Method for producing phthalocyanine compound

Abstract

To provide a method for producing a phthalocyanine compound having excellent solubility in a solvent and optical characteristics, which can shorten a reaction time, especially to shorten a cyclization reaction time when a metal iodide is used among metal compounds introduced in a phthalocyanine pigment.SOLUTION: Provided is a method for producing a phthalocyanine compound comprising a step of subjecting a phthalonitrile compound to a cyclization reaction with a metal compound, where the cyclization reaction is performed with a water content controlled in a range of 0.05 to 0.40 mass% relative to 100 mass% of a reaction solution and, especially, the above metal compound is a metal iodide.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a novel method for producing a phthalocyanine compound. In particular, the present invention relates to a method for producing a phthalocyanine compound having excellent optical properties.

Background Art

[0002] Phthalocyanine compounds useful as near-infrared absorbing dyes or their precursors, high-grade pigments or dyes, etc. have absorption in the near-infrared region in a wide range of fields such as near-infrared absorbing dyes or their precursors, high-grade pigments or dyes, and are used in optical recording media using semiconductor lasers, liquid crystal display devices, near-infrared absorbing dyes, near-infrared sensitizers, photothermal converters such as heat-sensitive transfer, heat ray absorbing materials, near-infrared absorbing materials such as near-infrared absorbing filters, color separation filters, color filters for liquid crystal displays, color filters for optics, color filters for plasma display displays, color brown tube selective absorption filters, color toners, inks for inkjet, etc.

[0003] As methods for producing the above phthalocyanine compounds, for example, Patent Documents 1 and 2 are known. Patent Document 1 discloses that when producing a phthalocyanine compound by cyclizing a phthalonitrile compound alone or with a metal compound, the above cyclization reaction is carried out in an organic compound having a specific amount of hydroxyl groups and / or carboxyl groups and while introducing an inert gas. A method for producing a phthalocyanine compound is disclosed. According to this method, it is described that the phthalocyanine compound can be industrially produced at low cost in a safer and more preferable method without using an oxygen source having a risk of explosion such as an oxygen-containing gas. Further, in the examples, n-octanol, diethylene glycol monomethyl ether, benzyl alcohol, benzoic acid, and naphthoic acid are used as the organic compound having the hydroxyl group and / or carboxyl group. In addition, Patent Document 2 discloses that when producing a phthalocyanine compound, when a phthalonitrile compound is subjected to a cyclization reaction alone or with a metal compound, by carrying out the cyclization reaction in a mixed solvent of a hydrocarbon-based solvent and a nitrile-based solvent, even during mass production of 20 liters or more, precipitation of impurities such as unreacted metal compounds during the production process of the phthalocyanine compound can be significantly suppressed and prevented, and the impurities will not clog the filter even after filtration after the reaction, and rapid filtration can be achieved.

[0004] Although various research and developments have been carried out for the industrial production of phthalocyanine compounds, there is still room for further improvement in reaction time and reaction efficiency (yield).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] An object of the present invention is to provide a method for producing a phthalocyanine compound that can shorten the reaction time and has excellent solubility in a solvent and optical properties. In particular, an object is to shorten the cyclization reaction time by a production method that can activate the complexation reaction of metal iodide among the metal compounds introduced into the phthalocyanine compound.

Means for Solving the Problems

[0007] As a result of intensive studies, the present inventors have found a method for producing a phthalocyanine compound that can shorten the cyclization reaction time. That is, the object of the present invention is achieved by the following <1> to <6>. <1> A method for producing a phthalocyanine compound, comprising a step of subjecting a phthalonitrile compound to a cyclization reaction with a metal compound, characterized in that the cyclization reaction is carried out in a reaction solution having a water content in the range of 0.05 to 0.40 mass% relative to 100 mass%. <2> The phthalonitrile compound is represented by the following formula (1):

[0008] [ka] and a phthalonitrile compound (1) represented by the following formula (2):

[0009] [ka] and a phthalonitrile compound (2) represented by the following formula (3):

[0010] [ka] and a phthalonitrile compound (3) represented by the following formula (4):

[0011] [ka] (However, in the above formulas (1) to (4), Z1 to Z 16 are each independently a hydrogen atom, SR 1 , OR 2 or a halogen atom, R 1 and R 2 each independently represents 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. The phthalonitrile compound (4) is represented by the formula: The phthalocyanine compound is represented by the following formula (5):

[0012] [ka] (However, Z1~Z16 is a hydrogen atom, SR 1 , OR 2 or a halogen atom, R 1 and R 2 each independently represents 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, and M represents a metal, a metal oxide, or a metal halide. The phthalocyanine compound is characterized in that it is represented by the formula: <1> 2. A method for producing the phthalocyanine compound according to claim 1 . <3> The water further contains a protic polar solvent other than water. <1> or <2> 2. A method for producing the phthalocyanine compound according to claim 1 . <4> The metal compound is a metal iodide. <1> ~ <3> 3. A method for producing the phthalocyanine compound according to claim 1 , <5> The volume of the reaction solution is 3 liters to 15 ml. 3 characterized in that <1> ~ <4> 3. A method for producing the phthalocyanine compound according to claim 1 , <6> A method for producing a phthalocyanine compound, comprising a step of subjecting a phthalonitrile compound to a cyclization reaction with a metal iodide, characterized in that the water content is adjusted to within a range of 0.05 to 0.40 mass% relative to 100 mass% of a reaction solution, and then heating. Effect of the Invention

[0013] In the method for producing a phthalocyanine compound of the present invention, the cyclization reaction time can be significantly shortened, and the obtained phthalocyanine compound can be used in a wide range of fields as a near-infrared absorbing dye or its precursor, a high-grade pigment or dye, etc. In particular, when a metal iodide is used as the metal compound, the above-mentioned effect is remarkable, and it becomes possible to efficiently produce on an industrial scale. [Brief description of the drawings]

[0014]

Figure 1

Mode for Carrying Out the Invention

[0015] The present invention will be described in detail below. In addition, a form in which two or more of the individual preferred forms of the present invention described below are combined is also a preferred form of the present invention. In this specification, the numerical range "Min~Max" means not less than the minimum value Min and not more than the maximum value Max. Further, when suitable numerical values are described stepwise for the upper limit value and the lower limit value, a numerical range obtained by appropriately combining the upper limit value and the lower limit value described separately is also a suitable numerical range. As described above, the method for producing a phthalocyanine compound of the present invention is a method for producing a phthalocyanine compound having a step of subjecting a phthalonitrile compound to a cyclization reaction with a metal compound, and the cyclization reaction is carried out with the water content in the range of 0.05 to 0.40% by mass based on 100% by mass of the reaction solution. Further, it is a preferred form that the metal compound is a metal iodide. According to the present invention, the time of the cyclization reaction can be significantly shortened. This is preferable from the viewpoint of productivity, and is particularly preferable during mass production when the reaction volume (the volume of the reaction solution charged into the reaction vessel) is 3 liters or more. In the present invention, when carrying out the cyclization reaction, a catalyst or an additive for suppressing corrosion may be added. In this case, when an insoluble substance such as calcium carbonate is used to suppress corrosion when using a metal halide or the like, it is desirable to filter and remove this after the reaction. Further, even when such an insoluble additive or the like is not used, during the cyclization reaction, hardly soluble by-products (impurities) generated by the polymerization of the phthalonitrile compound often occur, or metal oxides are generated or remain. Therefore, in order to obtain a phthalocyanine compound with high purity, it is desirable to perform filtration after the cyclization reaction.

