcohol (5)) is an alcohol having the same substituent R as the terminal group R in the ester side chain of specific compound (1). In the general formula (5), R is the same as R in the general formula (2), and the preferred examples are also the same.

[0038] The content of the specific alcohol (5) is preferably 0.01% by mass to 10% by mass, based on 100% by mass of the mixed liquid obtained by mixing the specific compound (1), the metal compound, and the specific alcohol (5), and more preferably 0.40% by mass to 5.00% by mass, based on 100% by mass of the mixed liquid. When the content of the specific alcohol (5) is within the above range, the purity of the obtained phthalocyanine compound is further improved, and the yield is further improved. The mixture obtained by mixing the specific compound (1), the metal compound, and the specific alcohol (5) before the cyclization reaction is also simply referred to as the "mixture."

[0039] The content of specific alcohol (5) is preferably 0.05 equivalents or more, more preferably 0.09 equivalents or more, and even more preferably 0.10 equivalents or more relative to 1 equivalent of specific compound (1). The content of specific alcohol (5) is preferably 2.0 equivalents or less, more preferably 1.2 equivalents or less, even more preferably less than 1.0 equivalent, and particularly preferably 0.7 equivalents or less relative to 1 equivalent of specific compound (1). When the content of the specific alcohol (5) relative to the specific compound (1) is within the above range, the yield is further improved and the purity of the obtained phthalocyanine compound is also superior. The content of the specific alcohol (5) in the mixed liquid can be calculated from the charged amount. Alternatively, the amount can be measured by analyzing the mixture by gas chromatography, for example.

[0040] (metal compound) The metal compound is not particularly limited, and may be any metal compound capable of forming the central metal of the phthalocyanine compound. Examples include metal compounds containing copper, zinc, magnesium, aluminum, vanadium, iron, nickel, cobalt, palladium, titanium, indium, etc. Among these, when a metal compound with low reactivity, such as a zinc compound, a magnesium compound, or a vanadium oxide compound, is used, the effects obtained by the production method of the present disclosure are considered to be remarkable. Specific examples of the metal compound include zinc iodide, zinc chloride, zinc bromide, zinc acetate, zinc stearate, copper iodide, copper chloride, copper bromide, copper acetate, copper stearate, aluminum chloride, aluminum fluoride, magnesium chloride, magnesium bromide, and vanadium oxide (VO). From the viewpoint of achieving a more efficient cyclization reaction, zinc iodide, zinc stearate, and the like are preferred.

[0041] For example, by using zinc iodide or zinc stearate as the metal compound, iodine, stearic acid, etc., which are generated as the reaction proceeds, are present between phthalocyanine molecules having a planar structure or are coordinated to the Z axis, allowing the solvent to enter between the phthalocyanine molecules and improving solubility. It is presumed that this prevents unreacted raw materials from being incorporated into the crystals that precipitate from the reaction solution of the generated phthalocyanine compound, thereby improving the efficiency of the cyclization reaction. Only one type of metal compound may be used, or two or more types may be used. However, from the viewpoint of the purity of the resulting phthalocyanine compound, when two or more types of metal compounds are used, it is preferable that the metal atoms constituting the central metal are of the same type. The amount of the metal compound added in the mixing step is preferably 0.20 to 0.5 equivalents relative to 1 equivalent of the phthalonitrile compound represented by the general formula (1), and from the viewpoint of yield, more preferably 0.25 to 0.3 equivalents.

