JPH0739551B2 - Method for producing copper phthalocyanine compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a copper phthalocyanine compound, and more specifically, to a reaction method in the method for producing a copper phthalocyanine compound constituted by a two-step reaction. It is about improvement.

<Prior Art> As a method for producing a copper phthalocyanine compound, a method of reacting phthalic acid and / or a derivative thereof with ammonia and / or urea, copper and / or a compound thereof in an organic solvent in the presence of a catalyst is conventionally preferred. Known,
Widely used industrially. From the viewpoint of economy and safety, phthalic anhydride is most widely used as the starting phthalic acid derivative.

In the case of producing copper phthalocyanine from phthalic anhydride, stoichiometrically, 1 mol of urea is required for 1 mol of phthalic anhydride, but in reality, the nitrogen atom in urea is sufficiently efficient to form a phthalocyanine skeleton. It does not participate in the reaction, but escapes to the outside of the reaction system as ammonia and becomes a loss.
The urea used in the reaction to compensate for this is in considerable excess compared to the stoichiometric amount. When urea is used in a large excess, it contains a large amount of decomposition products of copper phthalocyanine urea, which not only lowers its purity but also causes excess ammonia to be released as waste, resulting in eutrophication of water quality, etc. Can also cause environmental pollution. Moreover, the excessive use of urea is economically disadvantageous.

From this point of view, ammonia generated during the production of copper phthalocyanine compound is circulated and reused and reacted with phthalic acid and / or its derivative in an organic solvent to reduce the usage amount of urea and / or its derivative and the amount of ammonia waste. A method for producing phthalic acid and / or a derivative thereof with ammonia (first step reaction), a reaction mixture of the first step with copper and / or a compound thereof, urea and And / or its derivative (reaction of the second step), and the ammonia-containing mixed gas generated in the reaction of the second step is circulated in the first step to react with phthalic acid and / or its derivative under pressure. And the like (Japanese Patent Publication No. 52-32886).

<Problems to be Solved by the Invention> However, phthalimide and / or phthalimide produced by the reaction of phthalic acid and / or its derivative with ammonia
Alternatively, when a hydrocarbon-based organic solvent such as alkylbenzene or light oil, which is highly safe in terms of occupational health, is used as the organic solvent, its derivative has a very low affinity for these organic solvents, and therefore, is in a safe suspended state. It could not exist, and a large amount adhered to the wall of the reactor, the stirring device, etc., causing an increase in the stirring load and an eccentricity of the center of gravity of the stirring device, making it difficult to continue the reaction in the first stage. In addition, it was impossible to transfer phthalimide or the like to the second-stage reactor.

Therefore, conventionally, an organic solvent having a high affinity for nitrobenzene, trichlorobenzene, phthalimide, etc. has been used as the organic solvent as described in JP-B-52-32886. However, nitrobenzene is designated as a deleterious substance and is a highly toxic substance, and special care must be taken when handling it. In addition, trichlorobenzene is not only a problem in terms of toxicity, but also has the drawback of producing pentachlorobiphenyl and the like in the copper phthalocyanine compound manufacturing process, and both are not necessarily preferable as organic solvents used in industrial processes. There wasn't.

<Means for Solving Problems> In view of the present situation, the present inventors have found that even if a hydrocarbon-based organic solvent that is safer in terms of occupational health is used, phthalimide and / or its derivative adheres to a reactor or the like. As a result of intensive research on a method of recycling and recycling the ammonia generated during the production of the copper phthalocyanine compound,
When phthalic acid and / or its derivative is reacted with ammonia or an ammonia-containing gas in the presence of a phthalocyanine compound in the first step, when an organic solvent having an extremely low affinity such as a hydrocarbon organic solvent is used However, it was found that the phthalimide and / or its derivative formed did not adhere to the reactor wall or the stirring device at all, and the phthalimide and / or its derivative was obtained in a fine and stable suspension state, thus completing the present invention. Came to let.