[0016] Although the reason why the rate of the cyclization reaction is improved by the presence of a specific amount of water during the cyclization reaction is not clear, it is considered as follows. However, it goes without saying that the technical scope of the present invention is not limited by the following inferences. That is, when the reaction solution is heated, a redox reaction occurs in the reaction system in addition to the cyclization reaction, and it is speculated that water, which is a protic polar solvent, may act as an oxidizing agent. Further, when a metal iodide is used as the metal compound, it catalytically acts on the phthalonitrile compound to further promote the cyclization reaction, and I2 generated as a side reaction is present between the phthalocyanine molecules having a planar structure, so that the solvent enters between the phthalocyanine molecules, improving the solubility and also contributing to the improvement of the efficiency of the cyclization reaction. Since the solubility of the charged raw materials and the generated compounds is improved in this way, promoting the reaction, it is considered that the reaction yield (raw material conversion rate) and the reaction rate are also increased thereby. As described above, the reaction solution during the cyclization reaction contains a phthalonitrile compound, a metal compound, a solvent, and optionally a catalyst and an additive. The present inventors have found that the reaction time can be shortened by adjusting the amount of water, which is a protic polar solvent, with respect to 100% by mass of the reaction solution (total amount of the solvent and the dissolved solute). In a normal cyclization reaction, an organic solvent is used. The organic solvent may be any inert solvent having low reactivity, preferably no reactivity, with the phthalonitrile compound as the starting material, for example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, and benzonitrile and other inert solvents; and pyridine, N,N-dimethylformamide, N-methyl-2-pyrrolidinone, N,N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethyl sulfoxide, sulfolane and other aprotic polar solvents and the like. In the cyclization reaction of the present invention, in addition to the above-mentioned inert solvent or aprotic polar solvent, it is preferably to contain a specific amount of water which is a protic polar solvent. Specifically, it is preferably to contain at least one solvent selected from hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, nitrogen compound solvents, sulfur compound solvents, and a specific amount of water. Moreover, it is particularly preferable to contain a hydrocarbon solvent or a halogenated hydrocarbon solvent and a specific amount of water. Particularly preferred solvents will be described in detail below.

[0017] (Hydrocarbon solvent or halogenated hydrocarbon solvent) The hydrocarbon solvent means a solvent composed of carbon and hydrogen. The halogenated hydrocarbon solvent means a solvent in which at least one hydrogen of the hydrocarbon solvent is substituted by a halogen. Such a hydrocarbon solvent or halogenated hydrocarbon solvent is not particularly limited as long as it is less likely to cause side reactions during the cyclization reaction and can rapidly perform cyclization. However, from the viewpoint of the solubility of the raw material phthalonitrile compound, metal compound, and the resulting phthalocyanine compound, a halogenated hydrocarbon solvent is preferred. Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, considering solubility, the difficulty of side reactions occurring, and the ease of industrial availability, a chlorine atom is preferred. The boiling point of the above-mentioned hydrocarbon solvent or halogenated hydrocarbon solvent is not particularly limited, but is preferably 80 to 260 °C, more preferably 120 to 240 °C, and still more preferably 140 to 200 °C. If the boiling point of the solvent is less than 80 °C, the reaction may be slow at temperatures below the boiling point. Also, a large amount of solvent may be required to dissolve the raw material, resulting in low productivity. Conversely, if it exceeds 260 °C, it may be necessary to maintain a high temperature for a long time in the subsequent drying (solvent removal) process or to increase the vacuum degree using special equipment, which may not be preferable. As the hydrocarbon solvent or halogenated hydrocarbon solvent, specifically, hydrocarbon solvents such as benzene (boiling point: about 80 °C), toluene (boiling point: about 111 °C), ethylbenzene (boiling point: about 136 °C), propylbenzene (isocumene) (boiling point: about 159 °C), isopropylbenzene (cumene) (boiling point: about 152 °C), o-xylene (boiling point: about 144 °C), m-xylene (boiling point: about 139 °C), p-xylene (boiling point: about 138 °C), 1-methyl-2-ethylbenzene (boiling point: about 165 °C), 1-methyl-3-ethylbenzene (boiling point: about 161 °C), 1-methyl-4-ethylbenzene (boiling point: about 162 °C), o-diethylbenzene (boiling point: about 184 °C), 1,2,3-trimethylbenzene (boiling point: about 176 °C), 1,2,4-trimethylbenzene (boiling point: about 169 °C), 1,3,5-trimethylbenzene (boiling point: about 164 °C), 1-methylnaphthalene (boiling point: about 245 °C), 2-methylnaphthalene (boiling point: about 241 °C), 1-ethylnaphthalene (boiling point: about 251 - 252 °C), 2-ethylnaphthalene (boiling point: about 252 °C), n-octane (boiling point: about 126 °C), n-decane (boiling point: about 174 °C); and halogenated hydrocarbon solvents such as chlorobenzene (boiling point: about 132 °C), 1,2-dichlorobenzene (boiling point: about 180 °C), 1,3-dichlorobenzene (boiling point: about 173 °C), 1,4-dichlorobenzene (boiling point: about 174 °C), 1,2,3-trichlorobenzene (boiling point: about 219 °C), 1,2,4-trichlorobenzene (boiling point: about 213 °C), 1,3,5-trichlorobenzene (boiling point: about 208 °C), 1,2,4,5-tetrachlorobenzene (boiling point: about 243 - 246 °C), 2-chlorotoluene (boiling point: about 159 °C), 3-chlorotoluene (boiling point: about 161 °C), 4-chlorotoluene (boiling point: about 162 °C), 1-chloronaphthalene (boiling point: about 259 °C), 2-chloronaphthalene (boiling point: about 256 °C) etc. can be mentioned. Among these, considering the rate of the cyclization reaction, the likelihood of side reactions occurring during the cyclization reaction, boiling point, solubility of the phthalonitrile compound, ease of industrial availability, etc., 1,2,4-trimethylbenzene, xylene, toluene, chlorobenzene, dichlorobenzene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, n-decane, etc. are preferred. More preferably, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, xylene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, dichlorobenzene, n-decane. Most preferably, from the viewpoints of the solubility and boiling point of the starting phthalonitrile compound, metal compound, and the resulting phthalocyanine compound, 1,2,4-trimethylbenzene and 2-chlorotoluene. In addition, the above hydrocarbon solvents and halogenated hydrocarbon solvents may each be used alone or in the form of a mixture of two or more, or one or more of each may be used in combination, but it is common to use them alone.

