Process for preparing metallophthalocyanine

Abstract: The present invention provides a deodorizer comprising a water-soluble metallophthalocyanine represented by the formula: wherein, "Met" is a central metal, X is an acidic group or alkali metal salt thereof, m and p are respectively an integer of from 1 to 15, and m + p is not more than 16. The deodorizer shows excellent deodorizing ability for an aldehyde-origin odor.

Description: The present invention relates to a process for preparing metallophthalocyanine. It is conventionally known that phthalocyanine derivatives can be used as a deodorizer for deodorizing bad smell in living atmosphere. The deodorizing process by using phthalocyaninepolycarboxylic acid and phthalocyaninepolysulfonic acid, for example, is noticed as an artificial enzymatic oxidation deodorizing process, and is partially put into practice. These phthalocyanine derivatives show excellent deodorizing ability for an ammonia odor (an amine-origin odor) an: a mercaptan odor (a sulfur-origin odor), however, show insufficient deodorizing ability for an aldehyde-origin odor which is one of main components of a tobacco odor. It has been reported that ironphthalocyanine shows relatively good deodorizing ability. However, the deodorizing ability is insufficient for the aldehyde-origin odor, and is not practical as a deodorizer. Further, ironphthalocyanine shows poor deodorizing ability for a sulfur-origin odor by comparison with cobaltphthalocyanine, and has poor stability in an alkali solution which is used for depositing it on a support. The deodorizing ability of the ironphthalocyanine, therefore, does not continue for a long period. JP-A-56-63355/1981 discloses an ironphthalocyanine derivative , and the like obtained by the urea method, and it is described that the phthalocyanine derivative has deodorizing ability for an aldehyde-origin odor. However, the deodorizing ability thereof is not sufficient. EP-A-0 675 170 discloses a process for production of copper phtalocyamine comprising heating, as reactants, a phtalic acid or reactive derivative there of, a nitrogen source and a copper compound in an inert solvent in the presence of a catalyst and at least one surfactant. This kind of metallophthalocyanine is generally produced by the urea method (the Weilar method, or the phthalic anhydride liquid phase method, in other words), phthalonitrile method , and the like. The phthalonitrile method uses phthalonitriles as a raw material, and has the merits that reaction time is relatively short and yield is excellent. However, the phthalonitriles used as a raw material are expensive, and consequently the production cost becomes high. Further, it is pointed out that the phthalonitriles are toxic, handling thereof requires attention from the view point of safety. On the other hand, the urea method, particularly the phthalic anhydride liquid phase method is a method in which a phthalic acid derivative (for example, trimellitic anhydride), urea, a metallizing agent, and a catalyst are heated in a solvent. The raw materials used in the urea method are relatively inexpensive and have low toxicity, therefore, the urea method is low-cost and safe. However, a hydrophobic organic solvent such as nitrobenzene and trichlorobenzene is usually used as a solvent. It is therefore necessary to distill, remove, and recover the solvent from a reaction mixture after completion of the reaction. When a solvent is distilled off from a reaction mixture, the reaction mixture is kept at high temperature under reduced pressure so that the mixture does not bump. This step takes a lot of time and labor, especially when a scale of the reaction becomes large. Therefore, the urea method has a demerit that the production process is complicated, especially on mass production. Further, the hydrophobic organic solvents are harmful for a human body and environment, and handling thereof requires attention from the view point of safety. The phthalic anhydride solid phase method does not use an organic solvent as a reaction solvent, therefore, it does not take a labor for separating and recovering the organic solvent. However, the yield of this method is low, and the method is not suitable for mass production. It is the object of the present invention to solve the above-described conventional problems and to provide a process for preparing metallophtalocyamine which enables high yield, low cost, safety and simplicity. Therefore, the present invention provides a process for preparing metallophthalocyanine according to the urea method, in which polyethylene glycol dialkyl ether is used as a reaction solvent. Fig. 1 is a graph which shows IR spectrum of (tetracarboxyphthalocyaninato)cobalt obtained in Example 13. Fig. 2 is a graph which shows IR spectrum of (tetracarboxyphthalocyaninato)cobalt obtained in Comparative Example 4. According to the urea method (the phthalic anhydride liquid phase method), a metallophthalocyanine compound is generally prepared by heating a phthalic acid derivative such as phthalic anhydride and phthalimide, urea, and metal halide in an inert organic solvent in the presence of a condensation catalyst. This method is well known to the art, and specifically described in "Dye and Chemical", Vol. 23, No. 10, pp 213 to 