JP4658084B2 - Method for producing phthalocyanine compound - Google Patents

Description

  The present invention relates to a novel method for producing a phthalocyanine compound. In particular, the present invention relates to a method capable of producing a phthalocyanine compound with few impurities. The present invention also relates to a method having good filterability after the reaction.

  The phthalocyanine compound obtained by the production method of the present invention has a high absorption coefficient in the near infrared region, and exhibits a high transmittance in the visible region of 400 to 610 nm, particularly in the vicinity of 400 to 460 nm. It is useful for near-infrared absorption filters such as for PDP).

  The need for near-infrared absorbing dyes is increasing as the field of use expands, and near-infrared for writing or reading in optical recording media, liquid crystal display devices, optical character readers, etc. using semiconductor lasers. Nearly used as absorption dyes, near-infrared sensitizers, thermal transfer, photothermal conversion agents such as thermal paper and thermal stencil, near-infrared absorption filters for plasma display (PDP), eye strain prevention agents, photoconductive materials, etc. Infrared absorbing materials or color separation filters used for image pickup tubes, color filters for liquid crystal displays, color cathode ray tube selective absorption filters, color toners, flash fixing toner dyes, inkjet inks, barcode inks for preventing falsification, and microorganisms Deactivators, photosensitive dyes for tumor treatment, heat ray shielding agents for automobiles or building materials, In addition, for near-infrared absorbing dyes used as resin classifiers, materials that satisfy all characteristics such as light resistance, heat resistance, solubility (or compatibility with resins), and methods for producing the same have been studied. I came. As those having the above properties, phthalocyanine compounds are attracting attention from the viewpoints of chemical and physical stability, fastness of pigments using such compounds, and deep colorability.

  Moreover, as a method for producing the phthalocyanine compound, for example, Patent Documents 1 and 2 are known.

  In Patent Document 1, tetrafluorophthalonitrile and vanadium trioxide are reacted at 150 ° C. in the presence of p-toluenesulfonic acid and calcium carbonate in a benzonitrile solvent. In this publication, as the organic solvent used in the reaction, an inert solvent that is not reactive with the starting materials and the reactor is recommended, and in order to prevent corrosion of the reactor, a metal oxide and It reacts at relatively low temperatures using paratoluenesulfonic acid.

Patent Document 2 discloses that when a phthalocyanine compound is produced by cyclizing a phthalonitrile compound alone or with a metal compound, the cyclization reaction is performed using an organic compound having a specific amount of hydroxyl group and / or carboxyl group. A method for producing a phthalocyanine compound is disclosed, which is carried out while introducing an inert gas. According to the method, it is described that a phthalocyanine compound can be produced industrially and inexpensively by a safer and preferable method without using an oxygen-containing gas having an explosion risk as an oxygen source (paragraph “ 0009 "). 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.
JP 2000-169743 A JP 2005-298491 A

  However, in the reaction described in Patent Document 1, since a metal oxide is used as a raw material, there is a problem that the reactivity and the performance of the obtained phthalocyanine compound are not stabilized due to fluctuations in physical properties such as the surface area of the raw material. Further, as a result of various studies by the present inventors, it has been found that there are the following problems in addition to the above problems. That is, in this method, in order to prevent impurities such as metal oxide from remaining in the target product, it is necessary to perform filtration after the reaction to remove insoluble impurities, but the filter is clogged, It became clear that the filtration time is very long or the filtration becomes difficult.

  In addition, the reaction described in Patent Document 2 is mainly aimed at improving the yield, and the improvement of the yield is achieved by using a metal compound in which an organic compound containing a hydroxyl group and / or a carboxyl group is a central metal source. It is achieved by promoting the cyclization reaction between the halogen-containing phthalonitrile compound and the metal compound by the preferential reaction to form a complex of the metal compound and the organic compound and the presence of this complex. (Paragraph “0035”). For this reason, no consideration is given to the purification of the phthalocyanine compound, which is the final product, and depending on the choice of the solvent, unreacted metal compounds and the like are present in the reaction solution as impurities, particularly during mass production, as in Patent Document 1. When it is attempted to filter in order to remove impurities, the filter may be clogged by the impurities, resulting in a problem that it takes a very long time for filtration or it becomes difficult to filter. In addition to the above problem, when used in the method of Patent Document 2, it is generally difficult to completely remove a compound having a hydroxyl group or a carboxyl group having a high boiling point from the target product in the purification step. is there. In addition, there is a problem that an undesirable side reaction occurs with a phthalonitrile compound having a functional group.

  Accordingly, the present invention has been made in view of the above-described problems, and provides a method for producing a phthalocyanine compound that can cause filtration after reaction with less precipitation of impurities even during mass production. It is intended.

  Another object of the present invention is to provide a method for producing a phthalocyanine compound that exhibits a high absorption coefficient in the near infrared region and a high transmittance in the visible region near 400 to 610 nm, particularly 400 to 460 nm.

  As a result of intensive studies to achieve the above object, the inventors of the present invention, in the method for producing a phthalocyanine compound, when the phthalonitrile compound is cyclized by itself or with a metal compound, the cyclization reaction is carried out by carbonization. By performing in a mixed solvent of hydrogen solvent and nitrile solvent, precipitation of impurities such as unreacted metal compounds during the production process of phthalocyanine compounds is significantly suppressed even during mass production of 20 liters or more. Since it can be prevented, it has been found that impurities can be filtered quickly without clogging the filter even if filtered after the reaction. In addition, the present inventors have found that the phthalocyanine compound thus obtained has a low impurity content, and thus has a high absorption coefficient in the near infrared region, and in the visible region of 400 to 610 nm, particularly 400 to 460 nm. Since it can show a high transmittance, it has been found that it is particularly useful for near-infrared absorption filters for plasma display panels (PDP). Based on the above findings, the present invention has been completed.

  That is, an object of the present invention is a method for producing a phthalocyanine compound by cyclizing a phthalonitrile compound alone or with a metal compound, and the cyclization reaction is a hydrocarbon which may be halogenated. This is achieved by a method for producing a phthalocyanine compound, which is performed in a mixed solvent of a system solvent and a nitrile solvent.

  In the method of the present invention, when a phthalonitrile compound is cyclized by itself or with a metal compound, the cyclization reaction is carried out in a mixed solvent of a hydrocarbon solvent and a nitrile solvent that may be halogenated. By carrying out, the content of impurities precipitated during the production process of the desired phthalocyanine compound can be significantly suppressed. For this reason, according to the method of the present invention, filter clogging is unlikely to occur, particularly during filtration after reaction in mass production, and smooth filtration is possible.

