JPS637546B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing copper phthalocyanine, and more specifically, a method for providing high-purity copper phthalocyanine in which the amount of impurities generated during the reaction is significantly reduced at a high yield. It is.

Many methods for producing copper phthalocyanine have been known, but among them, the so-called urea method (Wyler method) is the most widely used. However, since this urea method inevitably uses excess urea and is carried out at high temperatures, a large amount of impurities are generated during the reaction, making it difficult to obtain a high yield, and it is difficult to completely remove these impurities. In many cases, the properties of copper phthalocyanine pigments are significantly impaired because they are mixed into the final product. In order to solve the biggest drawback of the urea method, which is industrially the cheapest and easiest method, we have developed methods that use phthalonitrile and indolenine compounds as raw materials, and methods other than urea, such as ammonia, as the nitrogen source. A method for carrying out the reaction under pressure is known, but each of these methods has its own drawbacks, and none of them are industrially advantageous.

The present invention solves the drawbacks of the prior art as described above,
As a result of intensive research to obtain high-purity copper phthalocyanine in high yield using the urea method, we have found that when using a solid catalyst with a particle size of approximately 0.1 microns or less as a catalyst in the urea method, the purity is significantly higher than in conventional methods. The present invention was completed based on the finding that copper phthalocyanine of 100% can be easily obtained in high yield.

That is, the present invention produces copper phthalocyanine from phthalic anhydride or its derivatives, urea, and copper salt, using a solid catalyst having a particle size of about 0.5 microns or less as a catalyst. It's a method.

To explain the present invention in detail, the phthalic acid or its derivative used in the present invention includes phthalic acid, phthalimide, mono-tetrahalogenophthalic acid, mono-tetrahalogenophthalimide, and the like. Urea used as a nitrogen source is used at a ratio of about 3 to 10 moles per mole of phthalic acid, etc. for phthalic acid or halogenophthalic acid, and at a ratio of about 2 moles per mole of phthalimide, etc. for phthalimide or halogenophthalimide. It is used in a proportion of ~8 mol. The catalysts used in the present invention and having specific properties that mainly characterize the present invention include ammonium molybdate,
Phosphorus-molybdic acid, molybdic acid, ammonium vanadate, tungsten oxide, antimony oxide,
It is a conventionally known catalyst in terms of chemical composition, such as boric acid, and its particle size is preferably about 0.001 to 0.5.
It is about 0.5 microns or less, such as microns.
The present inventor found that when using the above-mentioned commercially available catalyst as it is, the yield of the target product obtained is at most about
It was about 80-90% and contained a large amount of by-products of unknown structure.
When used after grinding to a particle size of 0.5 microns or less, the yield of the target product rapidly increases after about 0.5 microns, reaching about 90 to 98%. Such catalysts are preferably used in amounts of about 0.00005 to 0.005 mole per mole of phthalic acid, etc.

The present invention is characterized by the use of the above-mentioned specific catalyst, and other reaction conditions are the same as those of the conventional urea method. That is, about 8 to 20 moles of urea, about 1 mole of a copper compound, and the above-mentioned catalyst per about 4 mole proportions of phthalic anhydride or its derivative (e.g., phthalimide) are mixed at about 160 to 200°C in an inert solvent such as nitrobenzene or trichlorobenzene. At a temperature of about 3
Copper phthalocyanine can be obtained in high yield by reacting for ~10 hours. The copper phthalocyanine obtained by the present invention has extremely high purity and high yield, and the amount of impurities that are thought to have been generated from urea during the synthesis of copper phthalocyanine is extremely small compared to copper phthalocyanine obtained by conventional methods. Even in the crude product state before pigmentation, the color tone is extremely clear. Therefore, the copper phthalocyanine obtained by the present invention is not only easy to purify or turn into a pigment by conventional methods, but also has significantly superior effects when used in various applications compared to copper phthalocyanine pigments produced by conventional methods. give. For example, when conventional copper phthalocyanine pigments are used in paints, gravure inks, etc., impurities are eluted and
It has the disadvantages of decreased light resistance and various suitability, and when used for coloring synthetic resins, impurities cause a decrease in electrical insulation and deterioration of the resin, and other disadvantages. It was also the main cause of dullness and blurring in color tone. These drawbacks are virtually completely overcome when using the copper phthalocyanine according to the invention.