[0042] The specific compound (1), the metal compound, and the specific alcohol (5) are mixed together, and after the mixing step, a cyclization reaction of the specific compound proceeds over time or by applying energy such as heating, to obtain the target phthalocyanine compound. The mixture obtained by mixing the specific compound (1), the metal compound, and the specific alcohol (5) may further contain a reaction solvent. Examples of the reaction solvent include inert solvents that have low or no reactivity with the specific compound (1). Specific examples include inert solvents such as benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, and benzonitrile; Examples of the solvent include aprotic polar solvents such as pyridine, N,N-dimethylformamide, N-methyl-2-pyrrolidinone, N,N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethyl sulfoxide, and sulfolane. Among these, in terms of the solubility of the specific compound (1) as a raw material and the ability to cope with an increase in the reaction temperature, benzonitrile, nitrobenzene, mesitylene, chlorobenzene, dichlorobenzene, trichlorobenzene, chloronaphthalene, methylnaphthalene, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, and the like are preferred, with benzonitrile, nitrobenzene, mesitylene, and the like being more preferred, and benzonitrile being even more preferred. That is, the mixture preferably contains benzonitrile as a reaction solvent. Benzonitrile is used as a reaction solvent because it has good solubility for specific compound (1), and it can coordinate to metal compounds to improve the solubility of the metal compounds. Benzonitrile also has an appropriate coordinating power that does not inhibit the coordination between specific compound (1) and metal compounds.

[0043] The content of water in the mixed liquid obtained in the mixing step is preferably less than 0.05% by mass relative to 100% by mass. According to the studies of the present inventors, by controlling the water content in the mixed solution to be subjected to the cyclization reaction to be less than 0.05% by mass, the hydrolysis reaction of the ester side chain of the specific compound (1) caused by water during the cyclization reaction is suppressed, and the production of an undesired phthalocyanine compound, which is a by-product formed by hydrolysis of the ester side chain, is suppressed, which is thought to contribute to improving the purity of the obtained phthalocyanine compound. Furthermore, it is presumed that the low water content suppresses the hydrolysis reaction of the nitrile contained in the specific compound (1), allowing the cyclization reaction to proceed more efficiently, which in turn contributes to improving the yield of the desired phthalocyanine compound. The water content in the mixed liquid is preferably less than 0.05% by mass, more preferably less than 0.04% by mass, and even more preferably less than 0.03% by mass, and the water content may be below the detection limit. The water content in the mixed solution, i.e., the water content, can be analyzed by Karl Fischer water content measurement, the details of which will be described in the Examples below.

[0044] The mixed solution to be subjected to the cyclization reaction has a higher concentration, i.e., a higher ratio of the total amount of the specific compound (1) and the metal compound relative to the total amount of the specific alcohol (5) functioning as a solvent and any reaction solvent contained therein, which is advantageous for the progress of the reaction because it can improve the frequency of contact between the components necessary for the cyclization reaction. However, if the concentration is too high, the viscosity of the mixed solution increases and the fluidity decreases, which may conversely decrease the reaction rate. Therefore, it is preferable to set the viscosity of the mixture appropriately.

[0045] The ratio of the amount of the solvent used to the amount of the specific compound (1) used is preferably 1.0 to 3.0 times, more preferably 2.0 to 3.0 times, and even more preferably 2.0 to 2.5 times, on a mass basis.

[0046] The manufacturing method of the present disclosure preferably further comprises a step of heating to 130°C to 170°C. By including the step of heating to 130°C to 170°C, the cyclization reaction of the phthalonitrile compound proceeds, and the target phthalocyanine compound can be obtained efficiently. In the present disclosure, as described above, a liquid in which the cyclization reaction has been initiated by heating and in which the reaction is progressing is referred to as a "reaction liquid," and is distinguished from a "mixed liquid" in which raw materials are mixed and which has not yet been heated (heated) to initiate the cyclization reaction. Note that the "mixed liquid" also encompasses a liquid immediately before the temperature is raised to a temperature at which the phthalocyanine cyclization reaction progresses.

[0047] In general, a higher reaction temperature is preferable because it allows the reaction to be accelerated beyond the activation energy, improves the solubility of the reaction raw materials, and reduces the viscosity of the reaction solution, improving its fluidity and thereby increasing the frequency of contact between the components contained in the reaction solution. From this viewpoint, the heating conditions are preferably a temperature of 130°C or higher, more preferably 135°C or higher, and even more preferably 140°C or higher. If the temperature in the heating step is much higher than 170° C., the reaction may proceed due to heating, and the reaction product may be decomposed. Therefore, from the viewpoints of the cyclization reaction and the purity of the resulting phthalocyanine compound, the temperature in the heating step is more preferably 170° C. or lower, and even more preferably 165° C. or lower. Here, the temperature in the heating step may be the ambient temperature or the liquid temperature of the mixed liquid (including the reaction liquid in which the cyclization reaction has progressed by heating).