  Further, as described above, the phthalocyanine compound produced by the method of the present invention has a high absorption coefficient in the near-infrared region because of a low content of impurities, and a visible region in the vicinity of 400 to 610 nm, particularly 400 to 460 nm. Can show a high transmittance. For this reason, the phthalocyanine compound produced by the method of the present invention is particularly useful for near-infrared absorption filters for plasma display panels (PDP).

  Furthermore, in the method of the present invention, since a poorly reactive solvent is used as a reaction solvent, side reactions are unlikely to occur, and the desired phthalocyanine compound can be obtained with a high yield. Furthermore, by selecting an optimum composition of the mixed solvent, it becomes easy to control the solubility of the target product at the time of crystallization, and to easily remove the solvent from the target product by drying.

  The present invention relates to a method for producing a phthalocyanine compound by cyclizing a phthalonitrile compound alone or with a metal compound, and the cyclization reaction is carried out using a hydrocarbon solvent (this In the specification, a method for producing a phthalocyanine compound, which is performed in a mixed solvent of a nitrile solvent (also simply referred to as “mixed solvent” in the present specification) and a nitrile solvent. Is to provide.

  Hereinafter, the present invention will be described in detail.

  The main feature of the present invention is that the cyclization reaction of a phthalonitrile compound alone or a phthalonitrile compound and a metal compound is performed in a mixed solvent of a hydrocarbon solvent and a nitrile solvent which may be halogenated. is there. In the present invention, when the cyclization reaction is performed, a catalyst or an additive for suppressing corrosion may be added. In the case where it is necessary to oxidize a metal compound, a gas containing oxygen may be introduced into the reaction system. Conversely, in the case where it is preferable that no oxygen is present, inert gas such as nitrogen is used. Gas may be introduced. When using an insoluble material such as calcium carbonate, which has an effect of inhibiting corrosion when using a metal halide or the like, it is necessary to remove it by filtration after the reaction. Even when this insoluble additive or the like is not used, during the cyclization reaction, a hardly soluble by-product generated by polymerization of the phthalonitrile compound is often generated, or a metal oxide is often generated or remains. In order to obtain a highly pure phthalocyanine compound, it is desirable to perform filtration after the cyclization reaction.

  According to the present invention, since the amount of impurities deposited during the production process can be significantly suppressed / prevented even during mass production where the reaction volume is 20 liters or more, the produced phthalocyanine compound Has a high purity, and the filter is not clogged or hardly clogged during filtration after the cyclization reaction, so that the purification process can be carried out very smoothly. In the present specification, the “impurity” refers to a substance (may be halogenated) other than the target phthalocyanine compound after the cyclization reaction of the phthalonitrile compound alone or the phthalonitrile compound and the metal compound. Hydrocarbon solvents and nitrile solvents), for example, unreacted metal compounds, metal compounds that have become different due to reactions such as oxidation during the reaction, substances generated by side reactions (for example, polymerization of phthalonitrile) And a catalyst that may be added to promote the reaction efficiently, an additive added to prevent corrosion of the apparatus, and the like. Here, the reason why the target phthalocyanine compound can be obtained with high purity by using a mixed solvent is not clear, but is considered as follows. The present invention is not limited by the following inference. That is, the nitrile solvent that is one of the mixed solvents dissolves the metal compound as a raw material, particularly a metal halide, and is excellent in reactivity, but when a nitrile solvent is used alone, It has the property that side reactions such as the formation of multimers by polymerization of phthalonitrile are likely to occur. On the other hand, the hydrocarbon solvent (which may be halogenated), which is the other solvent, has low solubility in metal compounds, particularly metal halides as raw materials, and is inferior in reactivity. It has the property of being difficult to wake up. For this reason, by appropriately mixing these two solvents, the side reaction is significantly suppressed and prevented while maintaining the solubility and cyclization reactivity in the metal compound as a raw material, particularly metal halide. It turns out that you can. In addition, since the phthalocyanine compound produced by such a method has a small impurity content, even if it is applied to a near-infrared absorption filter for plasma display panels (PDP), the absorption coefficient is reduced in the near-infrared region and visible. It is possible to suppress / prevent a decrease in transmittance in the area. For this reason, the near-infrared absorption filter using the phthalocyanine compound produced by the method of the present invention has a high absorption coefficient in the near-infrared region and a high transmittance in the visible region of 400 to 610 nm, particularly around 400 to 460 nm. Therefore, it is useful for near-infrared absorption filters for plasma display panels (PDP).

  The mixed solvent according to the present invention contains a hydrocarbon solvent that may be halogenated and a nitrile solvent as essential components. Among these, the hydrocarbon solvent is not particularly limited as long as it does not easily cause a side reaction during the cyclization reaction, and may be a hydrocarbon solvent composed only of carbon and hydrogen or the hydrocarbon solvent. It may be a halogenated hydrocarbon solvent (halogenated hydrocarbon solvent) in which at least one hydrogen is substituted with a halogen. Preferably, the hydrocarbon solvent that may be halogenated has a boiling point of 80-260 ° C, more preferably 100-250 ° C, most preferably 140-190 ° C. At this time, if the boiling point of the hydrocarbon solvent is less than 80 ° C., the reaction is slow and impractical at a temperature below the boiling point, and a large amount of solvent is required to dissolve the raw material, and the productivity may be low. On the other hand, 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 degree of vacuum using special equipment. May not be preferable. Specifically, hydrocarbon solvents that may be halogenated include benzene (boiling point: about 80 ° C.), toluene (boiling point: about 111 ° C.), ethylbenzene (boiling point: about 136 ° C.), propylbenzene (cumene). (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 to 252 ° C), 2- Hydrocarbon solvents such as ethyl naphthalene (boiling point: about 252 ° C), n-octane (boiling point: about 126 ° C), n-decane (boiling point: about 174 ° C); and chlorobenzene (boiling point: about 132 ° 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-tri Chlorobenzene (boiling point: about 213 ° C.), 1,3,5-trichlorobenzene (boiling point: about 208 ° C.), 1,2,4,5-tetrachlorobenzene (boiling point: about 243 to 246 ° C.), 2- Halogenated carbonization such as chlorotoluene (boiling point: about 159 ° C), 4-chlorotoluene (boiling point: about 162 ° C), 1-chloronaphthalene (boiling point: about 259 ° C), 2-chloronaphthalene (boiling point: about 256 ° C) Examples include hydrogen-based solvents. Of these, considering the difficulty of side reactions during cyclization, boiling point, solubility of phthalonitrile compounds, industrial availability, etc., 1,2,4-trimethylbenzene, xylene, toluene, Chlorobenzene, dichlorobenzene, chlorotoluene, n-decane and the like are preferable, 1,2,4-trimethylbenzene, xylene, chlorotoluene, dichlorobenzene and n-decane are most preferable, and 1,2,4 are most preferable. -Trimethylbenzene, chlorotoluene. The above hydrocarbon solvents and halogenated hydrocarbon solvents may 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. However, it is generally used alone.