That is, the present invention provides the production of a copper phthalocyanine compound from phthalic acid and / or a derivative thereof, ammonia and / or an ammonia-containing mixed gas, copper and / or a compound thereof, and urea and / or a derivative thereof. a) reacting phthalic acid and / or its derivative with ammonia and / or an ammonia-containing gas in a hydrocarbon-based organic solvent in the first step in the presence of a copper phthalocyanine compound, and (b) in the first step in the second step. The present invention provides a method for producing a copper phthalocyanine compound, which comprises reacting the reaction mixture obtained in the above reaction with copper and / or a compound thereof and urea and / or a derivative thereof in the presence of a catalyst.

The phthalic acid and its derivative used in the present invention include:
Examples thereof include phthalic acid, phthalic anhydride, phthalic acid salt, phthalic acid ester, phthalimide, phthalamic acid and the like, and halogen atom of these compounds, nitro group, sulfamoyl group, substituted derivative with carboxyl group and the like. Among them, phthalic acid, Phthalic anhydride, phthalates, phthalates and halogen atoms of these compounds,
Substituted derivatives of a nitro group, a sulfamoyl group, a carboxyl group and the like are preferable from the viewpoint of high ammonia recycling efficiency.

Examples of copper and its compounds include copper; cuprous or cupric halides, oxides, hydroxides, sulfates, nitrates, acetates, phthalates, and the like, among which cuprous chloride , Cuprous oxide is preferred. Examples of urea and its derivatives include urea and biuret.

The ratio of these used to 1 mol of phthalic acid and / or its derivative is usually such that ammonia and / or the ammonia-containing mixed gas is in the range of 0.2 to 5 mol, preferably 0.8 to 3 mol as ammonia, and copper and / or the compound thereof. Usually in the range of 0.2 to 0.3 mol, usually 1.2 to 3 mol of urea and / or its derivative, preferably 1.5 to 2.
It is in the range of 5 moles.

As the phthalocyanine compound to be present in the reaction of the first step in the method of the present invention, any compound having a phthalocyanine ring may be used, and any of a metal phthalocyanine compound and a metal-free phthalocyanine compound can be used, but among them, a copper phthalocyanine compound is preferable. Preferably, for example, copper phthalocyanine, chlorinated copper phthalocyanine, brominated copper phthalocyanine, chlorinated brominated copper phthalocyanine, phthalimidomethylated copper phthalocyanine, sulfamoyl copper phthalocyanine, N-substituted or N, N-disubstituted sulfamoyl copper phthalocyanine, carbamoyl copper Phthalocyanine, aminomethylated copper phthalocyanine, N-substituted or
N, N-disubstituted aminomethylated copper phthalocyanine, nitro copper phthalocyanine, copper phthalocyanine sulfonic acid or a salt thereof, carboxyl copper phthalocyanine or a salt thereof,
Copper phthalocyanine carboimide etc. can be mentioned.

The amount used is phthalic acid and / or its derivative 100
Usually 0.5 parts by weight or more, preferably 0.5 to 20 parts by weight.
In the range of parts by weight, phthalimide and /
Alternatively, the effect of dispersing the derivative is sufficiently exhibited, and the increase in the stirring load that occurs when a large amount of phthalocyanine compound is added and the decrease in the production efficiency of the copper phthalocyanine compound per volume of the reaction device are hardly present, and the ammonia can be reused. The range of 2 to 10 parts by weight is particularly preferable in terms of efficiency.

As the organic solvent used in the present invention, any of various already known organic solvents can be used, but among them, decane, dodecane, aliphatic hydrocarbons such as tetralin or alicyclic hydrocarbons; tert-butylbenzene, Alkylbenzenes such as tert-amylbenzene, tert-hexylbenzene, tetralin, isopropyltoluene, etc .; alkylbenzene mixtures such as Hysol P manufactured by Nippon Petrochemical Co., Solvesso 150 manufactured by Esso Standard Oil Co., Swazol 1800 manufactured by Maruzen Oil Co., Ltd .; diesel oil, kerosene, etc. A single hydrocarbon mixture or a mixture of two or more hydrocarbon mixtures is preferable in terms of occupational health safety. Aromatic nitro compounds such as nitrobenzene and o-nitrotoluene; halogenated hydrocarbons such as trichlorobenzene, chloronaphthalene and hexachlorobutadiene; sulfur compounds such as sulfolane and dialkylsulfone have industrial hygiene problems, but they can be used. Of course.

