JPH10139782A - Production of copper phthalocyanine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound having a clear color tone and excellent in pigment suitability in a high yield by reacting phthalimide, copper or a copper salt and urea in the presence of a compound such as amides, amines and sulfoxides. SOLUTION: This copper phthalocyanine is obtained by forming phthalimide from phthalic anhydride with ammonia gas in trichlorobenzene in >=70% conversion, adding copper or a copper salt with 280-690mol% urea based on the phthalimide in the reaction solution and heating the solution in the presence of at least one kind of compounds of formula I (R<1> to R<3> are each H, a 1-15C alkyl or an aryl, R<1> and R<2> together may form a heterocyclic ring) (e.g.; N- methyl-2-pyrrolidone), formula II (e.g.; N-methylphthalimide), formula III (R<4> is similar to R<1> ; A is S, NH or O) (e.g.; N,N,N',N'-tetramethylthiourea), formula IV (e.g.; dibutylamine), and formula V (e.g.; dimethylsulfoxide).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing copper phthalocyanine which does not produce by-products in the presence of trichlorobenzene.

[0002]

2. Description of the Related Art Trichlorobenzene has been widely used as a reaction solvent for obtaining copper phthalocyanine having a vivid color tone in high yield. There was also a problem.

[0003]

The present inventor has proposed a method for solving the above-mentioned disadvantages by converting phthalimide and copper or a copper salt and urea in the presence of compounds represented by the general formulas (1) to (5). It has been found that the production of copper phthalocyanine by heat reaction in trichlorobenzene significantly reduces the amount of by-products produced, and has completed the present invention.

[0004]

According to the present invention, phthalimide and copper or a copper salt and urea are represented by the following general formulas (1) to (5).
The present invention relates to a method for producing copper phthalocyanine, wherein the reaction is carried out in trichlorobenzene in the presence of at least one compound represented by the formula:

[0005]

Embedded image

Wherein A is S, NH, or O;
R ¹ , R ² , R ³ and R ⁴ are the same or different and are H or an alkyl or aryl group having 1 to 15 carbon atoms;
R ¹ and R ² and R ³ and R ⁴ may each form a carbocyclic or heterocyclic ring, and at least one of R ¹ , R ² , R ³ and R ⁴ is not H. Further, according to the present invention, after converting phthalic anhydride to 70% or more phthalimide with ammonia gas in trichlorobenzene, copper or a copper salt and urea are added to the reaction solution by the general formula (1) to
The present invention relates to a method for producing copper phthalocyanine, comprising adding at least one kind of the compound represented by (5) and causing a heat reaction.

[0007]

Embedded image

Wherein A is S, NH, or O;
R ¹ , R ² , R ³ and R ⁴ are the same or different and are H or an alkyl or aryl group having 1 to 15 carbon atoms;
R ¹ and R ² and R ³ and R ⁴ may each form a carbocyclic or heterocyclic ring, and at least one of R ¹ , R ² , R ³ and R ⁴ is not H. The trichlorobenzene used in the present invention is 1,2,3
-Trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene or a mixture thereof; industrially, 1,2,3-trichlorobenzene and 1,2,4-trichlorobenzene are It is advantageously available at low cost. The amount of urea used in the present invention is an amount generally used in a method for producing copper phthalocyanine by reacting phthalimide and copper or a copper salt with urea under heating. The required amount of urea to obtain a high yield is about 230 mol% based on phthalimide as disclosed in JP-A-3-161489 (Example 4). 2 times the amount of phthalimide
When urea of 80 to 690 mol% is used, the effect of suppressing the formation of by-products is further increased. Mole% is more preferred.

The general formulas (1) to (5) used in the present invention
The compounds represented by are disclosed in JP-A-4-108866 as accelerators used in the production of copper phthalocyanine, and are exactly the same compounds as those exemplified in many examples. However, in the production method, phthalic anhydride is used, and it is necessary to use a larger amount of urea as compared with the case of using phthalimide as in the present invention, which is disadvantageous not only in cost but also in excess urea. The purity and clarity of the color tone of the final product are inferior to those of the present invention due to by-products generated by use. Further, when the gas generated when producing copper phthalocyanine in the present invention is used when producing phthalimide from phthalic anhydride,
The differences between the aforementioned costs and the clarity of purity and color of the final product are more pronounced.