  In the present invention, the nitrile solvent is not particularly limited, but it is preferable that the nitrile solvent dissolves a metal compound as a raw material, particularly a metal halide, and has excellent reactivity. Specific examples include benzonitrile, acetonitrile, and propiononitrile. Among these, considering the solubility and reactivity of the metal compound, the stability of the solvent itself, benzonitrile, acetonitrile, and the like are preferable, and benzonitrile is more preferable. The nitrile solvents may be used alone or in the form of a mixture of two or more, but are generally used alone.

  In the present invention, it is essential to perform the cyclization reaction in a mixed solvent of a hydrocarbon solvent and a nitrile solvent. In this case, the ratio of the hydrocarbon solvent to the nitrile solvent in the mixed solvent should be such that the cyclization reaction can proceed well with little or no side reaction (with little or no precipitation of impurities). There is no particular limitation. Specifically, the nitrile solvent is 1 to 30% by mass, more preferably 3 to 20% by mass, and most preferably 5% in the mixed solvent (based on the total mass of the hydrocarbon solvent and the nitrile solvent). The ratio is such that it is contained in an amount of ˜15% by mass. At this time, if the amount of the nitrile solvent is less than 1% by mass, the solubility of the raw material including the metal compound is excessively lowered, the raw material is not sufficiently dissolved, and stirring becomes difficult or cyclization occurs. The reaction may not proceed sufficiently, and the side reaction may proceed at a speed that cannot be ignored due to the slow cyclization reaction. Conversely, if the amount of the nitrile solvent exceeds 30% by mass, the raw material including the metal compound is excessively dissolved in the mixed solvent, and the target product (phthalocyanine compound) is crystallized by crystallization in the subsequent process. May be difficult, side reactions may easily occur due to the excessive presence of a nitrile solvent, the content of impurities in the final product phthalocyanine compound may increase, and the yield of the reaction may decrease. is there. According to the method of the present invention, the solubility of the target product (phthalocyanine compound) can be appropriately changed by changing the mixing ratio of the hydrocarbon solvent and the nitrile solvent in the mixed solvent. Therefore, depending on the solubility of the target product (phthalocyanine compound), the mixing ratio of the hydrocarbon solvent and the nitrile solvent in this mixed solvent is appropriately set in the subsequent crystallization step so that the target product can be satisfactorily separated in the crystallization step. The phthalocyanine compound can be selectively crystallized by a simple operation of changing.

  The amount of the mixed solvent to be used is not particularly limited as long as the cyclization reaction can proceed satisfactorily with little or no side reaction (with little or no impurities). In consideration of the reactivity and, further, the filtration rate after reaction and crystallization, 0.5 to 30 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 1 part by mass of the starting phthalonitrile compound. Parts, particularly preferably in the range of 1 to 5 parts by weight. At this time, if the amount of the mixed solvent used is less than the lower limit, the raw material is not sufficiently dissolved, so that the cyclization reaction does not proceed efficiently, or by-products increase, and the yield of the desired phthalocyanine compound may decrease. There is sex. In addition to the above, when the amount of the mixed solvent is small, the slurry concentration becomes high, so that stirring becomes difficult during the reaction, a special stirrer is required, and stirring reaction is inferior and uniform reaction cannot be performed. In some cases. On the other hand, if the mixed solvent is used excessively beyond the upper limit, the mixed solvent is used more than necessary, which not only reduces productivity but also may be uneconomical such as a slow reaction rate. In addition to the above, if an excessive amount of solvent is present, a large amount of heat is required to remove the solvent in a later step, a long time is required, or special equipment and equipment are required for the solvent removal operation. There is a possibility. In the present invention, the mixed solvent may be charged all at once during charging, or may be added continuously or divided during the reaction as necessary. Further, the mixed solvent may be prepared by adding the hydrocarbon solvent and the nitrile solvent together or separately.

  In the method of the present invention, the cyclization reaction may be performed in the presence of another solvent in addition to the mixed solvent. Thus, other solvents are not particularly limited as long as they do not induce side reactions or precipitation of impurities and do not hinder the cyclization reaction according to the present invention. For example, ketone, aldehyde, alcohol, carboxylic acid and the like can be mentioned. In addition, each other solvent may be used individually or may be used with the form of a 2 or more types of mixture. In addition, the amount of other solvent used when using another solvent is not particularly limited as long as it does not induce side reaction or precipitation of impurities, and can accelerate the cyclization reaction. It differs depending on the type and amount of the compound, hydrocarbon solvent, and nitrile solvent. Preferably, the amount of the other solvent is 0.2 parts by mass or less with respect to 1 part by mass of the mixed solvent. At this time, if the amount of the other solvent used exceeds 0.2 parts by mass, the amount of the other solvent is too large and the effect of the mixed solvent itself is not sufficiently exhibited, causing side reactions and precipitation of impurities, As a result, the yield of the target phthalocyanine compound may be reduced.

  In the present invention, the cyclization reaction may be performed by introducing a gas containing oxygen into the reaction system when it is necessary to oxidize the metal compound, and conversely, when oxygen is preferably absent. An inert gas such as nitrogen may be introduced into the gas. Thereby, a phthalocyanine compound having a high yield and excellent performance (for example, an absorption coefficient in the near-infrared region, a visible light transmittance, etc.) can be more easily produced as a target product. By controlling the oxygen concentration inside the reactor in this manner, the cyclization reaction proceeds efficiently, and undesirable side reactions are suppressed, thereby making it possible to obtain a high-purity phthalocyanine compound in a high yield. .

  Examples of the oxygen-containing gas that can be used at this time include pure oxygen, air, and an oxygen / nitrogen mixed gas, and an oxygen / nitrogen mixed gas is preferable. Further, the inert gas that can be used is not particularly limited as long as it is inert to the cyclization reaction of the present invention, and examples thereof include nitrogen gas, helium gas, argon gas, carbon dioxide gas, etc. Nitrogen gas.

  The appropriate range of the oxygen concentration inside the reactor varies depending on the raw material and the type of the target phthalocyanine compound, but is preferably 21 vol% or less, more preferably 10 vol% or less. If the oxygen concentration is higher than necessary, an undesired oxidation reaction may occur and the yield of the target phthalocyanine compound may decrease, and there may be safety problems such as being within the explosion range of the mixed solvent used. There is.