[0018] (Nitrile solvents) Examples of nitrile solvents include benzonitrile, acetonitrile, propionitrile, etc. Among these, considering the solubility and reactivity of the metal compound, the stability of the solvent itself, etc., benzonitrile, acetonitrile, etc. are preferred, and more preferably benzonitrile. In addition, the above nitrile solvents may each be used alone or in the form of a mixture of two or more, but it is common to use them alone. (Protic polar solvents) Examples of protic polar solvents include alcohols, amines, and phenols in addition to water, which is preferably used in the production method of the present invention. When used in combination with water, alcohol is preferred. Although water is not particularly limited, general industrial pure water or ion-exchanged water can be used. That is, it is water sourced from rivers, groundwater, lakes, seawater, well water, etc., and purified by precipitation, coagulation, filtration, distillation, ion exchange, ultrafiltration, reverse osmosis, etc. Also, the ionic conductivity at 25°C is preferably 10 μS / cm or less, more preferably 5 μS / cm or less. The alcohols include monohydric alcohols and polyhydric alcohols. Examples thereof include primary alcohols such as methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, and 1-octanol; secondary alcohols such as isopropanol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, cyclohexanol, 2-heptanol, and 3-heptanol; tert-butanol, tert-pentanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol mono-n-butyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol monophenyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, and tripropylene glycol mono-n-butyl ether. Among them, alcohols having 2 or more carbon atoms are preferred. Examples of the alcohols having 2 or more carbon atoms include ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, tert-butanol, and tert-pentanol. Examples of the amine (solvent) include diethylamine, dimethylamine, and oleylamine.

[0019] Examples of the phenol include phenol, cresol, o-cresol, m-cresol, p-cresol, and xylenol. It is preferable to use water alone, but other protic polar solvents may be used in combination. The water content is preferably adjusted to a range of 0.05 to 0.40% by mass with respect to 100% by mass of the reaction solution, from the viewpoint of shortening the reaction time. More preferably, it is 0.10 to 0.40% by mass, and particularly preferably 0.15 to 0.30% by mass. When the water content is within the above numerical range, the cyclization reaction proceeds rapidly and the optical properties of the phthalocyanine obtained after the cyclization reaction are good. When using a protic polar solvent other than water in combination, it is preferably adjusted to the range of 0.05 to 0.95% by mass based on 100% by mass of the reaction solution. More preferably, it is 0.05 to 0.50% by mass, still more preferably 0.05 to 0.40% by mass, and particularly preferably 0.10 to 0.30% by mass. When the content of the protic polar solvent other than water is within the above numerical range, water works efficiently, the cyclization reaction proceeds rapidly, and the optical properties of the phthalocyanine obtained after the cyclization reaction are good. In addition, considering the compatibility of the protic polar solvent with the reaction solvent and water when used in combination with water, alcohol is preferred.Preferred alcohols are both monohydric and polyhydric alcohols. Considering the compatibility with the reaction solvent and the boiling point, alcohols having 4 or more carbon atoms are particularly preferred. For example, primary alcohols such as 1-butanol, 1-pentanol, 1-hexanol, 1-octanol, etc., secondary alcohols such as 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, cyclohexanol, 2-heptanol and 3-heptanol, tert-butanol, tert-pentanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol mono-n-butyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol monophenyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol, tripropylene glycol monomethyl ether and tripropylene glycol mono-n-butyl ether can be exemplified.

[0020] In addition, when water and a protic polar solvent other than water are used in combination, the content of the total protic polar solvent is preferably in the range of 0.10 to 1.00% by mass, more preferably 0.15 to 0.80% by mass, still more preferably 0.15 to 0.60% by mass, and particularly preferably 0.15 to 0.50% by mass with respect to 100% by mass of the reaction solution, so that the effects of the present invention can be achieved. The total amount of all solvents contained in the reaction solution is not particularly limited as long as the reaction rate of the cyclization reaction is high and the cyclization reaction can proceed well with little or no side reaction (little or no generation of impurities). However, considering reactivity (reaction rate), prevention or suppression of side reactions, and further the filtration rate after the reaction or crystallization, it is preferably 0.5 to 30 parts by mass, more preferably 0.7 to 15 parts by mass, still more preferably 1 to 5 parts by mass, and particularly preferably 1 to 3 parts by mass with respect to 1 part by mass of the phthalonitrile compound as the starting material. By setting it within the above range, the cyclization reaction proceeds efficiently and the yield of the target phthalocyanine compound is improved. Also, the efficiency and productivity in the subsequent steps are further enhanced. In the present invention, the solvent used as the main component in the cyclization reaction is an aprotic polar solvent such as a hydrocarbon solvent or a halogenated hydrocarbon solvent. However, considering the reaction time of the cyclization reaction, suppression or prevention of precipitation of impurities, and improvement of the yield of the target product, the content of the hydrocarbon solvent or the halogenated hydrocarbon solvent is preferably 60.00 to 99.95% by mass, more preferably 80.00 to 99.95% by mass, still more preferably 90.00 to 99.95% by mass, and further preferably 95.00 to 99.95% by mass with respect to 100% by mass of the reaction solvent. All the solvents to be used may be charged at once at the time of charging the raw materials (that is, the compounds necessary for producing the desired phthalocyanine compound), or may be continuously or dividedly added during the reaction as necessary. It is a particularly preferred mode to charge together an aprotic polar solvent such as a hydrocarbon solvent or a halogenated hydrocarbon solvent and a protic polar solvent such as water, and adjust the water content to the above numerical range before the cyclization reaction (before heating). The water content in the reaction solution is the total water content including the moisture contained in the raw materials.

[0021] The method for measuring the water content is measured by the method described in the examples described later. When the equipment used in the examples is difficult to obtain due to obsolete versions, etc., other equipment having equivalent performance can be used. In the production method of the present invention, when it is necessary to oxidize a metal compound, a gas containing oxygen may be introduced into the reaction system. Conversely, when it is preferable that no oxygen is present, an inert gas such as nitrogen may be introduced. Examples of the oxygen-containing gas that can be used in the present invention include pure oxygen, air, an oxygen / nitrogen mixed gas, etc. Further, as the inert gas that can be used, there is no particular limitation as long as it is inert to the cyclization reaction of the present invention, and examples thereof include nitrogen gas, helium gas, argon gas, carbon dioxide gas, etc. In addition, as a method for replacing the inside of the reactor with a gas, there are a method of flowing the gas, or a method of pressurizing the inside of the reactor with a gas and then repeating the process of depressurizing and returning to normal pressure. Appropriately controlling the concentration in the gas phase part inside the reactor can be easily achieved, for example, by measuring using an oxygen concentration meter or the like. An example of the production conditions will be described below. When blowing an inert gas into the reaction vessel, an example is to provide a nitrogen inlet at the upper part of the reaction vessel and blow it in. In that case, an exhaust port should be provided. As the inert gas, nitrogen, which is the most abundant gas in the atmosphere and is extremely inert under normal temperature and pressure and is cheaper compared to noble gases such as argon, is preferable. The introduction amount of the nitrogen, for example, on a laboratory scale (0.1 to 3 liters), it is preferably blown in at a flow rate of 0.1 (ml / min) to 300 (ml / min), and more preferably at a flow rate of 10 (ml / min) to 150 (ml / min). On an industrial production scale (3 liters to 15m 3 ) it is preferably blown in at a flow rate of 0.2 (l / min) to 1500 (l / min), and more preferably at a flow rate of 0.2 (l / min) to 300 (l / min). By the above operation, it is possible to prevent water from entering the reaction vessel from the outside. In addition, when moisture enters the reaction system, from the viewpoint of industrially stable operation management such as corrosion prevention of the reactor and strict control under the cyclization reaction conditions described later, in order to perform safe and stable production, appropriately install a moisture separation tube or the like in the reactor to separate excess moisture outside the reactor and carry out the reaction.