The general formulas (1) to (5) used in the present invention
Preferred examples of the compound represented by the formula (1) include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, acetanilide, N-methylacetanilide and the like. 2)
About (3), there are N-methylphthalimide, N, N′-diacetamide and the like, and (3) about N, N, N ′,
There are N′-tetramethylurea, N, N, N ′, N′-tetramethylthiourea, 1,3-dimethyl-2-imidazolidone, 1,1,3,3-tetramethylguanidine and the like. Is dibutylamine, diisobutylamine, 2-ethylhexylamine, diallylamine, dioctylamine, benzylamine, dibenzylamine,
Indole and the like, and (5) include dimethylsulfoxide, diethylsulfoxide and the like. As the copper salt used in the present invention, all copper salts usually used for the synthesis of copper phthalocyanine can be used, and examples thereof include copper halide, copper oxide, copper phosphate, copper nitrate, copper hydroxide, and copper hydroxide.
There are copper acetate, copper sulfate and the like, and copper (I) chloride is most preferred. The reaction temperature in the present invention is from 120 to 220 ° C, preferably from 150 to 210. The reaction of the present invention can use all catalysts usually used for synthesizing phthalocyanine. There are tungsten compounds such as ammonium and ammonium phosphotungstate, arsenic vanadium compounds, boric acid, and halides or oxyhalides of titanium, tin and antimony, among which ammonium molybdate is excellent. As the ammonia gas used in the present invention, a commercially available one may be used as it is, but it is more cost-effective to use the gas generated during the production of copper phthalocyanine as it is, in which case, in addition to ammonium gas, urea is used. The resulting ammonium salt, for example, ammonium carbonate, ammonium cyanurate or the like is mixed in, but does not adversely affect the reaction, but rather increases the effect of suppressing the generation of by-products.

[0011]

The present invention will be described below with reference to examples. In the examples, “parts” and “%” are by weight unless otherwise specified. Example 1 In a 1-liter glass reactor equipped with a stirrer with an anchor-type stirring blade, a thermometer, a cooler and an external heating device,
262 parts of trichlorobenzene, 138 parts of urea, 0.3 part of ammonium molybdate, anhydrous copper (I) chloride 24.8
g, 147 parts of phthalimide and 0.8 g of N, N, N ', N'-tetramethylurea, and 1 hour in 2 hours while stirring.
The temperature was raised to 70 ° C., and the mixture was stirred at 170 ° C. for 5 hours. After the volatile components were distilled off at 140 ° C. and 100 mmHg, 2 liters of water was added to the residue, and the mixture was stirred at 90 ° C. for 2 hours, filtered, washed with warm water and dried to obtain 136 parts of copper phthalocyanine. As a result of gas chromatography analysis, no harmful by-product was detected in the obtained copper phthalocyanine and the recovered solvent. Example 2 The same procedure as in Example 1 was repeated except that the amount of urea was changed to 276 parts, and copper phthalocyanine 138 was obtained.
Got a part. Trace amounts of harmful by-products were detected in the obtained copper phthalocyanine and the recovered solvent. Comparative Example 1 In a 1-liter glass reactor equipped with a stirrer with an anchor-type stirring blade, a thermometer, a cooler and an external heating device,
262 parts of trichlorobenzene, 180 parts of urea, 0.3 parts of ammonium molybdate, 24.8 parts of anhydrous copper chloride (I)
g, 148 parts of phthalic anhydride and 0.8 g of N, N, N ', N'-tetramethylurea were added and stirred for 1 hour in 2 hours.
The temperature was raised to 70 ° C., and the mixture was stirred at 170 ° C. for 5 hours. After the volatile components were distilled off at 140 ° C. and 100 mmHg, 2 liters of water was added to the residue, and the mixture was stirred at 90 ° C. for 2 hours, filtered, washed with warm water and dried to obtain 136 parts of copper phthalocyanine. As a result of gas chromatography analysis, no harmful by-product was detected in the obtained copper phthalocyanine and the recovered solvent.

Comparative Example 2 The same operation as in Example 1 was carried out except that N, N, N ′, N′-tetramethylurea was not added, but 137 parts of copper phthalocyanine were obtained. Obtained. Trace amounts of harmful by-products were detected in the obtained copper phthalocyanine and the recovered solvent.