  The appropriate supply rate of oxygen also varies depending on the raw material and the type of the target phthalocyanine compound. However, the oxygen-containing gas is preferably supplied every hour (the supply amount of oxygen molecules is 1 mol of the phthalonitrile compound). The cyclization reaction is carried out while feeding at 0.003 to 0.05 mol per hour), more preferably 0.005 to 0.03 mol per hour. In particular, when vanadium halide is used as a raw material, the cyclization reaction should be performed while supplying 0.005 to 0.03 mol per hour (per hour) with respect to 1 mol of the phthalonitrile compound. Is preferred. At this time, if the oxygen supply rate is too high, an undesired oxidation reaction may occur as a side reaction. On the other hand, if the supply rate of oxygen is too small, the cyclization reaction may be slow and take a long time, or the side reaction may proceed relatively faster and the yield may decrease.

  Examples of the method of replacing the inside of the reactor with gas include a method of circulating a gas or a method of repeatedly depressurizing and returning to normal pressure after the inside of the reactor is pressurized with gas. Appropriate control of the concentration of the gas phase inside the reactor can be easily achieved by measuring the oxygen concentration using an oxygen concentration meter or the like. The gas flow rate is not particularly limited. For example, when a cooling pipe is installed in the reactor, the linear velocity with respect to the cross-sectional area of the connection portion between the reactor and the cooling pipe is 0.01 to 10 cm / sec, Preferably it is 0.1-5 cm / sec, More preferably, it is 0.2-3 cm / sec. When the linear velocity is 0.01 cm / sec or less, substitution with gas becomes insufficient, and the reaction becomes disadvantageous. If it is higher than 10 cm / sec, the solvent used in the reaction may be scattered, which may be industrially unfavorable.

  The metal compound used in the method of the present invention is not particularly limited as long as it can produce a target phthalocyanine compound by cyclization reaction with a phthalonitrile compound, but metal, metal oxide, metal carbonyl, metal There are halides and organic acid metals. These metal compounds may be used alone or in the form of a mixture of two or more, and are appropriately selected depending on the structure of the target phthalocyanine compound. The metal compound has a metal corresponding to “M” 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 halides such as chloride, bromide, and iodide of the metal, such as vanadium trichloride, vanadium chloride, Titanium chloride, copper 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, iodide Indium, aluminum iodide, gallium iodide, copper bromide, zinc bromide, cobalt bromide, aluminum bromide, gallium bromide; vanadium monoxide, vanadium trioxide, vanadium tetroxide, vanadium pentoxide, titanium dioxide, mono Iron oxide, iron sesquioxide, iron tetroxide, manganese oxide, nickel monoxide, Cobalt monoxide , Cobalt oxide, cobalt dioxide, cuprous oxide, cupric oxide, copper sesquioxide, barium oxide, zinc oxide, germanium monoxide, and germanium dioxide, etc .; copper acetate, zinc acetate, cobalt acetate, And organic acid metals such as copper benzoate and zinc benzoate; and complex compounds such as acetylacetonate and metal carbonyls such as cobalt carbonyl, iron carbonyl and nickel carbonyl. Of these, metals, metal oxides, and metal halides are preferable, and metal oxides and metal halides are more preferable in view of industrial availability. In addition, the quality of the surface area and the like may vary depending on the production method and Lot of the metal oxide, which affects the reactivity because the solubility and dispersibility change during the reaction, resulting in a decrease in yield. Product quality may not be stable. For this reason, metal halides are particularly preferred, and vanadium trichloride and copper chloride are particularly preferably used. When vanadium trichloride or copper chloride is used, the central metal is vanadium or copper, respectively.

  The cyclization reaction in the present invention can be performed in the same manner as a generally known method except that the cyclization reaction is performed in the presence of a mixed solvent. For example, the reaction conditions between the phthalonitrile compound and the metal compound are not particularly limited as long as the reaction proceeds. For example, the mixed solvent can be used in the same amount as described above. Moreover, a metal compound is prepared so that it may become the range of 1-3 mol with respect to 4 mol of phthalonitrile compounds, Preferably it is 1.05-2 mol. The reaction temperature is 80 to 250 ° C, preferably 100 to 220 ° C, more preferably 120 to 200 ° C. At this time, if the reaction temperature is too low, the reaction rate becomes very slow and impractical, whereas if the reaction temperature is too high, side reactions are likely to occur and the yield of the target product is reduced. The reaction time is 0.1 to 24 hours, preferably 0.5 to 20 hours, and more preferably 1 to 18 hours.

  After the cyclization reaction, it can be obtained efficiently and with high purity by filtration, crystallization, washing and drying. The said filtration, crystallization, filtration, washing | cleaning, and a drying process are not restrict | limited in particular, The process similar to the various processes used with the synthesis method of a conventionally well-known phthalocyanine compound can be used. As described above, according to the present invention, the phthalocyanine compound produced by the method of the present invention is used because the content in the product of impurities that may cause a decrease in the purity of the phthalocyanine compound and hinder the transmission of visible light is small. The filter that has been used has a high near-infrared light absorption performance, while it has a high transmittance in the visible region, particularly 400 to 610 nm, particularly 400 to 460 nm. The mixed solvent used in the cyclization reaction is composed of a hydrocarbon solvent and a nitrile solvent. By changing the mixing ratio in these mixed solvents, the solubility of the target product (phthalocyanine compound) is appropriately changed. Is possible. For this reason, the mixing ratio of the hydrocarbon-based solvent and the nitrile-based solvent in this mixed solvent is changed in the subsequent crystallization process so that the target object can be satisfactorily separated in the crystallization process depending on the solubility of the target object (phthalocyanine compound). The phthalocyanine compound can be selectively crystallized by a simple operation of appropriate changes. Further, since the reaction product after the cyclization reaction has a small impurity content, the filter is not clogged even in the filtration step after the reaction, and the filtration can be performed smoothly.

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

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

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

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

A phthalonitrile compound (4) represented by
By a cyclization reaction either alone or in a mixed solvent of a metal compound and a hydrocarbon solvent that may be halogenated and a nitrile solvent, the following formula (5):

A phthalocyanine compound represented by The method of the present invention is characterized in that the cyclization reaction is carried out in a mixed solvent of a hydrocarbon solvent and a nitrile solvent which may be halogenated, and the raw material phthalonitrile compound and metal The structure of the compound and the phthalocyanine compound to be produced is not particularly limited, and is appropriately selected depending on the desired near infrared absorption wavelength, the transmittance at the maximum absorption wavelength, the transmittance in the visible light region, and the like. For this reason, methods other than the constituent features described above can be applied in the same manner as in the prior art. For example, Japanese Patent Application Laid-Open No. 2001-106869, Japanese Patent No. 3721298, Japanese Patent Application Laid-Open No. 2004-018561 and Japanese Patent Application Laid-Open No. 2002-2002. -114790 etc. are mentioned.