[0022] (metal compound) The metal compound used in the production method of the present invention is not particularly limited as long as it can undergo a cyclization reaction with a phthalonitrile compound to produce the target phthalocyanine compound. However, metals, metal oxides, metal carbonyls, metal halides, metal organic acids, etc. are preferred. 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.

[0023] In addition, the metal compound has a metal corresponding to "M" in the following formula (5) representing the phthalocyanine compound obtained after the reaction. Specifically, metals such as iron, copper, zinc, vanadium, titanium, indium, magnesium, and tin; metal halogen compounds of the metal such as chlorides, bromides, iodides, etc., for example, vanadium trichloride, vanadium chloride, titanium chloride, copper(I) chloride, copper(II) chloride, 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, aluminum iodide, gallium iodide, copper bromide, zinc bromide, cobalt bromide, aluminum bromide, gallium bromide; metal oxides such as vanadium monoxide, vanadium trioxide, vanadium tetroxide, vanadium pentoxide, titanium dioxide, iron monoxide, iron sesquioxide, iron tetroxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt sesquioxide, cobalt dioxide, cuprous oxide, cupric oxide, copper sesquioxide, barium oxide, zinc oxide, germanium monoxide, and germanium dioxide; metal organic acids such as copper acetate, zinc acetate, cobalt acetate, copper benzoate, zinc benzoate; as well as complex compounds such as acetylacetonate and metal carbonyls such as cobalt carbonyl, iron carbonyl, nickel carbonyl, etc.

[0024] Among these, those preferably are metals, metal oxides, and metal halides, more preferably metal halides. From the viewpoint of reactivity, vanadium iodide, copper iodide, and zinc iodide are even more preferable, copper iodide and zinc iodide are particularly preferable, and zinc iodide is most preferable. When zinc iodide is used, the central metal "M" will be zinc. The reason why it is preferable to use iodides among metal halides is that they have excellent solubility in solvents and resins, the spectrum of the obtained phthalocyanine compound is sharp, and it is likely to fall within the desired wavelength range of 640 to 750 nm. Although the detailed mechanism by which the spectrum becomes sharp when iodides are used during the cyclization reaction is unknown, it is presumed that when iodides are used, iodine remaining in the phthalocyanine compound after the reaction causes some interaction with the phthalocyanine compound, so that iodine exists between the layers of the phthalocyanine compound. However, it is not limited to the above mechanism. In order to obtain the same effect as when a metal iodide is used in the cyclization reaction, the obtained phthalocyanine compound may be treated with iodine.

[0025] In the present invention, since the cyclization reaction is characterized by being carried out in the presence of a specific amount of water, except for this point, the cyclization reaction can be carried out in the same manner as conventional known methods such as the method described in JP-A-64-45474. Therefore, the conditions of the cyclization reaction are not particularly limited as long as the reaction proceeds. They may be appropriately designed with reference to the examples section. (Conditions of the cyclization reaction) In the cyclization reaction, for example, the same amount of the solvent contained in the reaction solution as described above can be used. Also, in the cyclization reaction, the metal compound is charged in the range of preferably 1 to 5 moles, more preferably 1 to 3 moles, and even more preferably 1 to 2 moles with respect to 4 moles of the phthalonitrile compound.

[0026] In the cyclization reaction, the reaction temperature is preferably 80 to 250 °C, more preferably 100 to 220 °C, and even more preferably 120 to 200 °C. Before heating, stirring may be performed at room temperature for about 30 minutes to 2 hours. By setting the reaction temperature as described above, the reaction rate is high, side reactions are less likely to occur, and the yield is further improved. In the cyclization reaction, the reaction time is preferably within 72 hours, more preferably within 48 hours, even more preferably within 36 hours, and particularly preferably within 24 hours in consideration of industrial implementation.

[0027] In the present invention, it is a particularly preferred form to carry out the cyclization reaction of the phthalonitrile compound and the metal iodide with the water content in the range of 0.05 to 0.40% by mass based on 100% by mass of the reaction solution. The cyclization rate is improved, and further, the solubility and optical properties of the target phthalocyanine compound are improved. That is, even if the cyclization time is shortened as described above, the target product can be obtained with high purity, so the productivity is very much improved. That is, the volume of the reaction solution in the reactor is preferably 3 liters to 15 m 3 , more preferably 3 liters to 10 m 3 , even more preferably 3 liters to 5 m 3 , 3 liters to 3 m 3 The production method in industrial production is the most preferred form.

[0028] More specifically, according to the present invention, in the cyclization reaction, the reaction time is preferably within 72 hours, more preferably within 48 hours, even more preferably within 36 hours, and particularly preferably within 24 hours, and the raw material conversion rate is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more. Also, according to the present invention, the yield of the finally obtained target product is also significantly high, and a yield of 70% or more, more preferably 75% or more, and even more preferably 80% or more can be obtained. An example of the production conditions during the cyclization reaction is shown below.

[0029] The shape of the reaction vessel to be used is not particularly limited, and examples include polygonal, cylindrical, etc. However, from the viewpoints of stirring effect, handleability, versatility, etc., a cylindrical shape is preferred. Also, a baffle plate may or may not be provided, but by providing a baffle plate, the uniformity of the reaction solution can be enhanced. The stirrer is composed of a power source such as an electric motor, a rotating shaft, a stirrer, etc., and the shape of its stirring blade is not limited. Examples of the stirrer include a disk turbine, a fan turbine, a curved fan turbine, a pitched blade turbine, a multi-stage fan turbine, a Faudler blade, a Blumargin type, an angled blade, a propeller type, a multi-stage blade, an anchor type, a gate type, a double ribbon blade, a screw blade, a Max blend blade, etc. The stirring power (industrial production scale) during the cyclization reaction is preferably 0.1~4.0 kW / m 3 , more preferably 0.1~3.0 kW / m 3 , still more preferably 0.2~2.0 kW / m 3 . That is, if the stirring power is less than 0.1 kW / m 3 , the uniformity of the reaction solution may decrease. On the other hand, if the stirring power exceeds 4.0 kW / m 3 , the reaction solution may splash onto the inner wall surface of the reaction vessel. In addition, regarding the pressure inside the container during the reaction, there is no need to control pressurization or depressurization. Usually, it can be carried out at normal pressure as long as no special operation is performed or no special raw material is used.

[0030] The material inside the reaction vessel is not particularly limited. For example, those made of stainless steel, preferably SUS such as SUS304, SUS316, SUS316L, etc. are preferred from the viewpoint of corrosion resistance. Also, it is desirable to perform glass lining processing or the like inside the reaction vessel to make it inert to the reaction raw materials and reaction products. The volume of the finally obtained reaction solution is preferably controlled to 10~80% by volume of the volume of the reaction vessel, and more preferably controlled to 20~70% by volume. After the above cyclization reaction, if necessary, filtration, crystallization, washing, and drying can be carried out to obtain the product efficiently and with high purity. The above filtration, crystallization, filtration, washing, and drying steps are not particularly limited, and the same steps as those used in various conventional methods for synthesizing phthalocyanine compounds can be used. According to the above steps, the content of impurities that can cause a decrease in the purity of the phthalocyanine compound or interfere with the transmission of visible light in the product is small.

