JP3470525B2 - Method for producing copper phthalocyanine - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing copper phthalocyanine in the presence of trichlorobenzene, which produces no by-products.

[0002]

BACKGROUND OF THE INVENTION Trichlorobenzene has been widely used as a reaction solvent for obtaining copper phthalocyanine having a vivid color tone in high yield. However, trichlorobenzene produces a by-product during the production of copper phthalocyanine, impairs the suitability for pigments and is hygienic. There was also a problem.

[0003]

DISCLOSURE OF THE INVENTION As a method for solving the above-mentioned drawbacks, the present inventor uses phthalimide and copper or a copper salt and urea in the presence of the compounds represented by the general formulas (1) to (5). By producing a copper phthalocyanine by heat-reacting in trichlorobenzene, it was found that the amount of by-products produced was significantly reduced, and the present invention was completed.

[0004]

According to the present invention, phthalimide and copper or copper salt and urea are combined with the following general formulas (1) to (5).
The present invention relates to a method for producing copper phthalocyanine, which comprises reacting with heat in trichlorobenzene in the presence of at least one compound represented by

[0005]

[Chemical 3]

(Wherein A is S, NH, or O,
R ¹ , R ² , R ³ and R ⁴ are the same or different H or an alkyl group having 1 to 15 carbon atoms or an aryl group,
R ¹ and R ² and R ³ and R ⁴ may each form a carbocycle or a heterocycle, and at least one of R ¹ , R ² , R ³ and R ⁴ is not H. Further, in the present invention, phthalic anhydride is converted to 70% or more phthalimide in trichlorobenzene by ammonia gas, and then copper or copper salt, urea and the general formula (1) to
The present invention relates to a method for producing copper phthalocyanine, which comprises adding at least one of the compounds represented by (5) and heating the mixture.

[0007]

[Chemical 4]

Where A is S, NH, or O,
R ¹ , R ² , R ³ and R ⁴ are the same or different H or an alkyl group having 1 to 15 carbon atoms or an aryl group,
R ¹ and R ² and R ³ and R ⁴ may each form a carbocycle or a heterocycle, and at least one of R ¹ , R ² , R ³ and R ⁴ is not H. ) Trichlorobenzene used in the present invention is 1,2,3
-Trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene or a mixture thereof, and industrially, 1,2,3-trichlorobenzene and 1,2,4-trichlorobenzene are It is inexpensive and advantageous. The amount of urea used in the present invention is the amount generally used in the method for producing copper phthalocyanine by heating and reacting phthalimide and copper or a copper salt and urea. The required amount of urea for obtaining a high yield is about 230 mol% with respect to phthalimide as described in JP-A-3-161489 (Example 4), but the required amount of urea is 1.2 to 3%. Double amount, ie 2 for phthalimide
When 80 to 690 mol% of urea is used, the effect of suppressing the formation of by-products is further increased, and when the sharpness of the color tone of the final product is taken into consideration, the amount is 1.5 to 2.0 times, that is, 350 to 460 relative to phthalimide. More preferred is mol%.

General formulas (1) to (5) used in the present invention
The compound represented by is a compound which is disclosed in JP-A-4-108866 as a promoter used in the production of copper phthalocyanine and is the same as many exemplified compounds. However, phthalic anhydride is used in the production method, and it is necessary to use a large amount of urea as compared with the case of using phthalimide as in the present invention, which is not only disadvantageous in terms of cost but also excess urea. The purity and color clarity of the final product are less than that of the present invention due to the by-products generated by use. Further, when the gas generated during the production of copper phthalocyanine in the present invention is used during the production of phthalimide from phthalic anhydride,
The aforementioned difference between the cost and the purity of the final product and the sharpness of the color tone becomes more remarkable.

General formulas (1) to (5) used in the present invention
As preferred examples of the compound represented by, for (1), there are N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, acetanilide, N-methylacetanilide, and the like. 2)
For, there are N-methylphthalimide, N, N'-diacetamide, etc., and for (3), N, N, N ',
There are N'-tetramethylurea, N, N, N ', N'-tetramethylthiourea, 1,3-dimethyl-2-imidazolidone, 1,1,3,3-tetramethylguanidine, etc., and (4) Is dibutylamine, diisobutylamine, 2-ethylhexylamine, diallylamine, dioctylamine, benzylamine, dibenzylamine,
Indole and the like, and (5) includes dimethyl sulfoxide, diethyl sulfoxide and the like. The copper salt used in the present invention may be any copper salt normally used in the synthesis of copper phthalocyanine, examples of which include copper halide, copper oxide, copper phosphate, copper nitrate, copper hydroxide,
There are copper acetate, copper sulfate and the like, and copper (I) chloride is most preferable. The reaction temperature in the present invention is 120 to 220 ° C, preferably 150 to 210. The reaction of the present invention can use all the catalysts usually used for synthesizing phthalocyanine, and examples thereof include ammonium molybdate, molybdic acid, ammonium phosphomolybdate, molybdenum compounds such as molybdenum oxide, tank stenoic acid. There are tungsten compounds such as ammonium and ammonium phosphotungstate, vanadium arsenide compounds, boric acid, and halides or oxyhalides of titanium, tin, antimony, and ammonium molybdate is particularly excellent. The ammonia gas used in the present invention may be a commercially available one as it is, but it is more cost-effective to use the gas generated during the production of copper phthalocyanine as it is. In that case, in addition to ammonium gas, urea may be used. The resulting ammonium salt, such as ammonium carbonate or ammonium cyanurate, is mixed, but does not adversely affect the reaction and rather enhances the effect of suppressing the production of by-products.