Alternatively, according to the present invention, the presence of a mixed solvent of a hydrocarbon solvent and a nitrile solvent that may be halogenated with the phthalonitrile compound represented by the above formulas (1) to (4), which is a starting material. The corresponding phthalocyanine compound can be produced in a high yield by reacting alone or with a metal compound. Depending on the type of NHR ¹ , SR ² or OR ³ substituent or the number of substituents, Even if the above-mentioned cyclization reaction is performed, the above-mentioned substituents of NHR ¹ , SR ² or OR ³ are not substituted at an advantageous reaction rate, and the desired phthalocyanine compound may not be obtained.

For this reason, such a phthalocyanine compound having 12 or more substituents of NHR ¹ , SR ² or OR ³ may be obtained by the above production method, but the phthalocyanine compound is represented by the formula: M′-NHR ⁴ An amino compound represented by the formula: a sulfur-containing compound represented by the formula: M′-SR ⁵ ; and an alcohol compound represented by the formula: M′-OR ⁶ (in the above formula, M ′ represents a hydrogen atom or an alkali metal atom; R ⁴ , R ^5, and R ⁶ can be appropriately selected depending on the structure of the desired phthalocyanine compound) and further substituted with at least one compound selected from the desired NHR ¹ , SR ^2, or OR ³ substituents Can efficiently introduce the target number, for example, selective absorption of light of near-infrared wavelength, compatibility with resin, high transmission in the visible region A phthalocyanine compound having a desired function such as a rate can be produced in a high yield.

  That is, the following formula (1):

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

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

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

A phthalonitrile compound (4) represented by
By a cyclization reaction either alone or in a mixed solvent of a metal compound and a hydrocarbon solvent that may be halogenated and a nitrile solvent, the following formula (5):

After obtaining the phthalocyanine compound (a) represented by formula (7), the phthalocyanine compound (a) is further represented by formula (7): amino compound represented by M′-NHR ⁴ and formula (8): M′-SR ⁵ A sulfur-containing compound and an alcohol compound represented by formula (9): M′-OR ⁶ (in the above formula, M ′ is a hydrogen atom or an alkali metal atom, and R ⁴ , R ^5, and R ⁶ are desired) The phthalocyanine compound can be appropriately selected depending on the structure of the phthalocyanine compound.) By performing a substitution reaction with at least one compound selected from the following formula (5):

The phthalocyanine compound (b) shown by these is manufactured. As described above, the method of the present invention is characterized in that the cyclization reaction is performed in a mixed solvent of a hydrocarbon solvent and a nitrile solvent which may be halogenated, and is a raw material. The structures of the phthalonitrile compound and the metal compound and the phthalocyanine compound to be produced are not particularly limited, and are appropriately selected depending on the desired near infrared absorption wavelength, the transmittance at the maximum absorption wavelength, the transmittance in the visible light region, and the like. For this reason, methods other than the constituent features described above can be applied in the same manner as in the prior art. For example, Japanese Patent Application Laid-Open No. 2001-106869, Japanese Patent No. 3721298, Japanese Patent Application Laid-Open No. 2004-018561 and Japanese Patent Application Laid-Open No. 2002-2002. -114790 etc. are mentioned.

In the following, phthalocyanine compound (a) and formula (7): amino compound represented by M′-NHR ⁴ (hereinafter referred to as “amino compound (7)”), formula (8): represented by M′-SR ⁵ A sulfur-containing compound (hereinafter referred to as “sulfur-containing compound (8)”), and an alcohol compound represented by formula (9): M′-OR ⁶ (hereinafter referred to as “alcohol compound (9)”). The substitution reaction will be briefly described.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  According to the method of the present invention, the target phthalocyanine compound can be produced with a yield of 70% or more. Further, as described above, the filter using the phthalocyanine compound produced by the method of the present invention has a low impurity content, so that it has absorption characteristics, particularly 400 to 610 nm, particularly transmittance in the vicinity of 400 to 460 nm, and visible light. High transmittance. For this reason, the phthalocyanine compound produced by the method of the present invention is particularly useful for near-infrared absorption filters for plasma display panels (PDP). In addition to the above advantages, in the method of the present invention, impurities such as unreacted metal do not precipitate, so even when the impurities are filtered and removed after the reaction, the filter is not clogged and the reaction can be performed quickly. The liquid can be filtered. In the method of the present invention, the reaction can be carried out by reducing the amount of a relatively high-boiling solvent having a relatively high polarity such as benzonitrile, so that the product can be easily dried. Furthermore, according to the method of the present invention, by appropriately selecting the mixing ratio of the hydrocarbon solvent and the nitrile solvent in the mixed solvent according to the solubility of the target product (phthalocyanine compound), the target product is not particularly changed without changing the solvent. Can be separated easily and satisfactorily in the crystallization process.

As described above, the phthalocyanine compound produced by the method of the present invention has a low content of impurities, which is one of the causes of hindering the transmission of light, and thus has a high transmittance in the visible region of 400 to 610 nm, particularly in the vicinity of 400 to 460 nm. Since it has a high rate and can exhibit a high absorption coefficient in the near infrared region, it is particularly useful for a near infrared absorption filter for plasma display panels (PDP). For example, when used for a near infrared absorption filter for PDP, 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (DL- 1-phenylethylamino) -fluoro} vanadyl phthalocyanine [abbreviation: VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F] Preferably used. At this time, the phthalocyanine compound produced by the method of the present invention [abbreviation: VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F] exhibits an excellent characteristic that the extinction coefficient of the maximum absorption wavelength when dissolved and diluted in chloroform is 105,000 or more.

  Hereinafter, specific examples will be described with reference to examples. In the present invention, the maximum absorption wavelength, extinction coefficient, and spectral transmittance were measured by the following methods.

<Measurement of maximum absorption wavelength (λmax), extinction coefficient, and spectral transmittance>
Using a spectrophotometer (manufactured by Shimadzu Corporation: UV-1650PC), the maximum absorption wavelength (λmax) and the extinction coefficient of the obtained phthalocyanine compound in the range of 400 to 1100 nm were measured in chloroform.

  Further, a solution was prepared in a 1 cm quartz cell so that the transmittance at λmax was 10%, and the visible light transmittance at that time was measured at wavelengths of 400 nm, 460 nm, 545 nm, and 610 nm.