[0031] Hereinafter, preferred embodiments of the production method of the present invention will be described. That is, the following formula (1):

[0032]

Chemical formula

[0033]

Chemical formula

[0034]

Chemical formula

[0035]

Chemical formula

[0036]

Chemical formula

[0037] In the above formulas (1) to (5), Z1 to Z 16It is defined by the structure of the desired phthalocyanine compound. Also, depending on the structure of the target phthalocyanine compound, the number of phthalonitrile compounds may be 1 to 3 types. For example, Z1 to Z4 (structural unit A), Z5 to Z8 (structural unit B), Z9 to Z 12 (structural unit C) and Z 13 ~Z 16 (structural unit D) are the same, the number of phthalonitrile compounds used as raw materials is one type.

[0038] Also, in the above formulas (1) to (5), Z1 to Z 16 are each independently hydrogen, a halogen atom (fluorine, chlorine, bromine, iodine), -SR 1 , -OR 2 and can be. Also, M is a metal, a metal oxide or a metal halide. As described above, the method of the present invention is characterized in that the cyclization reaction is carried out with the water content in the range of 0.05 to 0.40% by mass with respect to 100% by mass of the reaction solution. The phthalonitrile compound and the metal compound as raw materials, and the structure of the phthalocyanine compound to be produced are not particularly limited, and are appropriately selected according to the desired light absorption wavelength, transmittance at the maximum absorption wavelength, transmittance in the visible light region, solubility in a solvent, and required durability. Therefore, for the components other than the above-described characteristic components, the same methods as in the prior art can be applied. For example, refer to the methods described in JP-A-2001-106689, Japanese Patent No. 3721298, JP-A-2004-018561, and JP-A-2002-114790, or in combination, they are applicable.

[0039] The production method of the present invention is characterized by the water content in the reaction solution. Generally, in the cyclization reaction of a phthalonitrile compound, the process proceeds through the coordination of a metal to a cyano group and the formation of a C-N bond between another cyano group in the molecule and a cyano group of another molecule. The substituents Z1 to Z 16 are not directly involved in the reaction. That is, the substituents Z1 to Z 16 are not particularly limited and can be applied to a wide range of phthalocyanine compounds. As described above, in the production on an industrial scale, metal halides are preferred for the above metal compounds, and metal iodides selected from vanadium iodide, copper iodide, and zinc iodide are particularly preferred. In that case, M becomes a metal selected from vanadium, copper, and zinc.

[0040] According to the present invention, by subjecting the phthalonitrile compounds represented by the above formulas (1) to (4), which are starting materials, to a cyclization reaction with a metal compound under specific conditions, the corresponding phthalocyanine compounds can be produced in a short time and in high yield. Depending on the structure of the target phthalocyanine compound, different reactions may be further carried out after the cyclization reaction of the present invention. For example, when the finally targeted phthalocyanine compound has -SR 1 , -OR 2 etc. as substituents, a method of subjecting the phthalocyanine compound synthesized by the cyclization reaction of the present invention to a substitution reaction with a sulfur compound or an alcohol compound can be preferably used. At that time, the phthalocyanine compound formed at the stage when the cyclization reaction is completed may be isolated and purified and then used in the next step, or the reaction solution may be directly used in the next step without isolation and purification. In the present invention, there is no particular limitation on the reaction method of this subsequent step, and conventionally known methods can be used.

[0041] As described above, the method of the present invention is characterized in that a specific amount of water is present during the "cyclization reaction". For example, once cyclized (that is, after obtaining the phthalocyanine compound (5)), there is no limitation on the water content, and other solvents (for example, at least one solvent selected from the group consisting of hydrocarbon solvents, halogenated hydrocarbon solvents, nitrile solvents, and protic polar solvents other than water) may be added to produce the desired phthalocyanine compound. The step after cyclization is also referred to as the subsequent step.

[0042] In addition, there are no particular restrictions on the substituents introduced by the reaction in the subsequent process, and they can be selected according to the desired physical properties and structure. There are also no particular restrictions on the compounds used in the reaction. For example, when a phthalocyanine compound having a substituted amino group is targeted, the phthalocyanine compound obtained by the cyclization reaction of the present invention can be reacted with aromatic amines such as aniline and benzylamine, or aliphatic amines such as n-butylamine, n-hexylamine, and 2-ethylhexylamine. According to the method for producing the phthalocyanine compound of the present invention, the target phthalocyanine compound can be produced in a yield (isolated yield) of 70% or more, or 80% or more, based on the starting phthalonitrile compound. Also, the above R 1 and R 2 each independently represent 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. In the present specification, examples of the substituent in the case of "which may have a substituent" include, but are not limited to, 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, an amino group, an alkylamino group, an alkylcarbonylamino group, an arylamino group, an arylcarbonylamino group, a carbonyl group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkoxysulfonyl group, an alkylthio group, a carbamoyl group, an aryloxycarbonyl group, an oxyalkyl ether group, a cyano group, etc. The types of these substituents may be the same or different even when a plurality of substituents are present.

[0043] The aralkyl group refers to a group in which a hydrogen atom of an alkyl group is substituted with an aryl group, and there are no particular restrictions on such an aryl group, and examples include a phenyl group, a benzyl group, a phenethyl group, an o-, m- or p-tolyl group, a 2,3- or 2,4-xylyl group, a mesityl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenylyl group, a benzhydryl group, a trityl group, a pyrenyl group, etc.

[0044] In addition, the alkyl group having 1 to 20 carbon atoms is, without particular limitation, a linear, branched or cyclic alkyl group having 1 to 20 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, etc. may be mentioned.

[0045] Next, a preferred form of the phthalocyanine compound having good solubility and optical properties will be described. Regarding the above optical properties, for example, as the near-infrared absorbing dye, when measuring the absorption spectrum of a solution of the phthalocyanine compound dissolved in a solvent, a phthalocyanine compound (referred to as dye α) showing an absorption maximum in the wavelength range of 640 to 750 nm is preferable. More preferably, the dye α is a compound represented by the following general formula (5).

[0046] [Chemical formula] In the formula, M represents a metal atom (preferably vanadium, copper, zinc), a metal oxide or a metal halide. Among these, the atoms at the α-position (Z 1 , Z 4 , Z 5 , Z 8 , Z 9 , Z 12 , Z 13 , Z 16 ), and the atoms at the β-position (Z 2 , Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 14 , Z 15is a substituent represented by the following formula (ii-a), (ii-b) or (ii-c), or may be substituted with a halogen atom or the like, or may be a hydrogen atom.