215, (1978), "Recent technique for preparing phthalocyanine pigment [I]", and the like. Examples of the phthalic acid derivative used as a raw material include trimellitic anhydride, pyromellitic dianhydride, 4-sulfophthalic acid, 4-sulfophthalic anhydride, 4-nitrophthalimide, 3-nitrophthalimide, 4-nitrophthalic anhydride , and the like. Phthalic anhydride, alkyl-substituted phthalic acid, alkoxy-substituted phthalic acid, 4-chloro-5-nitrophthalimide, ammonium salt of phthalic acid, metal salt (Na salt, K salt) of phthalic acid, phthalate, phthalamide, phthalyl halogenate, phthalimide, o-cyanobenzoic acid, o-cyanobenzoate, and the like can also be used as the raw material. Examples of the metal halide include copper (I) chloride, cobalt chloride (6 hydrate), iron (II, III) chloride, nickel chloride, aluminum chloride, and the like. Sulfate of polyvalent metal (for example, cobalt sulfate, copper sulfate, aluminum sulfate, chromium sulfate), nitrate (for example, copper (II) nitrate), phosphate of polyvalent metal, borate of polyvalent metal, or the like can also be used instead of the metal chloride. Examples of the condensation catalyst include ammonium molybdate, molybdic acid, Bodiummolybdate, silicomolybdic acid, phosphomolybdic acid, molybdenum oxide, ammoniumphosphomolybdate, phosphotungstomolybdic acid, molybdenum carbonyl, and the like. In general, ammonium molybdate is preferred. As the inert organic solvent, a polyethylene glycol dialkyl ether is used. The polyethylene glycol dialkyl ether (polyglyme) represents the compound represented by the following formula (II): R 1 O(CH 2 CH 2 O) n R 2 wherein, R 1 and R 2 independently represents an alkyl group having 1 to 8, preferably 1 to 4 carbon atoms, and n represents an integer of not less than 2, preferably from 2 to 10, more preferably from 3 to 5). Specific examples thereof include diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), polyethylene glycol dimethyl ether (a mixture of polyglymes in which n is 2 or 3 or more), diethylene glycol diethyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, , and the like. These can be used alone or in combination. The polyethylene glycol dimethyl ether (generally referred to as polyglyme) represented by the formula (II) in which both R 1 and R 2 represent a methyl group is preferred. The particularly preferable examples include a polyglyme having a boiling point of not less than 180°C, for example, triglyme, tetraglyme, and the like. The polyglyme has excellent miscibility with the phthalic acid derivative and the product, is inactive against the above-described reaction components such as the phthalocyanine derivatives , and the like, is water-miscible, and has no toxicity. By using the polyglyme as the inert organic solvent, the reactants does not flocculate, and the finely dispersed condition is maintained throughout the reaction. As a result, a uniform slurry reaction, and a condensation reaction at high temperature (from about 180 to about 200°C) are possible. Furthermore, the polyglyme can be removed by washing with water and handling thereof is safe. In the method of the present invention for preparing the deodorizer or metallophthalocyanine, the above-described reaction components are heated in an inert organic solvent to conduct a condensation reaction, by first. The urea is used in an amount of not less than 3 mol, preferably from 3 to 6 mol, the condensation catalyst is used in an amount of from 0.1 to 5% by mol, preferably from 0.1 to 1% by mol, and the metal halide is used in an amount of not less than 1/4 mol, preferably from 1/4 to 1/2, wherein the amount of the reactants is based on 1 mol of the phthalic acid derivative(s). The amount used of the inert organic solvent is not particularly limited to, but in case of the polyglyme, it is used in an amount of 2-fold or more, preferably from 4 to 6-fold, based on the weight of the phthalic acid derivative. In particular, when a deodorizer is prepared, a phthalic acid derivative having a nitro group such as 3-nitrophthalic acid, 4-nitrophthalic acid, triammonium sulfophthalate, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, 3-nitrophthalimide, 4-nitrophthalimide, 4-chloro-5-nitrophthalimide, and the like, together with a phthalic acid derivative having an acidic group such as trimellitic anhydride, pyromellitic anhydride, 3-sulfophthalic anhydride, 4-sulfophthalic anhydride, trimellitic acid, pyromellitic acid, 3-sulfophthalic acid, 4-sulfophthalic acid, and Na, K, and NH 3 salts thereof, and amide derivatives thereof, and the like, are used as the phthalic acid derivative. The both phthalic acid derivatives are used in suitable ratio as shown in the following examples for the condensation reaction. The condensation reaction is kept at temperature of from 180 to 200°C for 2 to 10 hours. In a preferred embodiment, the reaction is kept at temperature of from about 130 to 160°C for 2 to 4 hours, or at temperature of from 180 to 200°C for 4 hours or more, preferably for 4 to 10 hours. After completion of the condensation reaction, the reaction mixture is cooled to about 100°C, hot water (about 80°C) is added to the reaction mixture, and the mixture is stirred for 2 to 3 hours with refluxing. Then, filtered at high temperature and washing with hot water