Example 1: 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} vanadyl phthalocyanine [abbreviation Synthesis of VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F] 100 mL with reflux condenser and gas inlet tube In a three-necked flask, 16.47 g (28.0 mmol) of 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile, 1.43 g of vanadium trichloride (9.1 mmol), calcium carbonate 1.91 g (19.1 mmol), 1,2,4-trimethylbenzene 19.8 g, and benzonitrile He was charged with 2.2g. While a mixed gas (oxygen 6.8 vol% / nitrogen balance) was blown into the liquid at a flow rate of 2 mL / min, the mixture was stirred at 160 ° C. for 8 hours to cause a cyclization reaction. The amount of oxygen molecules supplied per hour was 0.334 mmol, and the molar ratio was 0.012 times the phthalonitrile compound used.

  The conversion of 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 97.3%. Next, 48 g of 1,2,4-trimethylbenzene was added and the temperature of the solution was adjusted to 100 ° C. Nitrogen was blown into the liquid at a flow rate of 4 mL / min for 30 minutes with stirring, and then 3.64 g (30.0 mmol) of DL-1-phenylethylamine and calcium carbonate 5 were continuously blown at a flow rate of 2 mL / min. .93 g (59.2 mmol) and 1,2,4-trimethylbenzene 2 g were added and stirred at 100 ° C. for 6 hours for amination reaction.

  The reaction solution was cooled to 35 ° C. under a nitrogen stream, and the precipitated insoluble matter was removed by filtration. Filtration was performed using Kiriyama filter paper (No. 4) having a diameter of 60 mm under reduced pressure with a Kiriyama funnel. Filtration was completed within 1 minute. The residue on the filter paper was washed with 10 g of 1,2,4-trimethylbenzene and filtered, and the washing solution was added to the first filtrate. A total of 97.5 g of filtrate was obtained.

  A mixed solvent of 600 g of 2-propanol and 150 g of water was placed in a 1 liter separable flask, and the filtrate was added dropwise over 30 minutes while stirring at 60 ° C. After maintaining the temperature at 60 ° C. for 10 minutes after completion of dropping, the mixture was cooled to 30 ° C. at a cooling rate of 15 ° C./hour while continuing to stir, and further allowed to cool for 30 minutes to precipitate crystals and filtered. The crystals on the obtained filter paper were washed with 7 g of 2-propanol + 3 g of water (mixed solvent).

The obtained crystals were again put into a 1 liter separable flask and washed by stirring in a mixed solvent of 210 g of acetone and 90 g of water at room temperature for 30 minutes. The crystals on the filter paper obtained by filtration were washed with 7 g of acetone + 3 g of water (mixed solvent). The obtained crystals were vacuum-dried at 60 ° C., and VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ } {Ph (CH ₃ ) CHNH} ₃ F 16.5 g was gotten. The yield based on 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 86.5%.

Example 2: 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} vanadyl phthalocyanine [abbreviation Synthesis of VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F], 1, which is the solvent for the cyclization reaction of Example 1 The cyclization reaction was carried out for 14 hours in the same manner as in Example 1 except that 19.8 g of o-xylene was used instead of 2,4-trimethylbenzene and the temperature of the cyclization reaction was 145 ° C. The conversion of 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 96.0%. Next, an amination reaction was performed in the same manner as in Example 1 except that o-xylene was used instead of 1,2,4-trimethylbenzene. The amination reaction was performed at 100 ° C. for 6 hours.

  The reaction solution was cooled and filtered in the same manner as in Example 1, and the residue on the filter paper was washed with 10 g of o-xylene. Filtration was completed within 1 minute.

Thereafter, crystallization, washing and drying were carried out in the same manner as in Example 1, and VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ } {Ph (CH ₃ ) CHNH} 15.9 g of ₃ F was obtained. The yield based on 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 83.4%.

Example 3: 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} vanadyl phthalocyanine [abbreviation Synthesis of VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F], 1, which is the solvent for the cyclization reaction of Example 1 A cyclization reaction was carried out at 160 ° C. for 7 hours in the same manner as in Example 1 except that 19.8 g of 4-chlorotoluene was used instead of 2,4-trimethylbenzene. The conversion of 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 98.3%. Next, an amination reaction was performed in the same manner as in Example 1 except that 4-chlorotoluene was used instead of 1,2,4-trimethylbenzene. The amination reaction was performed at 100 ° C. for 6 hours.

  The reaction solution was cooled and filtered in the same manner as in Example 1, and the residue on the filter paper was washed with 10 g of 4-chlorotoluene. Filtration was completed in 3 minutes.

Thereafter, crystallization, washing and drying were carried out in the same manner as in Example 1, and VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ } {Ph (CH ₃ ) CHNH} 16.1 g of ₃ F was obtained. The yield based on 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 84.5%.

Example 4: 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} vanadyl phthalocyanine [abbreviation Synthesis of VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F], 1, which is the solvent for the cyclization reaction of Example 1 A cyclization reaction was carried out at 160 ° C. for 12 hours in the same manner as in Example 1 except that 27.0 g of n-decane was used instead of 2,4-trimethylbenzene and the amount of benzonitrile was changed to 3 g. The conversion of 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 95.5%. Next, in the same manner as in Example 2, 48 g of o-xylene was added to bring the temperature of the reaction solution to 100 ° C. The amination reaction was then carried out in the same manner as in Example 2. The amination reaction was performed at 100 ° C. for 6 hours. The reaction solution was cooled and filtered in the same manner as in Example 2, and the residue on the filter paper was washed with 10 g of o-xylene. Filtration was completed in 1-2 minutes. Thereafter, crystallization, washing and drying were carried out in the same manner as in Example 1, and VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ } {Ph (CH ₃ ) CHNH} ₃ F 15.5 g was obtained. The yield based on 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 81.3%.

Example 5: 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} vanadyl phthalocyanine [abbreviation Synthesis of VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F] The gas supplied in Example 1 was supplied with an oxygen concentration of 6. The cyclization reaction was carried out in the same manner as in Example 1 except that air was used instead of the 8% mixed gas. The amount of oxygen molecules supplied per hour was 1.03 mmol, which was 0.037 times in molar ratio to the phthalonitrile compound used. The cyclization reaction was carried out at 160 ° C. for 5 hours, and the conversion of 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 99.3%. there were. Thereafter, in the same manner as in Example 1, the amination reaction was performed by stirring at 100 ° C. for 6 hours.