[0048] The heating method is not particularly limited, and can be performed by using a heating device (heater, etc.). The heating device can be one having a temperature adjustment function. In the present disclosure, the temperature under the heating conditions is preferably the temperature of the liquid. Heating the mixture promotes the reaction of the components contained in the mixture. From the viewpoint of reactivity, the treatment time for the heating step is, for example, preferably 3 hours to 168 hours, and more preferably 12 hours to 96 hours.

[0049] (Other processes) The manufacturing method of the present disclosure may include other steps in addition to the above-described mixed solution and heating. Other steps include a cooling step in which the reaction liquid reacted in the heating step is cooled. The cooling method in the cooling step is not particularly limited, and may be performed using a cooling device (such as a fan) or by allowing to cool naturally. The cooling temperature is not particularly limited and can be, for example, 0° C. to 30° C. In the present disclosure, the cooling temperature refers to the environmental temperature at which cooling is performed. After cooling, filtration or the like may be carried out or the solvent may be removed.

[0050] There are no particular limitations on the reaction vessel that can be used in the cyclization reaction, and any known reaction vessel can be used. When using a solvent, raw materials, etc. whose boiling point is equal to or lower than the reaction temperature, a pressure-resistant vessel or a sealed vessel such as an autoclave can be used. The manufacturing method of the present disclosure is preferably carried out under an inert atmosphere.

[0051] The phthalocyanine compound obtained by the production method of the present disclosure is preferably a phthalocyanine compound represented by the following general formula (3).

[0052] [ka]

[0053] In the general formula (3), M represents zinc, magnesium, or vanadium oxide (V=O), and Z 11 , Z 12 , Z 13 , Z 14 , Z 15 , Z 16 , Z 17 , Z 18 , Z 19 , Z 20 , Z 21 , Z 22 , Z 23 , Z 24 , Z25 , and Z 26 (Hereinafter, Z 11 ~Z 26 and (sometimes referred to as "substituted or unsubstituted") each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, or a substituent represented by general formula (4). However, Z 11 ~Z 26 At least one of these is a substituent represented by the following general formula (4).

[0054] [ka]

[0055] In general formula (4), L represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Z in the above general formula (3) 11 ~Z 26 are each independently Z in the general formula (1) of the specific compound (1) described above. 1 ~Z 4 The preferred embodiments are also the same. L and R in the above general formula (4) are the same as L and R in the above general formula (2), and preferred examples are also the same.

[0056] The compound represented by general formula (3) is preferably a compound represented by the following general formula (3A) or (3B).

[0057] [ka]

[0058] X in the general formula (3A) and the general formula (3B) represents a hydrogen atom or a halogen atom, and is preferably a hydrogen atom or a fluorine atom. M in the general formula (3A) and the general formula (3B) is the same as M in the above general formula (3). L and R in the general formula (3A) and the general formula (3B) are the same as L and R in the above general formula (4).

[0059] Hereinafter, exemplary compounds of the compound represented by general formula (3) will be described by clearly indicating the structure and each substituent, but it goes without saying that the exemplary compounds represented by general formula (3) are not limited to the following examples.

[0060] [ka]

[0061] [ka]

[0062] The phthalocyanine compound obtained by the production method of the present disclosure can be used for various applications. The resulting phthalocyanine compound can be used as a coloring material in ink-jet inks, thermal transfer recording sheets, printing inks, paints, and the like. [Example]

[0063] The present disclosure will be described in detail below based on examples. However, the present disclosure is not limited to the following examples, and the contents described in the following examples (e.g., raw materials, conditions, and methods) may be modified as appropriate within the scope of the present disclosure. In the following description, "%" means "% by mass" unless otherwise specified.