of the reaction mixture are repeated for several times to remove an inert organic solvent and an inorganic impurity. Since the organic solvent used in the present invention is water-soluble, the organic solvent can be easily separated from the reaction product by washing with water. The resulting solid is optionally washed with acetone or DMF, and dried to obtain metallophthalocyanine. When the above-described reaction is conducted by using a phthalic acid derivative having a nitro group and a phthalic acid derivative having a carboxyl group or sulfonic acid group for preparing a deodorizer (nitrocarbamoilphthalocyaninato)metal or (nitrosulfamoilphthalocyaninato)metal are obtained. Metallophthalocyanine having an acid amide group is generally water-insoluble. However, the metallophthalocyanine can be made to water-soluble by hydrolyzing the acid amide group. That is, the acid amide group is converted to an acidic group, and water-soluble phthalocyanine having the acidic group (for example, (nitrocarboxyphtharocyaninato)metal or (nitrosulfophthalocyaninato)metal is water-soluble. The method for hydrolyzingmetallophthalocyanine having an acid amide group is well known to those skilled in the art. For example, after removal of an organic solvent in the condensation reaction, a wet cake of the obtained water-insoluble metallophthalocyanine is dispersed in a 5 to 30% aqueous alkali (for example, sodium hydroxide and potassium hydroxide) solution, and the mixture is stirred for 2 to 12 hours with refluxing. After cooling, a mineral acid (for example, concentrated hydrochloric acid, sulfuric acid) is added to obtain a slurry. The slurry is filtered, re-dispersed in hot water or water to remove salt components, inorganic and organic impurities, optionally washed with acetone or DMF, and dried, to obtain a water-soluble metallophthalocyanine. When the condensation product is (nitrosulfophthalocyaninato)metal, alcohols (for example, methanol) are added into the reaction mixture, and the mixture is stirred for 2 to 3 hours with refluxing. Then, the reaction mixture is filtered at high temperature and washed with methanol to remove an inert organic solvent and an inorganic impurity, and the like. Solubility of (nitrosulfophthalocyaninato)metal into alcohols is poor, the (nitrosulfophthalocyaninato)metal can be made to a slurry, and it easily can be separated from the organic solvent used in the reaction. The (nitrocarboxyphthalocyaninato)metal or (nitrosulfophthalocyaninato)metal (a nitrophthalocyanine derivative) is then reduced in liquid phase by using a reducing agent. Examples of the reducing agent include sodium sulfide, sodium polysulfide, a sulfur compound such as Na 2 S 2 O 4 , hydrazine-raney nickel, Sn-HCl, Fe-HCl, SnCl 2 -HCl, Fe(OH) 2 , catalytic H 2 , and the like. The reaction mixture is kept at temperature of not less than room temperature and from about 60 to 70°C for 2 to 3 hours and 3 to 10 hours. When sodium sulfide 9 hydrate is used as a reducing agent, the amount used is preferably from about 5 to 10-fold mol as to a mono- or dinitrophtalocyanine derivative, and preferably from about 10 to 20-fold mol as to a tri or tetranitrophtalocyanine derivative. It has been reported that a phthalic acid derivative is not suitable as a raw material for directly synthesizing a phthalocyanine pigment which is fine by comparison with phthalonitrile and 1,3-diiminoisoindolines since the phthalic acid derivative is not easily condensed in a hydrophilic organic solvent and scarcely forms metallophthalocyanine ("Dye and Chemical", Vol. 23, No. 11, pp 225 to 227, (1978), "Recent technique for preparing phthalocyanine pigment [II]"). Therefore, a hydrophilic organic solvent has been said unsuitable as an organic solvent used in the urea method. For example, when an alcohol-based water-soluble solvent such as polyethylene glycol or ethylene glycol monoethyl ether is used as a solvent, intended metallophthalocyanine is scarcely obtained or the yield is low. However, the present inventors have found that water-soluble metallophthalocyanine can be synthesized at high yield by the urea method when the specific hydrophilic organic solvent, that is, a polyethylene glycol dialkyl ether having high boiling point (for example, polyglyme), is used. For example, when 4-nitrophthalimide (1) is used as a phthalic acid derivative having a nitro group, trimellitic anhydride (2) or pyromellitic dianhydride (3) is used as a phthalic acid derivative having an acidic group and these are mixed at a suitable ratio and subjected to a condensation reaction by the urea method in polyglyme, in the process of the present invention, there is obtained nitrometallophthalocyaninecarbamic acid. This compound is then hydrolyzed, and reduced in an aqueous medium by using a reducing agent such as sodium sulfide 9 hydrate to obtain water-soluble metallophthalocyanine (4) having a carboxyl group as an acidic group. In the formula, "Met" is central metal, preferably cobalt or iron, and m and p is the same as defined above. Further, for example, when 4-nitrophthalic anhydride (5) or 4-nitrophthalimide (1) is used as a phthalic acid derivative having a nitro group, 4-sodiosulfophthalic anhydride (6) is used as a phthalic acid derivative having an acidic group and these