[0011]

EXAMPLES The present invention will be described below with reference to examples. In the examples, "parts" and "%" are based on weight unless otherwise specified. Example 1 In a 1 liter glass reactor equipped with an anchor-type stirrer with stirring blades, 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 were added, and the mixture was 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 as it was. 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 chromatographic analysis, no harmful by-products were detected in the obtained copper phthalocyanine and the recovered solvent. Example 2 When the amount of urea in Example 1 was changed to 276 parts and the same method was performed except for that, copper phthalocyanine 138 was obtained.
I got a part. A trace amount of harmful by-products was detected in the obtained copper phthalocyanine and the recovered solvent. Comparative Example 1 In a 1-liter glass reactor equipped with an anchor-type stirrer with stirring blades, a thermometer, a cooler, and an external heating device,
262 parts of trichlorobenzene, 180 parts of urea, 0.3 parts of ammonium molybdate, anhydrous copper (I) chloride 24.8
g, 148 parts of phthalic anhydride and 0.8 g of N, N, N ', N'-tetramethylurea were added, and the mixture was 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 as it was. 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 chromatographic analysis, no harmful by-products were 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 in Example 1, and 137 parts of copper phthalocyanine was obtained. Was obtained. A trace amount of harmful by-products was 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. Finely weigh 2 parts of copper phthalocyanine into a 100 ml beaker, and
-Add 80 ml of dimethylformamide 130-140
After stirring at ℃ for 2 hours, it was filtered with a glass filter, and the obtained filtrate was concentrated under reduced pressure with an evaporator and then desiccated.
It was left to stand until the constant weight was reached. The value obtained by dividing the weight of the obtained concentrated residue by the weighted value of copper phthalocyanine was taken as the amount of impurities (%). In addition, the sharpness of the color tone of the obtained copper phthalocyanine was visually determined, and from the clearer one, A, B, C
The rank is attached. The following table shows the judgment results of the amount of impurities and the sharpness. 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]

Stirrer with anchor type stirring blades, thermometer,
262 parts of trichlorobenzene and 148 parts of phthalic anhydride were put into a 1 liter glass reactor equipped with a condenser and an external heating device, and the temperature was raised to 130 ° C. with stirring.
While introducing ammonium gas, maintain the temperature at 130 ° C for 5
Stir 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. in 2 hours with stirring, and 170
The mixture was stirred at 0 ° C for 5 hours. After distilling off the volatile components 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 chromatographic analysis, no harmful by-products were detected in the obtained copper phthalocyanine and the recovered solvent. Example 4 The procedure of Example 3 was repeated except that the gas generated during the production of copper phthalocyanine was introduced under the same conditions as in Example 1 instead of the ammonium gas, and 138 parts of copper phthalocyanine was obtained. 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, and 136 parts of copper phthalocyanine was obtained. A trace amount of harmful by-products was 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, and 135 parts of copper phthalocyanine was obtained. A trace amount of harmful by-products was detected in the obtained copper phthalocyanine and the recovered solvent.

Claims (4)

(57) [Claims] 1. A phthalimide and copper or a 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). Method for producing copper phthalocyanine. [Chemical 1] (In the formula, A is S, NH, or O, and R ¹ , R ² ,
R ³ and R ⁴ are the same or different H or have 1 to 1 carbon atoms
5 is an alkyl group or aryl group, and R ¹ and R
² and R ³ and R ⁴ may form a carbocycle or a heterocycle, respectively, and at least one of R ¹ , R ² , R ³ and R ⁴ is not H. ) 2. In trichlorobenzene, phthalic anhydride is converted to 70% or more phthalimide by ammonia gas, and then copper or copper salt, urea and the general formula (1) to
A method for producing copper phthalocyanine, which comprises adding at least one of the compounds represented by (5) and heating the mixture to react. [Chemical 2] (In the formula, A is S, NH, or O, and R ¹ , R ² ,
R ³ and R ⁴ are the same or different H or have 1 to 1 carbon atoms
5 is an alkyl group or aryl group, and R ¹ and R
² and R ³ and R ⁴ may form a carbocycle or a heterocycle, respectively, 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 phthalic anhydride or phthalimide is reacted with copper or a copper salt and urea by heating. 4. Urea of 280 to 69 relative to phthalimide
The method for producing copper phthalocyanine according to any one of claims 1 to 3, wherein 0 mol% is used.