Next, the reaction solution was cooled and filtered in the same manner as in Example 1, and the residue on the filter paper was washed with 10 g of 1,2,4-trimethylbenzene. Filtration was completed in 1-2 minutes. Further, crystallization, washing, and drying were performed in the same manner as in Example 1. As a result, 12.8 g of VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ } {Ph (CH ₃ ) CHNH} ₃ F was obtained. The yield based on 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 67.1%.

Example 6: 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} vanadyl phthalocyanine [abbreviation Synthesis of VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F] The gas supplied in Example 1 was supplied with an oxygen concentration of 6. The cyclization reaction was carried out in the same manner as in Example 1 except that the mixed gas air had a composition of (oxygen 3.0 vol% / nitrogen balance) instead of the 8% mixed gas. The amount of oxygen molecules supplied per hour was 0.147 mmol, and the molar ratio with respect to the phthalonitrile compound used was 0.0053. The cyclization reaction was carried out at 160 ° C. for 15 hours, and the conversion of 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 96.6%. there were.

Next, in the same manner as in Example 1, the amination reaction was performed by stirring at 100 ° C. for 6 hours. Next, the reaction solution was cooled and filtered in the same manner as in Example 1, and the residue on the filter paper was washed with 10 g of 1,2,4-trimethylbenzene. Filtration was completed within 1 minute. Further, crystallization, washing, and drying were performed in the same manner as in Example 1. As a result, 16.0 g of VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ } {Ph (CH ₃ ) CHNH} ₃ F was obtained. The yield based on 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 83.9%.

Example 7: 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (benzylamino) -vanadyl phthalocyanine [abbreviation; VOPc (2,5- Synthesis of Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ A cyclization reaction was carried out in the same manner as in Example 1, and after completion of the cyclization reaction, 1, 2, 4 -Trimethylbenzene 30g was added and the reaction liquid was cooled to 60 degreeC. 18.0 g (168 mmol) of benzylamine, 1.30 g (13.0 mmol) of calcium carbonate, and 2 g of 1,2,4-trimethylbenzene were added and stirred at 60 ° C. for 3 hours for amination reaction. The reaction solution was cooled and filtered in the same manner as in Example 1, and the residue on the filter paper was washed with 10 g of 1,2,4-trimethylbenzene. Filtration was completed in 1 minute. A total of 94.8 g of filtrate was obtained.

  A mixed solvent of 500 g of 2-propanol and 100 g of water was placed in a 1 liter separable flask, and the filtrate was added dropwise over 30 minutes while stirring at 60 ° C. After maintaining the temperature at 60 ° C. for 10 minutes after completion of dropping, the mixture was cooled to 30 ° C. at a cooling rate of 15 ° C./hour while continuing to stir, and further allowed to cool for 30 minutes to precipitate crystals and filtered. The crystals on the obtained filter paper were washed with 8 g of 2-propanol + 2 g of water (mixed solvent).

The obtained crystal was again put into a 1-liter separable flask, and washed in a mixed solvent of 140 g of 2-propanol and 60 g of water at room temperature for 30 minutes. The crystals on the filter paper obtained by filtration were washed with 7 g of 2-propanol + 3 g of water (mixed solvent). The obtained crystal was vacuum-dried at 60 ° C. to obtain 16.5 g of VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ . The yield based on 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 85.1%.

Example 8: 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (benzylamino) -copper phthalocyanine [abbreviation: CuPc (2,5- Synthesis of Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) _{4 In} a 100 mL _three- necked flask equipped with a reflux condenser and a gas blowing tube, 3- (2,6- Dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile 16.47 g (28.0 mmol), copper chloride () 0.76 g (7.7 mmol), calcium carbonate 0.91 g (9.1 mmol), 19.8 g of 1,2,4-trimethylbenzene, and 2.2 g of benzonitrile were charged. While a mixed gas (oxygen 6.8 vol% / nitrogen balance) was blown into the liquid at a flow rate of 2 mL / min, the mixture was stirred at 160 ° C. for 9 hours to cause a cyclization reaction. The conversion of 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 96.5%. Next, 48 g of 1,2,4-trimethylbenzene was added, and then the liquid temperature was raised to 90 ° C. 18.0 g (168 mmol) of benzylamine, 1.68 g (16.8 mmol) of calcium carbonate, and 2 g of 1,2,4-trimethylbenzene were added, and the mixture was stirred at 90 ° C. for 4 hours for amination reaction. The reaction solution was cooled and filtered in the same manner as in Example 1, and the residue on the filter paper was washed with 15 g of 1,2,4-trimethylbenzene. Filtration was completed in 2 minutes. A total of 116.0 g of filtrate was obtained.

  A mixed solvent of 800 g of acetonitrile and 40 g of water was placed in a 2 liter separable flask, and the filtrate was added dropwise over 30 minutes while stirring at 60 ° C. After maintaining the temperature at 60 ° C. for 10 minutes after completion of dropping, the mixture was cooled to 30 ° C. at a cooling rate of 15 ° C./hour while continuing to stir, and further allowed to cool for 30 minutes to precipitate crystals and filtered. The crystals on the obtained filter paper were washed with 18 g of acetonitrile + 2 g of water (mixed solvent).

The obtained crystals were again put into a 2 liter separable flask and washed by stirring in a mixed solvent of 200 g of acetone and 100 g of water at room temperature for 30 minutes. The crystals on the filter paper obtained by filtration were washed with 12 g of acetone + 6 g of water (mixed solvent). The obtained crystal was vacuum-dried at 60 ° C. to obtain 13.0 g of CuPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ . The yield based on 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 67.2%.
Example 9: 4,5-octakis (phenylthio) -3,6- {tetrakis (2,6-dimethylphenoxy) -tetrakis (2-ethylhexylamino)} vanadyl phthalocyanine [abbreviation: VOPc (PhS) ₈ {2,6 Synthesis of — (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH} ₄ ] 3- (2,6-dimethylphenoxy) -4,5 of Example 1 -Instead of bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile, 13.51 g of 3- (2,6-dimethylphenoxy) -4,5-bis (phenylthio) -6-fluorophthalonitrile (28. The cyclization reaction was performed in the same manner as in Example 1 except that 0 mmol) was used. The cyclization reaction was performed at 160 ° C. for 8 hours, and the conversion of 3- (2,6-dimethylphenoxy) -4,5-bis (phenylthio) -6-fluorophthalonitrile was 97.1%. Next, 30 g of 1,2,4-trimethylbenzene was added, and the liquid temperature was adjusted to 70 ° C. Nitrogen was blown into the liquid at a flow rate of 4 mL / min for 30 minutes under stirring, and then 29.0 g (224 mmol) of 2-ethylhexylamine was added while continuing to blow nitrogen at a flow rate of 2 mL / min. The amination reaction was carried out with stirring for a period of time. The reaction solution was cooled and filtered in the same manner as in Example 1, and the residue on the filter paper was washed with 10 g of 1,2,4-trimethylbenzene. Filtration was completed in 3 minutes. A total of 103.5 g of filtrate was obtained.