[0064] Example 1 In a 1 L (liter) three-neck flask were placed 129 mL of benzonitrile and 60 g of 3,6-difluoro-4,5-di([4-phenoxycarbonyl]phenoxy)-1,2-phthalonitrile, and the mixture was heated to an internal temperature of 130° C., and 30 mL of benzonitrile was distilled off under reduced pressure. The internal temperature was cooled to 25°C, and 8.46 g of zinc (II) iodide, 0.96 g of phenol, and 0.96 mL of benzonitrile were added and mixed. (Mixing Step) A 0.5 g sample was taken from the resulting mixed liquid, and the moisture content was measured using a Karl Fischer moisture meter (manufactured by Kyoto Electronics Manufacturing Co., Ltd.) As a result, the moisture content of the mixed liquid was 0.01%. Thereafter, the mixture was heated to an internal temperature of 145°C and reacted for 48 hours. (Heating Step)

[0065] The reaction solution was cooled to 70° C., and 255 mL of methanol was added dropwise. The internal temperature was cooled to 25° C., and the precipitated crystals were filtered and washed with 210 mL of methanol to obtain 109 g of wet crystals of Exemplified Compound 1. The entire amount of the obtained wet crystals was placed in a 1000 mL three-neck flask, 359 mL of methanol was added, and the mixture was stirred under reflux heating conditions for 1 hour. After the internal temperature was cooled to 25°C, the crystals were filtered and washed with 60 mL of methanol. The obtained crystals were dried at 80°C, thereby obtaining 43 g of a green powder of Exemplified Compound 3A-3. The yield was 82%. The green powder was analyzed by HPLC and found to be 95.2% pure. The purity of the compound was determined by dissolving the obtained phthalocyanine compound in N-methyl-2-pyrrolidone and measuring the area ratio at a measurement wavelength of 254 nm using high performance liquid chromatography (HPLC, apparatus name: Shimadzu LC-2010A, eluent: water / THF).

[0066] <Examples 2 to 8> A phthalocyanine compound was obtained in the same manner as in Example 1, except that the specific compound (1), i.e., the phthalonitrile compound and the specific alcohol (5) used in Example 1 were changed to the compounds listed in Table 1 below. The water content of the mixed solution, the yield, and the purity of the obtained phthalocyanine compound, all measured in the same manner as in Example 1, are also shown in Table 2.

[0067] [Table 1]

[0068] [Table 2]

[0069] The phthalocyanine compounds obtained in Examples 1 to 8, which are the production methods of the present disclosure, were all obtained in good yield, and the purity of the obtained phthalocyanine compounds was particularly high.

[0070] <Examples 9 to 19> A phthalocyanine compound was obtained in the same manner as in Example 1, except that the content of the compound represented by general formula (5) used in Example 1, the metal compound used, and the solvent were changed as shown in Tables 3 and 4, and the heating conditions for the mixed liquid were changed to the conditions shown in Table 4. The water content of the mixed solution, the yield, and the purity of the obtained phthalocyanine compound, all measured in the same manner as in Example 1, are also shown in Table 4.

[0071] [Table 3]

[0072] [Table 4]

[0073] According to Examples 9 to 19, which are the production methods of the present disclosure, the yields were all good and the purity of the obtained phthalocyanine compounds was high.

[0074] <Comparative Example 1> A phthalocyanine compound was synthesized with reference to the description in Example 1 of JP 2022-133059 A. Specifically, a phthalonitrile intermediate (1) was synthesized with reference to paragraph

[0072] of JP 2022-133059 A. The obtained phthalonitrile intermediate (1) was used to carry out a cyclization reaction under the conditions described in Tables 5 and 6. The reaction solution was cooled to 70° C., and 255 mL of methanol was added dropwise. The internal temperature was cooled to 25° C., and the precipitated crystals were filtered and washed with 210 mL of methanol to obtain a phthalocyanine compound.

[0075] <Comparative Example 2> A phthalocyanine compound was obtained in the same manner as in Example 1, except that ethanol, a comparative alcohol, was used instead of the compound represented by general formula (5) used in Example 1. The water content of the mixed solution, the yield, and the purity of the obtained phthalocyanine compound, all measured in the same manner as in Example 1, are also shown in Table 6.