The amount of impurities contained in the copper phthalocyanine obtained in the above example was measured by the following method. 2 parts of copper phthalocyanine was weighed accurately in a 100 ml beaker, and N, N
-Add 80 ml of dimethylformamide and add 130-140
After stirring at 2 ° C. for 2 hours, the mixture was filtered through a glass filter, and the obtained filtrate was concentrated under reduced pressure using an evaporator, and then desiccated.
The mixture was left until the weight became constant. The value obtained by dividing the weight of the obtained concentrated residue by the weighed value of copper phthalocyanine was defined as the amount of impurities (%). The sharpness of the color tone of the obtained copper phthalocyanine was visually judged, and A, B, C
The order was given. The results of the determination of the amount of impurities and the sharpness are shown in the table below. It can be seen that when phthalic anhydride is used as a raw material, the amount of impurities is large and the color tone is unclear.

[0014]

[Table 1]

A stirrer with an anchor-type stirring blade, a thermometer,
262 parts of trichlorobenzene and 148 parts of phthalic anhydride were placed in a 1-liter glass reactor equipped with a cooler and an external heating device, and the temperature was increased to 130 ° C. while stirring.
5 at 130 ° C while introducing ammonium gas
Stirred for hours. Subsequently, 180 parts of urea, 0.3 part of ammonium molybdate, 24.8 g of anhydrous copper (I) chloride, N,
0.8 g of N, N ′, N′-tetramethylurea was added, and the temperature was raised to 170 ° C. for 2 hours with stirring.
Stirred at C for 5 hours. After the volatile components were distilled off at 140 ° C. and 100 mmHg, 2 liters of water was added to the residue, and 9
The mixture was stirred at 0 ° C. for 2 hours, filtered, washed with warm water and dried to obtain 139 parts of copper phthalocyanine. As a result of gas chromatography analysis, no harmful by-product was detected in the obtained copper phthalocyanine and the recovered solvent. Example 4 In Example 3, 138 parts of copper phthalocyanine was obtained in the same manner as in Example 3, except that a gas generated when producing copper phthalocyanine was introduced under the same conditions as in Example 1 instead of ammonium gas. Obtained. No harmful by-products were detected in the obtained copper phthalocyanine and the recovered solvent. Comparative Example 3 The procedure of Example 3 was repeated, except that N, N, N ', N'-tetramethylurea was not added, except that 136 parts of copper phthalocyanine was obtained. Trace amounts of harmful by-products were detected in the obtained copper phthalocyanine and the recovered solvent. Comparative Example 4 The procedure of Example 4 was repeated, except that N, N, N ′, N′-tetramethylurea was not added, except that 135 parts of copper phthalocyanine was obtained. Trace amounts of harmful by-products were detected in the obtained copper phthalocyanine and the recovered solvent.

Claims (4)

[Claims] A phthalimide and copper or copper salt and urea are heated and reacted in trichlorobenzene in the presence of at least one compound represented by the following general formulas (1) to (5). A method for producing copper phthalocyanine. Embedded image (Where A is S, NH, or O, and R ¹ , R ² ,
R ³ and R ⁴ are the same or different H or C 1 to C 1
5 alkyl or ants - a le radical, R ¹ and R
² and R ³ and R ⁴ may each form a carbocyclic or heterocyclic ring, and at least one of R ¹ , R ² , R ³ and R ⁴ is not H. ) 2. After the phthalic anhydride in trichlorobenzene is converted to phthalimide by 70% or more with ammonia gas, copper or a copper salt, urea and a compound represented by the general formula (1) are added to the reaction solution.
A method for producing copper phthalocyanine, comprising adding at least one of the compounds represented by (5) and reacting by heating. Embedded image (Where A is S, NH, or O, and R ¹ , R ² ,
R ³ and R ⁴ are the same or different H or C 1 to C 1
5 alkyl or ants - a le radical, R ¹ and R
² and R ³ and R ⁴ may each form a carbocyclic or heterocyclic ring, and at least one of R ¹ , R ² , R ³ and R ⁴ is not H. ) 3. The method according to claim 2, wherein the ammonia gas is a gas generated when a phthalic anhydride or phthalimide and copper or a copper salt are reacted with urea under heating. 4. Urea to phthalimide is 280-69.
The method for producing copper phthalocyanine according to any one of claims 1 to 3, wherein 0 mol% is used.