[0047]

Chemical formula

[0048] Here, in order to show an absorption maximum in the wavelength range of 700 to 750 nm, it is preferable that the atom at the α-position is substituted. When the substituent is (ii-a), R 3 , R 5It is preferable that at least one of them is bonded to the ortho - or meta - position, and more preferably bonded to the ortho - position. When the substituent is (ii - c), Z 1 ~Z 16 Among the 16 atoms of, the number of atoms substituted with (ii - c) is preferably 4 to 16, more preferably 8 to 16, and still more preferably 12 to 16. The atom at the β - position may or may not be substituted (remaining as a hydrogen atom), but from the viewpoint of solubility, it is preferably substituted with a substituent represented by (ii - a), (ii - b) or (ii - c), or a halogen atom, etc., and from the viewpoint of suppressing the degree of aggregation by disrupting the planarity of the molecule, a substituent represented by (ii - c) or a halogen atom is more preferable. As described above, since the dye α is less likely to form an aggregate, when measuring the absorption spectrum of a solution containing the dye α, it is likely to show an absorption maximum in the wavelength range of 700 to 750 nm. Subsequently, in order to show an absorption maximum in the wavelength range of 640 to 700 nm, the atom at the β - position is preferably substituted. When the substituent is (ii - a), R 3 、R 5 It is preferable that at least one of them is bonded to the para - position. When the substituent is (ii - b), Z 1 ~Z 16 Among the 16 atoms of, the number of atoms substituted with (ii - b) is preferably 4 to 10, more preferably 4 to 9, and still more preferably 4 to 8. The atom at the α - position may or may not be substituted (remaining as a hydrogen atom), but in order to have a sharp absorption peak with a reduced shoulder peak when added to a resin or the like, the atom at the α - position is preferably a hydrogen atom or substituted with a halogen atom. As described above, the dye α is likely to form an aggregate, and when producing a solution or a resin composition containing the dye α, it is likely to show an absorption maximum in the wavelength range of 640 to 700 nm.

[0049] Hereinafter, a particularly preferred form of the phthalocyanine compound that can be used for optical filter applications and its production method will be described.

[0050] The above phthalocyanine compound has the following general formula (IV):

[0051]

Chemical formula

[0052] Examples of the substituent which the above OR 8 group may have include, for example, an electron-withdrawing group such as an alkoxycarbonyl group (-COOR 9 ), a halogen group (halogen atom), a cyano group (-CN), a nitro group (-NO2); an electron-donating group such as an alkyl group (-R 10 ), an alkoxy group (-OR 11 ); etc., and one or more of these may be included. Among these, from the viewpoint of becoming more excellent in light selective transmittance due to being likely to form an associative molecular structure, an electron-withdrawing group is preferable. As the electron-withdrawing group, an alkoxycarbonyl group, a chloro group (chlorine atom) or a cyano group is preferable, and more preferably, a methoxycarbonyl group, a methoxyethoxycarbonyl group, a chloro group or a cyano group. Note that R 9 constituting the alkoxycarbonyl group (-COOR 9 ) is preferably an alkyl group or an alkoxy group having 1 to 8 carbon atoms, and R 10 constituting the alkyl group (-R 10 ) is preferably an alkyl group having 1 to 8 carbon atoms. As the alkoxycarbonyl group, a methoxycarbonyl group or a methoxyethoxycarbonyl group is preferable, and as the alkyl group, a methyl group or a dimethyl group is preferable.

[0053] The above OR 8When the group has substituents, the number of the substituents is not particularly limited, but for example, it is preferably 1 to 4, more preferably 1 or 2. In addition, one OR 8 When the group has two or more substituents, the substituents may be the same or different. Also, the position of the substituent in the OR 8 group is not particularly limited.

[0054] The above X 1 and Y 1 Among them, at least one of X 2 and Y 2 Among them, at least one of X 3 and Y 3 Among them, at least one of X 4 and Y 4 Among them, at least one represents an OR 8 group which may have a substituent. Preferably, it is a phenoxy group which may have a substituent (that is, a phenoxy group or a phenoxy group having a substituent). More preferably, all of X 1 ~X 4 and Y 1 ~Y 4 represent a phenoxy group which may have a substituent. Among them, a phenoxy group having a substituent is preferred, and as the substituent, an electron-withdrawing group is preferred as described above.

[0055] In the above general formula (IV), M represents a metal atom, a metal oxide, or a metal halide. The metal atom and the metal atom constituting the metal oxide or metal halide are the same as the description of M above. Since they are more excellent in solubility or dispersibility in a solvent and a resin component, visible light transmittance, and light resistance, those having any one of copper, vanadium, and zinc as a central metal are preferable. More preferably, it is copper or zinc. The phthalocyanine compound having copper as a central metal has excellent light resistance and does not deteriorate by light regardless of the resin component (binder resin) in which it is dispersed. The phthalocyanine complex (phthalocyanine compound) having zinc as a central metal is suitable because it has excellent solubility in a solvent and a resin component and it is easy to obtain a laminate having higher light selective transmittance.

[0056] The halogen atom constituting the above metal halide is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0057] The compound represented by the above general formula (IV) can be synthesized, for example, by using an ordinary method described in Japanese Patent Publication No. 6-31239. Specifically, one selected from the group consisting of a metal, a metal oxide, a metal carbonyl, a metal halide, and a metal organic acid (collectively also referred to as a "metal compound") and the following general formula (II):

[0058]

Chemical formula

[0059] The metal compound is not particularly limited as long as it reacts with the phthalonitrile derivative to give a compound represented by the general formula (IV). For example, metals such as iron, copper, zinc, vanadium, titanium, indium, and tin; metal halide compounds of the metal such as chlorides, bromides, and iodides; metal oxides of the metal such as vanadium oxide, titanyl oxide, and copper oxide; metal organic acids of the metal such as acetates; complex compounds of the metal such as acetylacetonate and metal carbonyls such as carbonyl iron; and the like can be mentioned. As described above, among the above metal compounds, more preferably a metal halide, Still more preferably, vanadium iodide, copper iodide, and zinc iodide, and particularly preferably zinc iodide. When zinc iodide is used, the central metal in the general formula (IV) is zinc.

[0060] When the reaction between the above metal compound and the phthalonitrile derivative (phthalonitrile compound) represented by the above general formula (II) is carried out in an organic solvent, examples of the organic solvent used as the main component include inert solvents such as benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, benzonitrile, etc.; aprotic polar solvents such as pyridine, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N,N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethyl sulfoxide, dimethyl sulfone, sulfolane, etc.; one or more of these can be used. Among them, it is preferable to use 1-chloronaphthalene, N-methyl-2-pyrrolidone, 1-methylnaphthalene, trimethylbenzene, benzonitrile, nitrobenzene, ethylene glycol. More preferably, they are trimethylbenzene and benzonitrile. And specific amounts of water which is a characteristic of the present invention, and alcohols, amines and phenols which are protic polar solvents other than water if necessary, are mentioned. Other protic polar solvents such as alcohols, amines and phenols are preferably in a form further containing them within a range not impairing the effects of the present invention, but the form using only water as the protic polar solvent is most preferable. The water content is used in the range of 0.05 to 0.40% by mass based on 100% by mass of the reaction solution. Regarding the content of only water, more preferably, it is 0.10 to 0.40% by mass, particularly preferably 0.15 to 0.30% by mass. When the water content is within the above numerical range, the cyclization reaction proceeds rapidly and the optical properties of the phthalocyanine obtained after the cyclization reaction become good. It is preferable that the total amount of the solvent used in the above cyclization reaction is such that the concentration of the phthalonitrile compound represented by the above general formula (II) is 1 to 50% by mass. More preferably, it is an amount such that the concentration is 10 to 40% by mass, particularly preferably 20 to 40% by mass. In addition, it is preferable to adjust the water content to the range of 0.06 to 0.45% by mass based on 100% by mass of the total amount of the solvent not containing the solute.