[0076] [Table 5]

[0077] [Table 6]

[0078] It can be seen that the phthalocyanine compound obtained by the method of Comparative Example 1, which uses the same phthalonitrile compound as a starting material but does not use the compound represented by general formula (5) and in which the mixed solution has a high water content, has a lower purity than the Examples. It can also be seen that the phthalocyanine compound obtained by the production method of Comparative Example 2, which uses a comparative alcohol whose terminal substituent is different from that of the phthalonitrile compound instead of the compound represented by general formula (5), also has a lower purity than the Examples. This is thought to be because the ester side chain of the phthalocyanine compound is hydrolyzed or solvolyzed during the cyclization reaction, causing a side reaction.

[0079] Comparison of the Examples and Comparative Examples reveals that the phthalocyanine compounds obtained by the production methods of the Examples, which include a step of mixing the phthalonitrile compound represented by general formula (1), a metal compound, and a compound represented by general formula (5), are of high purity.

Claims

1. The method includes a step of mixing a phthalonitrile compound represented by the following general formula (1), a metal compound, and a compound represented by the following general formula (5): A method for producing a phthalocyanine compound. 【Chemical 1】 In general formula (1), Z １ , Z ２ , Z ３ , and Z ４ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, or a substituent represented by the following general formula (2): １ , Z ２ , Z ３ , and Z ４ At least one of the groups is a substituent represented by the following general formula (2). 【Chemistry 2】 In general formula (2), L represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. 【Chemistry 3】 In the general formula (5), R is the same as R in the general formula (2).

2. 2. The method for producing a phthalocyanine compound according to claim 1, wherein the content of the compound represented by the general formula (5) is 0.01% by mass to 10% by mass relative to 100% by mass of a mixed liquid obtained by mixing the phthalonitrile compound represented by the general formula (1), the metal compound, and the compound represented by the general formula (5).

3. 3. The method for producing a phthalocyanine compound according to claim 2, wherein the content of the compound represented by the general formula (5) is 0.40% by mass to 5.00% by mass relative to 100% by mass of the mixed solution.

4. 2. The method for producing a phthalocyanine compound according to claim 1, wherein the compound represented by the general formula (5) is contained in an amount of 0.05 to 2.0 equivalents relative to 1 equivalent of the phthalonitrile compound represented by the general formula (1).

5. The method for producing a phthalocyanine compound according to claim 1 , wherein in the mixing step, benzonitrile is further mixed as a reaction solvent.

6. 2. The method for producing a phthalocyanine compound according to claim 1, wherein a water content relative to 100 mass% of a mixed liquid obtained by mixing the phthalonitrile compound represented by the general formula (1), the metal compound, and the compound represented by the general formula (5) is less than 0.05 mass%.

7. The method for producing a phthalocyanine compound according to claim 1 , further comprising a step of heating the mixture to a temperature of 130° C. or higher and 170° C. or lower.

8. 2. The method for producing a phthalocyanine compound according to claim 1, wherein the phthalocyanine compound is a phthalocyanine compound represented by the following general formula (3): 【Chemistry 4】 In the general formula (3), M represents a metal atom or an oxide of a metal atom. Z １１ , Z １２ , Z １３ , Z １４ , Z １５ , Z １６ , Z １７ , Z １８ , Z １９ , Z ２０ , Z ２１ , Z ２２ , Z ２３ , Z ２４ , Z ２５ , and Z ２６ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, or a substituent represented by general formula (4). However, Z １１ , Z １２ , Z １３ , Z １４ , Z １５ , Z １６ , Z １７ , Z １８ , Z １９ , Z ２０ , Z ２１ , Z ２２ , Z ２３ , Z ２４ , Z ２５ , and Z ２６ At least one of the groups is a substituent represented by the following general formula (4). 【Chemistry 5】 In general formula (4), L represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

9. 9. The method for producing a phthalocyanine compound according to claim 8, wherein M in the general formula (3) is zinc, magnesium, or oxyvanadium (V=O).

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