As the catalyst used in the reaction in the second step, any of various catalysts already known as catalysts for synthesizing copper phthalocyanine can be used, but molybdenum compounds such as molybdenum oxide and ammonium molybdate are particularly preferable. The amount used is usually in the range of 0.005 to 0.015 equivalents in terms of metal based on 1 mol of phthalic acid and / or its derivative.

In the method of the present invention, the first stage phthalic acid and / or
Alternatively, the reaction of the derivative with ammonia and / or an ammonia-containing mixed gas can be carried out in the presence or absence of a catalyst, but when a catalyst is used, it can be used for the synthesis of copper phthalocyanine in the second step. It is convenient to use the catalyst used. When a catalyst is used in the first-step reaction, it is not always necessary to add a new catalyst in the second-step reaction.

The reaction in the first step and the second step may be carried out under normal pressure or under pressure, and the reaction pressure depends on the type of organic solvent to be used and the reaction temperature. Usually in the range of 0-10kg / cm ² G, the second stage is usually 0
It may be determined in the range of ˜15 kg / cm ² G, preferably in the range where the second stage is the same as or slightly higher than the first stage. The reaction temperature is usually 100 to 300 ° C, preferably 140 to 250 ° C.
Is the range.

<Effects of the Invention> As described above, according to the method of the present invention, in the process of circulating and reusing ammonia generated during the production of copper phthalocyanine, toxic acid as a reaction solvent for the reaction of phthalic acid and / or its derivative with ammonia can be obtained. Since it becomes possible to use a hydrocarbon solvent such as alkylbenzene or light oil in place of nitrobenzene, trichlorobenzene, etc., which have many problems in terms of aspects, the significance of the present invention is great in terms of occupational health. Further, the phthalimide and the like produced by the reaction are dispersed in a fine suspension state, and as a result, the reaction with the ammonia and / or the ammonia-containing mixed gas proceeds more smoothly, so that the use of the ammonia generated in the second-stage reaction is utilized. The effect is increased and the economic advantage is great.

<Example> Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the examples, all parts and% are by weight.

Example 1 222 parts of phthalic anhydride and 16 parts of copper phthalocyanine were added to a reactor (A) equipped with a stirrer, a reflux device and a gas blowing pipe.
Parts, 2 parts of ammonium molybdate and 300 parts of tert-amylbenzene were charged and heated to 170 ° C. with stirring. On the other hand, 222 parts of phthalic anhydride was added to the pressure resistant reactor (B).
315 parts of urea, 48 parts of cuprous chloride, 2 parts of ammonium molybdate and 550 parts of tert-amylbenzene were charged, heated with stirring, heated to 200 ° C in 5 hours, and kept at 200 ° C for 2 hours. . The ammonia-containing gas generated along with the reaction is taken out from the pressure resistant reactor (B) while adjusting with a valve so that the reaction pressure is maintained at ² to 5 kg / cm ² , and introduced into the reactor (A) through a conduit, The reaction was carried out under normal pressure (first step reaction). After the reaction was completed, the phthalimide and the like produced in the reactor (A) were in a suspended state as fine needle crystals, and no adhesion to the reactor wall or the stirring device was observed. High-performance liquid chromatographic analysis of the produced phthalimide showed that unreacted phthalic anhydride was not detected (0.1% or less), and it consisted of phthalimide 99.5% and ammonium phthalate 0.5%. Next, the generated reaction product such as phthalimide is taken out and transferred to the evacuated pressure resistant reactor (B).
After adding 0 parts, cuprous chloride (48 parts) and tert-amylbenzene (250 parts), the mixture was heated with stirring, heated to 200 ° C in 5 hours, and kept at 200 ° C for 2 hours (second step). reaction). After allowing to cool, the reaction mixture was taken out, and the solvent was distilled off under reduced pressure. The residue was added to 2500 parts of 1% hydrochloric acid aqueous solution,
The mixture was stirred at about 70 ° C for 1 hour and then passed. The cake was thoroughly washed with warm water and then dried to obtain 223 parts of copper phthalocyanine having a purity of 95.2%.