are mixed at a suitable ratio and subjected to a condensation reaction by the urea method in polyglyme, there is obtained (nitrosulfophthalocyaninato)metal. Next, this compound is reduced in an aqueous-phase by using a reducing agent such as sodium sulfide 9 hydrate to obtain a water-soluble metallophthalocyanine (7) having a sodium sulfonate group as an acidic group. In the formula, "Met" is central metal, preferably cobalt or iron, and m and p is the same as defined above. Metallophthalocyanine having an amino group as a substituent and metallophthalocyanine having an acidic group or alkali metal salt thereof as a substituent may be mixed, and the mixture may also be used as a deodorizer for effectively deodorizing an aldehyde-origin odor. However, the metallophthalocyanine having an amino group as a substituent is water-insoluble, and such a deodorizer can not be dissolved in a aqueous solvent for use. The number of an amino group of the metallophthalocyanine having an amino group as a substituent is from 1 to 16, generally from 4 to 8, preferably 4 or 8. The number of an acidic group or alkali metal salt thereof of the metallophthalocyanine having an acidic group or alkali metal salt thereof as a substituent is from 1 to 16, generally from 4 to 8, preferably 4 or 8. The mixing ratio of the metallophthalocyanine having an amino group as a substituent and the metallophthalocyanine having an acidic group or alkali metal salt thereof as a substituent can be appropriately controlled depending on desired deodorizing ability and the number of a substituent. For example, 10 to 90% by weight, preferably 20 to 80% by weight of the metallo- phthalocyanine having an amino group as a substituent and 10 to 90% by weight, preferably 20 to 80% by weight of the metallophthalocyanine having an acidic group or alkali metal salt thereof can be combined. The metallophthalocyanine having an amino group as a substituent and the metallophthalocyanine having an acidic group or alkali metal salt thereof as a substituent used herein can be prepared by appropriately selecting and using phthalic acid derivatives as a raw material. According to the process of the present invention, a metallophthalocyanine represented by the following formula (III) can be preferably prepared. In the formula, R represents a nitro group, halogen atom, alkyl group, alkoxy group, amino group, carboxyl group, alkali metal salt of carboxyl group, and the like, "Met" represents polyvalent metal such as Cu, Co, Fe, Ni, Al, and Cr. The metallophthalocyanine thus obtained is useful as a deodorizer, photorecording material, photoconductive material, dye and pigment for coloring, functional colorant or the like. For example, water-insoluble (tetranitrophthalocyaninato)copper is useful as a precursor of a functional phthalocyanine for various uses. Also, this nitrophthalocyanine can be reduced to obtain (tetraaminophthalocyaninato)copper. Further, a variety of (diazophthalocyaninato)copper derivatives can be obtained by diazotization of the amino compound. The deodorizer consisting of a metallophthalocyanine of the present invention can deodorize bad smell consisting of an amine-origin odor such as an ammonia odor and of a sulfur-origin odor such as a mercaptan odor, and can show high deodorizing ability for an aldehyde-origin odor which is one of main components of a tobacco odor. It therefore remove a variety of bad smell in living atmosphere in various forms. The deodorizing ability of the deodorizer shows excellent durability since µ-oxo dimerization or removal of the central metal in an alkali solution does not occur. The process of the present invention for preparing a deodorizer or metallophthalocyanine has the following merits by comparison with the conventional urea method. The process shorten the production period and reduce the production cost, and is very advantageous when a scale of the production becomes large. i) The solvent can be removed from the reaction product by simple procedure, that is, filtration and water-washing, and therefore no step is required for distilling the solvent under reduced pressure after completion of the reaction. ii) Reaction and purification can be conducted on one step continuous procedure. iii) There occur no problem that the reaction product adheres and sticks to the wall of a vessel, and becomes impossible to stir. iv) The solvent has no toxicity and handling thereof is safe. v) As a result, a metallophthalocyanine which has high purity and stable quality is obtained by simple and safe process in high yield. The following examples further illustrate the present invention in detail. Example 1 Synthesis of (aminotricarboxyphthalocyaninato)cobalt. Into a 3000 ml four neck flask made of glass equipped with necessary equipment such as a stirrer, reflux condenser, and the like were charged 144.2 g of trimellitic anhydride, 48.1 g of 4-nitrophthalimide, 270 g of urea, 5.0 g of ammonium molybdate, 71.4 g of cobalt chloride 6 hydrate, and 1000 ml of triglyme. The resulting mixture was uniformly stirred for about 15 minutes at room temperature, then the mixture was stirred for 6 to 7 hours at temperature of from 125 to 130°C, and subsequently further stixred for 7 to 8 hours at temperature of from 180 to 190°C. After cooling, 1500 ml of hot water of about 80°C was gradually added to the reaction mixture, and further stirred for 3 hours with refluxing. After filtration at high temperature, the mixture was washed with 10 L of hot water. The wet cake was dispersed in 2.0 L of 20% aqueous potassium hydroxide solution, and hydrolyzed for 12 hours with refluxing. About 780 ml of concentrated hydrochloric acid was added with maintaining the temperature not more than 20°C in an ice bath to regulate pH thereof to 1 to 2, then the mixture was stirred for about one hour at room temperature. After filtration, the resulted wet cake was desalted by washing with 10 L of water, then dried to obtain 97.4 g of (nitrotricarboxyphthalocyaninato)cobalt. 