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. Note that "%" or "%" in the middle of the sentence is based on weight.

Reference example 1 A porcelain pot mill with a capacity of 250 parts was filled with porcelain balls with a diameter of 6 mm to 2/3 of its capacity, and 20 parts of coarse crystals of the commercially available reagent ammonium molybdate (manufactured by Kokusan Kagaku) were added, and the rotation speed was increased. The mixture was ground at 120 rpm for 1 hour to obtain ground ammonium molybdate. When this product was observed using an electron microscope, the average particle diameter was 10 mμ or less.

Reference Example 2 A porcelain ball mill with a capacity of 1000 parts was filled with 0.5-inch porcelain balls to 50% of the capacity, and commercially available industrial ammonium molybdate (manufactured by Taiyo Koko) was added to the mill.
100 parts of ammonium molybdate was added thereto and operated for 6 hours to obtain a ground product of ammonium molybdate. When this material was observed using an electron microscope, the average particle diameter was 10 m.
It was μ.

Example 1 60 parts of phthalic anhydride, 74 parts of urea, 10.5 parts of cuprous chloride
Part, ammonium molybdate obtained in Reference Example 1
0.04 parts and 300 parts of trichlorobenzene at 180℃~
The mixture was heated and stirred at 200°C for 5 hours, and after the reaction, the solvent was removed by distillation under reduced pressure, followed by treatment with hot water, filtration, dilute acid treatment, filtration, washing with water, and drying to obtain clear blue crude copper phthalocyanine. Further, the composition was purified according to a conventional method to obtain 55.6 parts of copper phthalocyanine (yield: 95.2%).

For comparison, the same amount of coarse ammonium molybdate before pulverization was used in place of the above ammonium molybdate, and the other operations were the same as in Example 1. The yield of copper phthalocyanine was 89.8%.
(52.4 parts).

Example 2 60 parts of phthalimide, 49 parts of urea, 10.5 parts of cuprous chloride
and 0.05 part of ammonium molybdate obtained in Reference Example 2 were added to 300 parts of trichlorobenzene, and the mixture was reacted at 180°C to 200°C for 4 hours. The following procedure was carried out in the same manner as in Example 1, with 56.1 parts of copper phthalocyanine (yield:
96.1%).

For comparison, the same amount of pre-pulverized catalyst was used in place of the above catalyst, and the other operations were carried out in the same manner as in Example 2. The yield of copper phthalocyanine obtained was as follows.
It was 90.2% (52.7 copies).

Example 3 180 parts of tetrachlorophthalic anhydride, 58 parts of urea, 5.1 parts of cupric chloride, 0.03 part of ammonium molybdate obtained in Reference Example 1 and 200 parts of nitrobenzene
The mixture was heated and stirred at ~200°C for 4 hours, and the same procedure as in Example 1 was carried out to obtain 38.6 parts of bright green copper phthalocyanine. (Yield 98%) For comparison, the same amount of unpulverized catalyst was used in place of the above catalyst, and the other operations were carried out in the same manner as in Example 3. The yield of copper phthalocyanine obtained was as follows. It was 91.5% (36.1 copies).

Example 4 40 parts of tetrabromophthalic anhydride, 58 parts of urea, 5.1 parts of cupric chloride, 0.03 part of ammonium molybdate obtained in Reference Example 2, and nitrobenzene
200 parts were heated and stirred at 180-200°C for 4 hours.

Thereafter, in the same manner as in Example 1, 38.7 parts of clear yellow-green copper phthalocyanine was obtained. (Yield 97.8%) For comparison, the same amount of pre-pulverized catalyst was used in place of the above catalyst, and the other operations were the same as in Example 4. The yield of copper phthalocyanine obtained was was 90.2% (35.7 copies).

Claims (1)

[Claims] 1. In producing copper phthalocyanine from phthalic anhydride or its derivatives, urea and copper salt,
A method for producing copper phthalocyanine, characterized in that a solid catalyst having a particle size of about 0.5 microns or less is used as a catalyst. 2. The method according to claim 1, wherein the catalyst is ammonium molybdate.