[0061] Regarding the above cyclization reaction, the reaction temperature is not necessarily constant depending on the type of raw material, the type of solvent, and other conditions, but is usually preferably set to 100 to 300 °C. More preferably, it is 120 °C or higher, and even more preferably, it is 130 °C or higher. Also, more preferably, it is 260 °C or lower, even more preferably, it is 240 °C or lower, and particularly preferably, it is 200 °C or lower. Further, the temperature may be increased stepwise to control the exothermic reaction. The reaction time is not particularly limited either, but is usually preferably within 72 hours, more preferably within 48 hours, even more preferably within 36 hours, and particularly preferably within 24 hours. By the production method of the present invention, the cyclization reaction time is significantly shortened as described above. The phthalocyanine compound obtained by the production method of the present invention preferably exhibits an absorption maximum in the wavelength range of 640 to 750 nm when measuring the absorption spectrum of the solution containing the phthalocyanine compound. Also, the transmittance at a wavelength of 430 nm is preferably 80% or more. More preferably, it is 83% or more, even more preferably, it is 85% or more, and most preferably, it is 87% or more. Further, the transmittance at the absorption maximum wavelength existing in the wavelength range of 640 to 750 nm is preferably 60% or less. More preferably, it is 50% or less, even more preferably, it is 40% or less, and even more preferably, it is 30% or less. By satisfying these numerical values, the optical properties become good and it can be suitably used for optical filter applications. In the production method of the phthalocyanine compound of the present invention, as described above, by having the step of a specific cyclization reaction, the reaction time can be shortened and a phthalocyanine compound having excellent optical properties can be obtained. To further enhance the optical properties, the post-treatment steps after the cyclization reaction will be described.

[0062] The conditions for the substituents introduced in the reaction in the post-treatment steps are, for example, when aiming for a phthalocyanine compound having a substituted amino group, the phthalocyanine compound obtained by the cyclization reaction of the present invention can be reacted with aromatic amines such as aniline and benzylamine, and aliphatic amines such as n-butylamine, n-hexylamine, and 2-ethylhexylamine (hereinafter also referred to as "amino compounds").

[0063] The amount of the amino compound used is appropriately selected according to the structure of the target phthalocyanine compound, and is not particularly limited as long as these reactions proceed to produce the desired phthalonitrile compound. However, it is usually 1 to 50 moles, preferably 2 to 40 moles, more preferably 3 to 20 moles, per 1 mole of the starting phthalonitrile compound.

[0064] The substitution reaction conditions using the amino compound are not particularly limited as long as an appropriate optimal range is selected so that the desired substituent can be introduced as designed. For example, if necessary, the substitution reaction can be carried out by mixing in the presence of an inert liquid that is non-reactive with the compounds used in the reaction and heating to a certain temperature.

[0065] Preferably, it is carried out by heating to a certain temperature in the amino compound to be reacted.

[0066] Examples of the inert liquid include nitriles such as benzonitrile and acetonitrile, amides such as N-methylpyrrolidone or dimethylformamide, or halogenated hydrocarbons such as o-chlorotoluene, which can be used alone or in the form of a mixture of two or more. Also, the amino compound can itself be used as a solvent to carry out the substitution reaction.

[0067] Also, the reaction temperature and time of the substitution reaction are not particularly limited as long as the substitution reaction can proceed sufficiently. However, the reaction temperature is preferably 40 to 250 °C, more preferably 50 to 200 °C, still more preferably 60 to 180 °C, particularly preferably 60 to 150 °C, and most preferably 60 to 120 °C. Also, the reaction time is preferably within 72 hours, more preferably within 48 hours, still more preferably within 36 hours, particularly preferably within 24 hours, and most preferably within 12 hours.

[0068] After the reaction, according to the conventional known synthetic method by the substitution reaction of phthalocyanine compounds By filtering out inorganic components and distilling off (washing) the amino compound, the target phthalocyanine compound can be efficiently obtained with high purity without going through complicated manufacturing processes. In addition, the optical filter containing the phthalocyanine compound obtained by the production method of the present invention is excellent in light selective transmittance as described above. Therefore, the phthalocyanine compound produced by the production method of the present invention is particularly useful for near-infrared absorption filters such as for infrared cut filters for imaging devices such as mobile phone cameras, digital cameras, in-vehicle cameras, video cameras, surveillance cameras, display elements (LEDs, etc.). Moreover, the phthalocyanine compound obtained by the production method of the present invention is excellent in solubility in organic solvents. Therefore, among optical filters, it is particularly useful as a green coloring dye used for coloring patterns of color filters.

[0069] [Preferred Applications] According to the production method of the present invention, since the decrease in reaction rate can be suppressed even on an industrial production scale, it can be suitably used in the field of production of phthalocyanine compounds for various applications. For example, as coloring applications, in the printing ink field such as lithographic ink, gravure ink, flexo ink, etc.; in the paint field such as lacquer, baking paint, etc.; in the field of coloring molded products such as polyolefins and thermoplastic polyesters; it can be suitably used in various applications in high-tech fields such as jet ink, color filters, electrophotographic powder toners, etc. In particular, as a display material or recording material, it can be suitably used for sublimation transfer dyes, inkjet inks, color separation filters used in image pickup tubes, color filters for liquid crystal displays, optical color filters, color toners, inks for anti-counterfeiting barcodes, dichroic dyes for guest-host type liquid crystal displays, dichroic dyes for polarizing plates, etc. In addition, the phthalocyanine compound obtained by the production method of the present invention is a compound with high solubility and broad absorption in the near-infrared region, and is useful as a near-infrared absorber, and can also be suitably used in fields such as display elements, imaging elements, photothermal conversion materials, heat shielding materials (especially heat ray absorption materials). In addition, a heat ray shielding material for the purpose of shielding heat rays, a heat ray absorbing laminated glass for automobiles, a heat ray shielding film or a heat ray shielding resin glass, a heat ray shielding filter, particularly preferably an optical filter for imaging devices such as cameras for mobile phones, digital cameras, in-vehicle cameras, video cameras, surveillance cameras, display elements (such as LEDs), filters for various displays, filters for plasma displays, image sensors, illuminance sensors, proximity sensors, near-infrared absorbers for non-contact fixing toners such as flash fixing, near-infrared absorbers for heat retaining and heat storage fibers, infrared absorbers for fibers having a camouflage performance (camouflage performance) against detection by infrared rays, optical recording media using semiconductor lasers, filters for liquid crystal displays, filters for organic EL displays, near-infrared absorbing dyes for writing or reading in optical character readers, near-infrared photosensitizers, photothermal exchange agents such as thermal transfer and thermal stencil, photothermal exchange agents for laser fusion for thermally fusing resins using laser beams, near-infrared absorbing filters, microbial inactivators, eye fatigue preventives, photoconductive materials, etc., and furthermore photosensitive dyes for tumor treatment having absorption in the long wavelength region with good tissue permeability, positioning marking agents for photos and films, and dyes for sorting during plastic recycling, and preheating aids during the molding process of PET bottles, etc. can be mentioned.

Examples

[0070] Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples do not limit the present invention, and all modifications carried out without departing from the spirit of the present invention are included in the technical scope of the present invention. The present invention will be specifically shown by way of examples, comparative examples, and property evaluations. In the examples and comparative examples, unless otherwise specified, % means mass% and parts mean parts by mass. In the following synthesis examples, etc., various analyses were carried out as follows. <Analysis of reaction progress> The progress of the cyclization reaction was analyzed using Hitachi's high-performance liquid chromatograph Chromaster. The column used was Inertsil ODS-3 manufactured by GL Sciences. Analysis was carried out at a column temperature of 40 °C, a UV measurement wavelength of 254 nm, with the developing solution having a composition of 70% acetonitrile - 30% (by volume) aqueous phosphoric acid solution (0.1%) and flowing at a flow rate of 0.5 mL / min.