85.0 g of the resulted powder was dispersed in 500 ml of water, and 66.0 g of sodium sulfide 9 hydrate was gradually added. The mixture was heated with stirring for 2 hours at temperature of 30°C and further for 5 hours at temperature of from 60 to 70°C. The mixture was cooled to room temperature, then, to this was added 2500 ml of water, pH thereof was regulated to about 4.0 with hydrochloric acid, further stirred for one hour, filtered, subsequently washed with about 15 L of water, dried, to obtain 90.3 g of a blue solid. The structure of the resulted compound is shown below. Example 2 Synthesis of (diaminodicarboxyphthalocyaninato)cobalt. Into a 3000 ml four neck flask made of glass equipped with necessary equipment such as a stirrer, reflux condenser, and the like were charged 96.1 g of trimellitic anhydride, 96.1 g of 4-nitrophthalimide, 270 g of urea, 5.0 g of ammonium molybdate, 71.4 g of cobalt chloride 6 hydrate, and 1000 ml of triglyme. The resulting mixture was uniformly stirred for about 15 minutes at room temperature, then the mixture was stirred for 6 to 7 hours at temperature of from 125 to 130°C, and subsequently further stirred for 7 to 8 hours at temperature of from 180 to 190°C. After cooling, 1500 ml of hot water of about 80°C was gradually added to the reaction mixture, and further stirred for 3 hours with refluxing. After filtration at high temperature, the mixture was washed with 10 L of hot water. The wet cake was dispersed in 2.0 L of 20% aqueous potassium hydroxide solution, and hydrolyzed for 12 hours with refluxing. About 780 ml of concentrated hydrochloric acid was added with maintaining the temperature not more than 20°C in an ice bath to regulate pH thereof to 1 to 2, then the mixture was stirred for about one hour at room temperature. After filtration, the resulted wet cake was desalted by washing with 10 L of water, then dried to obtain 130.9 g of (dinitrodicarboxyphthalocyaninato)cobalt. 75.0 g of the resulted powder was dispersed in 500 ml of water, and 125.0 g of sodium sulfide 9 hydrate was gradually added. The mixture was heated with stirring for 2 hours at temperature of 30°C and further for 5 hours at temperature of from 60 to 70°C. The mixture was cooled to room temperature, then, to this was added 2500 ml of water, pH thereof was regulated to about 4.0 with hydrochloric acid, further stirred for one hour, filtered, subsequently washed with about 15 L of water, dried, to obtain 74.6 g of a blue solid. The structure of the resulted compound is shown below. Example 3 Synthesis of (triaminocarboxyphthalocyaninato)cobalt. Into a 3000 ml four neck flask made of glass equipped with necessary equipment such as a stirrer, reflux condenser , and the like were charged 48.1 g of trimellitic anhydride, 144.2 g of 4-nitrophthalimide, 270 g of urea, 5 g of ammonium molybdate, 71.4 g of cobalt chloride 6 hydrate, and 1000 ml of triglyme. The resulting mixture was uniformly stirred for about 15 minutes at room temperature, then the mixture was stirred for 6 to 7 hours at temperature of from 125 to 130°C, and subsequently further stirred for 7 to 8 hours at temperature of from 180 to 190°C. After cooling, 1500 g of hot water of about 80°C was gradually added to the reaction mixture, and further stirred for 3 hours with refluxing. After filtration at high temperature, the mixture was washed with 10 L of hot water. The wet cake was dispersed in 2.0 L of 20% aqueous potassium hydroxide solution, and hydrolyzed for 12 hours with refluxing. About 780 ml of concentrated hydrochloric acid was added with maintaining the temperature not more than 20°C in an ice bath to regulate pH thereof to 1 to 2, then the mixture was stirred for about one hour at room temperature. After filtration, the resulted wet cake was desalted by washing with 10 L of water, then dried to obtain 156.0 g of (trinitrocarboxyphthalocyaninato)cobalt. 