Comparative Example 1 The first stage reaction was carried out in the same manner as in Example 1 except that 14 parts of copper phthalocyanine was not charged in the reactor (A). After completion of the reaction, the phthalimide, etc. produced in the reactor (A) adhered to the stirrer in bulk and adhered to the reactor wall thickly, less than 30% of which could be transferred in a dispersed state. It had to be scraped mechanically to get it out. When the phthalimide and the like that was taken out in this way and finely pulverized was analyzed by high performance liquid chromatography, 2% unreacted phthalic anhydride, 80% phthalimide,
Made up of 18% ammonium phthalate. Next, the produced phthalimide or the like was transferred to a pressure resistant reactor (B), and a second stage reaction was carried out in the same manner as in Example 1 to synthesize copper phthalocyanine. Copper phthalocyanine with a purity of 88.7% 218
Parts were obtained.

Example 2 The reaction of the first step and then the second step was carried out in the same manner as in Example 1 except that 14 parts of copper phthalocyanine charged in the reactor (A) was replaced with 9 parts of N-phenylsulfamoyl copper phthalocyanine. And copper phthalocyanine was obtained. The phthalimide and the like formed after the completion of the reaction in the first step were in a completely suspended state, and adhesion to the stirrer or the vessel wall was not recognized. The unreacted phthalic anhydride was not detected (less than 0.1%) by high-performance liquid chromatograph analysis of the produced phthalimide etc., and it consisted of phthalimide 99.4% and ammonium phthalate 0.6%.

Example 3 167 parts of phthalic anhydride and 83 parts of sodium hydrogen 4-chlorophthalate were used instead of 222 parts of phthalic anhydride charged to the reactor (A), and chlorine having a chlorine content of 5.8% was used instead of 16 parts of copper phthalocyanine. The first stage reaction was carried out in the same manner as in Example 1 except that 17 parts of copper phthalocyanine was used. The produced phthalimide, 4-chlorophthalimide, etc. were in a completely suspended state, and no adhesion to the stirrer or the vessel wall was observed. Next, the produced phthalimide, 4-chlorophthalimide and the like were transferred to a pressure resistant reactor (B) and a second stage reaction was carried out in the same manner as in Example 1 to synthesize a copper phthalocyanine compound.
7.8% chlorinated copper phthalocyanine (chlorine content 5.8%) 23
4 copies were obtained.

Comparative Example 2 The first stage reaction was carried out in the same manner as in Example 3 except that 17 parts of chlorinated copper phthalocyanine was not charged in the reactor (A). After the reaction was completed, phthalimide and 4 formed
-Chlorophthalimide, etc. adheres to the stirrer in a lump form and also adheres to the vessel wall thickly, and less than 30% can be transferred in a dispersed state. In order to take out the whole amount, it must be mechanically scraped off. I had to do it. Next, the produced phthalimide, 4-chlorophthalimide and the like were charged into a pressure resistant reactor (B) and a second step reaction was carried out in the same manner as in Example 1 to synthesize a copper phthalocyanine compound. 220 parts of phthalocyanine (chlorine content 5.8%) were obtained.

Example 4 Instead of 222 parts of phthalic anhydride, 210 parts of phthalic anhydride and 18 parts of nitrophthalimide are used, and tert-amylbenzene is used.
Example 1 except that 300 parts of kerosene was used instead of 300 parts.
In the same manner as above, the first step reaction and then the second step reaction were carried out to obtain copper phthalocyanine. The phthalimide and nitrophthalimide produced after the completion of the reaction in the first step were in a completely suspended state, and no adhesion to the stirrer or the vessel wall was observed.

Claims (2)

[Claims] 1. A method for producing a copper phthalocyanine compound from phthalic acid and / or a derivative thereof, ammonia and / or an ammonia-containing mixed gas, copper and / or a compound thereof, and urea and / or a derivative thereof. a) reacting phthalic acid and / or its derivative with ammonia and / or an ammonia-containing gas in a hydrocarbon-based organic solvent in the first step in the presence of a copper phthalocyanine compound, and (b) in the first step in the second step. The method for producing a copper phthalocyanine compound, which comprises reacting the reaction mixture obtained in the reaction of 1) with copper and / or a compound thereof and urea and / or a derivative thereof in the presence of a catalyst. 2. The method for producing a copper phthalocyanine compound according to claim 1, wherein the ammonia-containing mixed gas generated in the second-step reaction is circulated and used in the first-step reaction.