[0071] The conversion rate of the phthalonitrile compound as the main raw material was calculated based on the ratio of the peak area of the phthalonitrile compound to the peak area of the main solvent (a mixed solvent of a protic polar solvent and a nitrile-based solvent). The selectivity (%) of the reaction was calculated using the following formula ((Raw material conversion rate (%) - Yield of by-products (%)) / Raw material conversion rate (%) × 100 (formula) The yield of by-products was calculated based on the ratio of the sum of the areas of all new peaks (considering the newly emerged peaks during the reaction as the peaks of by-products) to the peak area of the main solvent.

[0072] As described above, the calculation of the yield and selectivity of by-products is a value calculated from a simple area ratio, but it serves as an indicator for judging whether side reactions proceed less during the cyclization reaction. <Measurement of water content> The water content in the reaction solution was measured according to the following method. The reaction solution in the reaction vessel was sampled, and 1.0 g of the sampled solution was measured using a Karl Fischer moisture meter (manufactured by Kyoto Electronics Industry Co., Ltd.) to measure the water content in the reaction solution. <Synthesis Example 1> (Synthesis of phthalocyanine (1)) (1) Step 1 Into a 2000 ml four-neck separable flask, 108 g (0.54 mol) of tetrafluorophthalonitrile, 69.0 g (1.18 mol) of potassium fluoride, and 252 g of acetone were charged. Further, 254 g (1.1 mol) of 3-chloro-4-hydroxybenzoic acid methoxyethyl ester and 432 g of acetone were charged into a dropping funnel. While stirring the reaction vessel under ice cooling, the 3-chloro-4-hydroxybenzoic acid methoxyethyl ester solution was dropped from the dropping funnel over about 2 hours, and then stirring was continued for another 2 hours. Thereafter, while slowly raising the reaction temperature to room temperature, stirring was carried out overnight. The reaction solution was filtered, and acetone was distilled off from the filtrate using a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered, and intermediate (1) was obtained as 217.4 g (yield 64.8%) by vacuum drying. The reaction of this step 1 is briefly shown below.

[0073] [Chemical formula] (2) Step 2 Into a 500 ml flat-bottom flask, 150.0 g (0.2414 mol) of the intermediate (1) obtained in step 1, 19.26 g (0.0603 mol) of zinc(II) iodide, 225.0 g of benzonitrile, and water were charged so as to have the moisture content of the following examples. The liquid depth of the reaction solution was about 8 cm. Thereafter, while flowing nitrogen (10 ml / min), using a flat stirring blade (vertical 2 cm * horizontal 4 cm * width 2 mm), stirring was carried out at a rotation speed of 200 rpm, and the oil bath in which the above flask was immersed was heated so that the internal temperature of the reaction solution became 160 °C, and a phthalocyanation reaction was carried out at the same temperature. The conversion rate of phthalocyanation was calculated by tracking the residual rate of the intermediate (1) as a raw material by HPLC. After completion of the reaction, 470 g of methyl cellosolve was added to the reaction solution, and then dropped into a mixed solution of 3.8 kg of methanol and 0.6 kg of water to precipitate crystals, and a wet cake was obtained after suction filtration. The obtained cake was stirred and washed again with a mixed solution of 1.9 kg of methanol and 0.3 kg of water, and suction filtered. The obtained cake was dried at 90 °C for 24 hours using a vacuum dryer to obtain 137.0 g (yield 89.1%) of the target phthalocyanine (1). The reaction in Step 2 is briefly shown below.

[0074]

Chemical formula

[0075]

Table 1

[0076]

Table 2

Industrial Applicability

[0077] According to the production method of the present invention, since a decrease in the reaction rate can be suppressed even on an industrial production scale, it can be suitably used in the production field of phthalocyanine compounds for various applications. For example, it can be used as a colorant or a near-infrared absorber in the optical field.

Claims

1. A method for producing a phthalocyanine compound having a step of subjecting a phthalonitrile compound to a cyclization reaction with a metal compound selected from copper iodide and zinc iodide in a reaction solution, wherein the phthalocyanine compound has the following formula (IV): 【Chemical 1】 (In the formula, M represents copper or zinc. X1 to X4 and Y1 to Y4 are the same or different and each represents a hydrogen atom (H), a fluorine atom (F), or an OR8 group which may have a substituent. The OR8 group represents a phenoxy group or a naphthoxy group. However, at least one of X1 and Y1, at least one of X2 and Y2, at least one of X3 and Y3, and at least one of X4 and Y4 each represents a phenoxy group which may have a substituent.) The phthalocyanine compound is represented by The solvent contained in the reaction solution includes at least one organic solvent selected from a hydrocarbon solvent, a halogenated hydrocarbon solvent, and benzonitrile, and a protic polar solvent, The protic polar solvent is only water, A method for producing a phthalocyanine compound, characterized in that the cyclization reaction is carried out with the water content in the range of 0.05 to 0.40% by mass based on 100% by mass of the reaction solution.

2. The method for producing a phthalocyanine compound according to claim 1, characterized in that the solvent contained in the reaction solution consists of at least one organic solvent selected from a hydrocarbon solvent, a halogenated hydrocarbon solvent, and benzonitrile, and only water.

3. The phthalonitrile compound has the following formula (II): [Chemical Formula 2] (In the formula, Xa and Ya are the same or different and each represents a hydrogen atom (H), a fluorine atom (F), or an OR8 group which may have a substituent. The OR8 group represents a phenoxy group or a naphthoxy group. However, at least one of Xa and Ya represents a phenoxy group which may have a substituent.) The method for producing a phthalocyanine compound according to claim 1 or 2, characterized in that it is a phthalonitrile derivative represented by

4. The method for producing a phthalocyanine compound according to any one of claims 1 to 3, characterized in that the phenoxy group which may have a substituent is a phenoxy group having one or more selected from an alkoxycarbonyl group, a halogen atom, a cyano group, a nitro group, an alkyl group, and an alkoxy group.

5. The method for producing a phthalocyanine compound according to any one of claims 1 to 4, characterized in that the metal compound is charged in an amount in the range of 1 to 5 moles with respect to 4 moles of the phthalonitrile compound, and a cyclization reaction is carried out at a reaction temperature of 100 to 300 °C.

6. The method for producing a phthalocyanine compound according to any one of claims 1 to 5, characterized in that the phthalocyanine compound is a phthalocyanine compound showing a maximum absorption in the wavelength range of 640 to 750 nm.

7. The method for producing a phthalocyanine compound according to any one of claims 1 to 6, characterized in that the phthalocyanine compound has a transmittance of 87% or more at a wavelength of 430 nm.

8. The method for producing a phthalocyanine compound according to any one of claims 1 to 7, characterized in that the boiling point of the hydrocarbon solvent or the halogenated hydrocarbon solvent is 140 to 200 °C.

9. The volume of the reaction solution is 3 liters to 15 m ３ The method for producing a phthalocyanine compound according to any one of claims 1 to 8, characterized in that it is as described above.

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