112.5 g of the resulted powder was dispersed in 500 ml of water, and 270.0 g of sodium sulfide 9 hydrate was gradually added. The mixture was heated with stirring for 2 hours at temperature of 30°C and further for 5 hours at temperature of from 60 to 70°C. The mixture was cooled to room temperature, then, to this was added 2500 ml of water, pH thereof was regulated to 5.5 to 6.0 until the solubility of the product reaches minimum value with hydrochloric acid and an aqueous sodium hydroxide solution, filtered, subsequently washed with about 15 L of water, dried, to obtain 122.9 g of a blue solid. The structure of the resulted compound is shown below. Example 4 Synthesis of (diaminodicarboxyphthalocyaninato)cobalt. In to a 3000 ml four neck flask made of glass equipped with necessary equipment such as a stirrer, reflux condenser , and the like were charged 96.1 g of trimellitic anhydride, 96.1 g of 4-nitrophthalimide, 270 g of urea, 5.0 g of ammonium molybdate, 48.7 g of anhydrous iron (I) chloride, and 1000 ml of tetraglyme. The resulting mixture was uniformly stirred for about 15 minutes at room temperature, then the mixture was stirred for 6 to 7 hours at temperature of from 125 to 130°C, and subsequently further stirred for 7 to 8 hours at temperature of from 180 to 190°C. After cooling, 1500 ml of hot water of about 80°C was gradually added to the reaction mixture, and further stirred for 3 hours with refluxing. After filtration at high temperature, the mixture was washed with 10 L of hot water. The wet cake was dispersed in 2.0 L of 20% aqueous potassium hydroxide solution, and hydrolyzed for 12 hours with refluxing. About 740 ml of concentrated hydrochloric acid was added with maintaining the temperature not more than 20°C in an ice bath to regulate pH thereof to 1 to 2, then the mixture was stirred for about one hour at room temperature. After filtration, the resulted wet cake was desalted by washing with 10 L of water, then dried to obtain 93.8 g of (dinitrodicarboxyphthalocyaninato)iron (III). 14.9 g of the resulted powder was dispersed in 500 ml of water, and 125.0 g of sodium sulfide 9 hydrate was gradually added. The mixture was heated with stirring for 2 hours at temperature of 30°C and further for 5 hours at temperature of from 60 to 70°C. The mixture was cooled to room temperature, then, to this was added 500 ml of water, pH thereof was regulated to about 4.0 with hydrochloric acid, further stirred for one hour, filtered, subsequently washed with about 15 L of water, dried, to obtain 14.8 g of a blue solid. The structure of the resulted compound is shown below. Example 5 Synthesis of sodium salt of (diaminodisulfonicphthalocyaninato)cobalt. Into a 3000 ml four neck flask made of glass equipped with necessary equipment such as a stirrer, reflux condenser, and the like were charged 96.1 g of sodium 4-sulfonate phthalic anhydride, 96.1 g of 4-nitrophthalimide, 270 g of urea, 5.0 g of ammonium molybdate, 71.4 g of cobalt chloride 6 hydrate, and 1000 ml of triglyme. The resulting mixture was uniformly stirred for about 15 minutes at room temperature, then the mixture was stirred for 6 to 7 hours at temperature of from 125 to 130°C, and subsequently further stirred for 7 to 8 hours at temperature of from 180 to 190°C. After cooling, 1500 g of methanol was gradually added to the reaction mixture, and further stirred for 3 hours with refluxing. After filtration at high temperature, the mixture was washed with 10 L of dropping methanol 14.9 g of the resulted powder was dispersed in 500 ml of water, and 125.0 g of sodium sulfide 9 hydrate was gradually added. The mixture was heated with stirring for 2 hours at temperature of 30°C and further for 5 hours at temperature of from 60 to 70°C. The mixture was cooled to room temperature, then, to this was added 500 ml of water, pH thereof was regulated to about 4.0 with hydrochloric acid, further stirred for one hour, filtered, subsequently washed with about 15 L of dropping methanol, dried, to obtain 14.8 g of a blue solid. The structure of the resulted compound is shown below. Example 6 Synthesis of (tetraaminophthalocyaninato)copper. Into a 5000 ml four neck flask made of glass equipped with necessary equipment such as a stirrer, reflux condenser, and the like were charged 500 g of 4-nitrophthalimide, 660 g of urea, 20 g of ammonium molybdate, 70 g of copper (I) chloride and 2500 ml of triglyme. The resulting mixture was stirred for 1 to 2 hours at temperature of from 125 to 135°C, and subsequently further stirred for 6 hours at temperature of from 160 to 180°C. After cooling, 2500 g of hot water of about 80°C was gradually added to the flask, and further stirred for 3 hours with refluxing. The reaction product was filtered at high temperature, and washed with 10 L of hot water. The filtered material was dried to obtain 460 g of (tetranitrophthalocyaninato) copper. 10.4 g of the resulted (tetranitrophthalocyaninato) copper was dispersed in 300 ml of water, and 49 g of sodium sulfide 9 hydrate was gradually added. The mixture was heated with stirring for 3 hours at temperature of 30°C and further for 5 hours at temperature of from 60 to 70°C. The mixture was cooled to room temperature, then, to this was added 2500 ml of water, pH thereof was regulated to about 4.0 with hydrochloric acid. This reaction product was further stirred for one hour, filtered, subsequently washed with about 15 L of water. The filtered material was dried to obtain 7.6 g of (tetraaminophthalocyaninato)copper. Example 7 Synthesis of (tetranitrophthalocyaninato)copper. Into a 5000 ml four neck flask made of glass equipped with necessary equipment such as a stirrer, reflux condenser , and the like were charged 500 g of 4-nitrophthalimide, 660 g of urea, 20 g of ammonium molybdate, 70 g of copper (I) chloride and 2500 g of triglyme. The resulting mixture was stirred for 1 to 2 hours at temperature of 130°C, and subsequently stirred for 2 hours at temperature of 160°C, then, further