  A mixed solvent of 540 g of 2-propanol and 54 g of water was placed in a 1 liter separable flask, and the filtrate was added dropwise over 30 minutes while stirring at 60 ° C. After maintaining the temperature at 60 ° C. for 10 minutes after completion of dropping, the mixture was cooled to 30 ° C. at a cooling rate of 15 ° C./hour while continuing to stir, and further allowed to cool for 30 minutes to precipitate crystals and filtered. The crystals on the obtained filter paper were washed with 9 g of 2-propanol and 1 g of water (mixed solvent).

The obtained crystal was again put into a 1 liter separable flask and washed by stirring in a mixed solvent of 175 g of acetone and 75 g of water at room temperature for 30 minutes. The crystals on the filter paper obtained by filtration were washed with 7 g of acetone + 3 g of water (mixed solvent). The obtained crystal was vacuum-dried at 60 ° C., and VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH} ₄ 13.3 g was obtained. The yield based on 3- (2,6-dimethylphenoxy) -4,5-bis (phenylthio) -6-fluorophthalonitrile was 78.1%.

Comparative Example 1: 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} vanadyl phthalocyanine [abbreviation Synthesis of VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F] The solvent for the cyclization reaction of Example 1 is 1, Instead of the mixed solvent of 2,4-trimethylbenzene and benzonitrile, 22 g of benzonitrile alone was used. Otherwise, the cyclization reaction was carried out for 7 hours under the same conditions as in Example 1. The conversion of 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 97.5%.

  Next, the amination reaction was started in the same manner as in Example 1. Since the progress of the reaction was slow, after reacting for 15 hours, 1.21 g (10.0 mmol) of DL-1-phenylethylamine was added and the reaction was further continued for 3 hours to complete the amination reaction.

  The reaction solution was cooled and filtered in the same manner as in Example 1, and the residue on the filter paper was washed with 10 g of benzonitrile. The time required for filtration was 70 minutes.

Thereafter, crystallization, washing and drying were carried out in the same manner as in Example 1, and VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ } {Ph (CH ₃ ) CHNH} ₃ F 12.4g was obtained. The yield based on 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 65.0%.

Comparative Example 2: 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) -tris (DL-1-phenylethylamino) -fluoro} vanadyl phthalocyanine [abbreviation Synthesis of VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F] The solvent for the cyclization reaction of Example 1 is 1, Instead of the mixed solvent of 2,4-trimethylbenzene and benzonitrile, 22 g of 1,2,4-trimethylbenzene alone was used. Otherwise, the cyclization reaction was carried out for 12 hours under the same conditions as in Example 1. The conversion of 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 96.6%.

  Next, the amination reaction was started in the same manner as in Example 1. The reaction was completed for 8 hours to complete the amination reaction.

  The reaction solution was cooled and filtered in the same manner as in Example 1, and the residue on the filter paper was washed with 10 g of 1,2,4-trimethylbenzene. The time required for filtration was 11 minutes.

Thereafter, crystallization, washing and drying were carried out in the same manner as in Example 1, and VOPc (2,5-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ } {Ph (CH ₃ ) CHNH} 11.9 g of ₃ F was obtained. The yield based on 3- (2,6-dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was 62.4%.

  The results of the reactions in Examples 1 to 3 and Comparative Examples 1 and 2 (filterability and yield of the reaction solution) are summarized in Table 1, and the evaluation results of the absorption performance are summarized in Table 2. In Table 1 below, “◎” indicates that the time required for filtration is less than 2 minutes; “◯” indicates that the time required for filtration is 2 minutes to 10 minutes. “Δ” indicates that the time required for the filtration is 10 minutes to 1 hour; and “x” indicates that the time required for the filtration is 1 hour or more.

Claims (8)

A method for producing a phthalocyanine compound having a cyclization reaction of a phthalonitrile compound alone or with a metal compound,
The cyclization reaction, rows that have a mixed solvent of halogenated may be hydrocarbon solvents and nitrile solvents,
The hydrocarbon solvent that may be halogenated is benzene, toluene, ethylbenzene, propylbenzene (cumene), isopropylbenzene (cumene), xylene, 1-methyl-2-ethylbenzene, 1-methyl-3-ethylbenzene, 1 -Methyl-4-ethylbenzene, o-diethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, 1-methylnaphthalene, 2-methylnaphthalene, 1- Ethylnaphthalene, 2-ethylnaphthalene, n-octane, n-decane, chlorobenzene, dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1, 2,4,5-tetrachlorobenzene, chlorotoluene, 1-chloro B naphthalene, and at least one selected from the group consisting of 2-chloro-naphthalene,
The method for producing a phthalocyanine compound, wherein the nitrile solvent is at least one selected from the group consisting of benzonitrile, acetonitrile, and propiononitrile .   The said nitrile solvent is a manufacturing method of the phthalocyanine compound of Claim 1 contained in the quantity of 1-30 mass% in the said mixed solvent. The hydrocarbon-based solvent that may be halogenated is at least one selected from the group consisting of 1,2,4-trimethylbenzene, xylene, toluene, chlorobenzene, dichlorobenzene, chlorotoluene, and n-decane . The manufacturing method of the phthalocyanine compound of Claim 1 or 2.   The hydrocarbon-based solvent that may be halogenated is at least one selected from the group consisting of 1,2,4-trimethylbenzene, xylene, chlorotoluene, dichlorobenzene, and n-decane. The manufacturing method of the phthalocyanine compound of any one of -3.   The said metal compound is a manufacturing method of the phthalocyanine compound of any one of Claims 1-4 which is a metal halide.   6. The method for producing a phthalocyanine compound according to claim 5, wherein the metal halide is a halide of vanadium.   The cyclization reaction is carried out while supplying oxygen-containing gas to the reaction solution so that the supply amount of oxygen molecules is 0.003 to 0.05 mol per hour with respect to 1 mol of phthalonitrile compound. The manufacturing method of the phthalocyanine compound of any one of 1-6. 4,5-octakis (2,5-dichlorophenoxy) -3,6- {tetrakis (2,6-dimethylphenoxy) having an absorption coefficient of 105,000 or more when dissolved and diluted in chloroform ) -Tris (DL-1-phenylethylamino) -fluoro} vanadyl phthalocyanine [abbreviation; VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F].