stirred for 4 hours at temperature of 180°C. After cooling to about 100°C, 2500 g of hot water of about 80°C was gradually added, and further stirred for 2 to 3 hours with refluxing. The reaction product was filtered at high temperature, then washed with 10 L of hot water. The product was dried to obtain 460 g of an intended compound at a yield of 93.6%. The result of the elemental analysis of this compound and the yield are shown in Table 2. Example 8 Synthesis of (tetracarboxyphthalocyaninato)cobalt. Into a 10000 ml four neck flask made of glass equipped with necessary equipment such as a stirrer, reflux condenser, and the like were charged 1152 g of trimellitic anhydride, 1800 g of urea, 10 g of ammonium molybdate, 360 g of cobalt chloride 6 hydrate and 3000 g of triglyme. The resulting mixture was stirred for 1 hour at temperature of 130°C, and subsequently stirred for 4 hours at temperature of 200°C. The mixture was cooled to about 100°C, 5000 ml of hot water of about 80°C was then gradually added to the reaction mixture, and further stirred for 2 to 3 hours with refluxing. After filtration at high temperature, the mixture was washed with 30 L of hot water. Then, the resulted wet cake was dropped into 6000 parts of 20 to 30% aqueous potassium hydroxide solution, and the mixture was stirred for 12 hours with refluxing. The reaction mixture was cooled using a water/ice bath, 4130 g of concentrated hydrochloric acid was added dropwise so that the temperature did not exceed 30°C, then the mixture was further stirred for one hour. The resulted slurry was filtered, and was desalted by washing with 80 to 100 L of water, then the product was dried to obtain 693.4 g of an intended compound at a yield of 61.9%. The result of the elemental analysis of this compound, the yield and molecule absorptivity coefficient ε are shown in Table 3. Example 9 Synthesis of (tetracarboxyphthalocyaninato)iron(III). Into a 5000 ml four neck flask made of glass equipped with necessary equipment such as a stirrer, reflux condenser, and the like were charged 384 g of trimellitic anhydride, 600 g of urea, 2 g of ammonium molybdate, 81 g of iron (III) chloride and 1500 g of tetraglyme. The resulting mixture was stirred for 1 hour at temperature of 130°C, and subsequently stirred for 6 hours at temperature of 180°C. The mixture was cooled to about 100°C, 2500 g of hot water of about 80°C was then gradually added to the reaction mixture, and further stirred for 2 to 3 hours with refluxing. After filtration at high temperature, the mixture was washed with 15 L of hot water. Then, the resulted wet cake was dropped into 3000 parts of 20 to 30% aqueous potassium hydroxide solution, and the mixture was stirred for 12 hours with refluxing. The reaction mixture was cooled using a water/ice bath, 2065 g of concentrated hydrochloric acid was added dropwise so that the temperature did not exceed 30°C, then the mixture was further stirred for one hour. The resulted slurry was filtered, and was desalted by washing with 20 to 50 L of water, then the product was dried to obtain 265 g of an intended compound at a yield of 71.2%. The result of the elemental analysis of this compound and the yield are shown in Table 2. Example 10 Synthesis of (octacarboxyphthalocyaninato)iron(III). Into a 5000 ml four neck flask made of glass equipped with necessary equipment such as a stirrer, reflux condenser, and the like were charged 300 g of trimellitic dianhydride, 600 g of urea, 10 g of ammonium molybdate, 100 g of iron (III) chloride and 1500 g of tetraglyme. The resulting mixture was stirred for 1 hour at temperature of 130°C, and subsequently stirred for 8 hours at temperature of 200°C. The mixture was cooled to about 100°C, 2500 ml of hot water of about 80°C was then gradually added to the reaction mixture, and further stirred for 2 to 3 hours with refluxing. After filtration at high temperature, the mixture was washed with 15 L of hot water. Then, the resulted wet cake was dropped into 3000 parts of 5 to 10% aqueous potassium hydroxide solution, and the mixture was stirred for 2 hours with refluxing. The reaction mixture was cooled using a water/ice bath, 520 g of concentrated hydrochloric acid was added dropwise so that the temperature did not exceed 30°C, then the mixture was further stirred for one hour. The resulted slurry was filtered, and was desalted by washing with 20 to 50 L of water, then the product was dried to obtain 160 g of an intended compound at a yield of 51.0%. The result of the elemental analysis of this compound and the yield are shown in Table 2. Example 11 Synthesis of cobaltphthalocyanine. Into a 10 L four neck flask made of glass equipped with necessary equipment such as a stirrer, reflux condenser, and the like were charged 741 g of phthalic anhydride, 1500 g of urea, 10 g of ammonium molybdate, 328 g of cobalt chloride 6 hydrate and 3500 g of triglyme. The resulting mixture was stirred for 1 hour at temperature of 130°C, and subsequently stirred for 6 hours at temperature of 200°C. The mixture was cooled to about 100°C, 4000 ml of hot water of about 80°c was then gradually added to the reaction mixture, and further stirred for 2 to 3 hours with refluxing. After filtration at high temperature, the mixture was washed with 30 L of hot water. After drying, 636 g of an intended compound was obtained at a yield of 89.1%. The result of the elemental analysis of this compound and the yield are shown in Table 2. The phthalocyanine producing material, metallizing agent and reaction solvent used in the above-described examples were substituted by the above-described phthalic acids or functional derivatives thereof and metallizing agents to synthesize various metallophthalocyanines. All results were excellent, and there could be synthesized metallophthalocyanines having high purity which'require no pigmentation treatment directly (by one pot). Comparative Example 1 Synthesis of (tetracarboxyphthalocyaninato)cobalt. Into a 100 ml four neck flask made of glass equipped with necessary equipment such as a stirrer, reflux condenser, and the like were charged 3.84 g of trimellitic anhydride, 12.0 g of urea, 0.5 g of ammonium molybdate, 1.30 g of cobalt chloride 6 hydrate and 60 g of nitrobenzene, and a condensation reaction was conducted according to the Weilar method. The nitrobenzene solvent was removed under reduced pressure from the reaction mixture, then, to this was added 100 ml of hot water, and the mixture was further stirred with heating. After filtration, the product was hydrolyzed with 60 ml of 20 to 30% aqueous potassium hydroxide solution, the mixture was filtered, washed with water and dried to obtain 3.65 g of an intended compound at a yield of 97.7%. The result of the elemental analysis of this compound, the yield and molecule absorptivity coefficient ε are shown in Table 2. Comparative Example 2 Synthesis of (tetracarboxyphthalocyaninato)cobalt. The same procedure as in Comparative Example 1 was conducted except that trichlorobenzene was used as a reaction solvent instead of nitrobenzene to obtain 3.90 g of an intended compound at a yield of 104.4%. The result of the elemental analysis of this compound, the yield and molecule absorptivity coefficient ε are shown in Table 3. Comparative Example 3 Synthesis of (tetracarboxyphthalocyaninato)cobalt. The same procedure as in Example 8 was conducted except that diethylene glycol was used as a reaction solvent instead of triglyme to obtain no intended phthalocyanine. Comparative Example 4 Synthesis of (tetracarboxyphthalocyaninato)iron(III). The same procedure as in Example 9 was conducted except that ethylene glycol monoethyl ether (ethyl cellosolve) was used as a reaction solvent instead of tetraglyme to obtain no intended phthalocyanine. Example 8 Comparative Example 1 Comparative Example 2 Yield(%) 61.9 97.9 104.4 ε (λ1) 37500 27500 42500 ε (λ2) 47000 37000 33800 Element analys. Calc. value Found value Calc. value Found value Calc. value Found value C 57.83 57.40 57.83 53.23 57.83 53.03 H 2.14 2.08 2.14 1.31 2.14 0.81 N 14.99 14.36 14.99 15.36 14.99 15.13 Metal 7.90 7.82 7.90 7.69 7.90 7.08 (Co) (Co) (Co) In Examples 1 to 5 and 7 to 11, the reaction product from which a solvent had been removed after the condensation reaction was a uniform slurry. On the other hand, in Comparative Examples 1 and 2, the reaction product was set and adhered to the wall of a vessel, and partially became impossible to stir. In comparative examples, high yield was obtained, the reason for this is that the product contained a large amount of impurities which were by-produced by this reaction. This is evident from the molecule absorptivity coefficients and the results of elemental analysis as to Example 8 and Comparative Examples 1 and 2 shown in Table 3. Further, to investigate purity of the product, infrared absorption spectra of (tetracarboxyphthalocyaninato)cobalt in Example 8 and Comparative Example 1 are shown in Figs. 1 and 2. Though both spectra have specific absorption derived from (tetracarboxyphthalocyaninato)cobalt, it is known from the spectra that a carbonyl absorption (ν c=o ) appears at about 1700 cm -1 at the same strength as the absorption derived from a phthalocyanine bone in Example 8, and on the other hand, in Comparative Example 1, the relative strength of the carbonyl absorption (ν c=o ) is weak and the purity is low. The same results were also obtained as to Comparative Example 2.

Claims: A process for preparing a metallophthalocyanine compound by the urea method, wherein polyethylene glycol dialkyl ether is used as a reaction solvent. A process for preparing a metallophthalocyanine compound which comprises the step of: heating a phthalic acid derivative, urea, and metal halide, in polyethylene glycol dialkyl ether, in the presence of a condensation catalyst. The process according to claim 2, wherein the phthalic acid derivative is at least one selected from phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, 4-sulfophthalic acid, alkyl-substituted phthalic acid, alkoxy-substituted phthalic acid, ammonium salts of phthalic acid, metal salts (Na salt, K salt) of phthalic acid, phthalate, phthalamide, phthalyl halogenate, phthalimide, o-cyanobenzoic acid, and o-cyanobenzoate. The process according to any of claims 1 to 3, wherein the polyethylene glycol dialkyl ether is polyglyme.

Inventors: YAMASAKI YASUHIRO, YAMASHITA TATSUTO, YAMASAKI, YASUHIRO, YAMASHITA, TATSUTO
Applicants: ORIENT CHEMICAL IND, ORIENT CHEMICAL INDUSTRIES, LTD.
Application year: 1997
Main classification: A61L9
IPC codes: A61L9, C09B47