JPH055866B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing copper phthalocyanine, and more particularly to a method for producing a high-purity copper phthalocyanine blue pigment in high yield and economically.

(Prior Art) Conventionally, the most common method for producing copper phthalocyanine is the so-called urea method, in which phthalic anhydride, a nitrogen source such as urea, and a catalyst are heated in a high-boiling organic solvent.

(Problems to be solved by the invention) The urea method as described above is currently widely adopted industrially, but as the reaction progresses, phthalic anhydride and a nitrogen source such as urea react with each other. As a result of the formation of high molecular weight intermediates, the reaction mixture becomes highly viscous and the uniform temperature distribution is disrupted, resulting in the formation of resinous solids due to localized overheating, which significantly reduces the yield and reduces the product quality. This results in a significant decrease in purity. In order to solve the above-mentioned drawbacks, it is necessary to use a large amount of solvent, especially a large amount of a solvent with high solubility, during the reaction. However, there is a problem in that using a large amount of solvent is industrially uneconomical because the production amount of copper phthalocyanine per lot decreases.

Therefore, there has been a strong demand for a method for obtaining high-yield, high-purity copper phthalocyanine blue pigments by the urea method using phthalic acids as starting materials.

In order to solve the above-mentioned drawbacks of the prior art and to meet the above-mentioned needs, the present inventor has conducted intensive research and found that when adding a surfactant to the reaction mixture when producing copper phthalocyanine by the urea method, The present invention was completed based on the finding that the amount of solvent used can be significantly reduced compared to conventional methods, and that highly purified copper phthalocyanine can be obtained in high yield.

(Means for Solving the Problems) That is, the present invention provides a method for producing copper phthalocyanine by heating a reaction mixture consisting of a nitrogen source such as phthalic acids and urea, a catalyst, and a solvent.
This is a method for producing copper phthalocyanine, characterized in that an anionic surfactant is added to the reaction mixture, and the amount of solvent is in a range of 2 to 3 times the weight of phthalic acids.

Next, to explain the present invention in more detail, the phthalic acids used in the present invention are all known per se, and include, for example, phthalic acid, phthalic anhydride,
These include phthalimide, phthalodinitrile, phthalic diamide, 1,3-diiminoisoindolenine, alkoxyiminoisoindolenine, and low halogenated products thereof.

Urea is the most common nitrogen source, but other nitrogen sources include biuret, guanidine,
Ammonia, inorganic ammonium salts, etc. can be used. These nitrogen sources such as urea, for example, contain about 2 to 1 mole of the above-mentioned phthalic acids.
It is generally used in a ratio of 10 moles.

In addition to powdered metallic copper, the copper sources used include various copper compounds such as copper chloride, copper oxide,
These copper sources include copper sulfate, copper acetate, etc.
Approximately 1.0 to 1.0 as copper per 4 moles of the above phthalic acids
It is generally used in a proportion of 2.0 mol.

In addition, as catalysts to be used as necessary, antimony trioxide, ammonium molybdate, molybdic acid, ammonium vanadate, boric acid,
These catalysts include arsenic pentoxide, zirconium chloride, titanium tetrachloride, etc.
It is generally used in a ratio of about 0.001 to 0.5 mole per mole.

Furthermore, as the surfactant used in the present invention and which primarily characterizes the present invention, any conventionally known nonionic, cationic, anionic, or amphoteric surfactant can be used, but those that are particularly preferred are is an anionic surfactant which is soluble in the solvent described below, such as alkylbenzene sulfonate, naphthalene sulfonate formalin condensate, lauryl sulfate, and the like. Such surfactants can be used in amounts of about 100 parts by weight of the reaction mixture.
It is preferably used in a proportion of 0.01 to 10 parts by weight.

The second characteristic of the present invention is the amount of solvent used. Examples of such solvents include solvents conventionally used in the method for producing copper phthalocyanine by the urea method, such as dichlorobenzene, trichlorobenzene, nitrobenzene, chlornaphthalene, nitrotoluene, and polyalkylbenzenes with high boiling points. can. In the present invention, the amount of these solvents used is important, and in the present invention, these solvents are used in a ratio of about 100 to 500 parts by weight, preferably 200 to 300 parts by weight, per 100 parts by weight of the above-mentioned phthalic acids. do.

According to detailed research by the present inventor, in the urea method, which is a conventional method for producing copper phthalocyanine,
The above-mentioned problems would occur unless a solvent with a weight exceeding about 5 times the weight of the commonly used phthalic anhydride was used, but in the present invention, the above-mentioned surfactant is added to the reaction mixture. As a result, it has been found that even if the amount of solvent used is reduced to the above range, high yield and high purity copper phthalocyanine can be obtained.

This remarkable effect occurred because, by adding a small amount of surfactant into the reaction mixture, no significant increase in viscosity was observed despite the progress of the reaction, and the reaction was very slow. It is thought that this is because it is done uniformly. Therefore, in the present invention, even if the amount of solvent used exceeds five times the amount of phthalic acids, the yield and purity do not improve any further, and as the amount of solvent used increases, the amount per lot increases. Since the production amount of copper phthalocyanine decreases, there is a cost disadvantage. Furthermore, if the amount of solvent used is less than 1 times the amount of phthalic acid, the reaction becomes non-uniform despite the addition of a surfactant, which is undesirable because the yield and purity decrease.

The temperature conditions, time conditions, post-treatment, etc. of the manufacturing method of the present invention using the above-mentioned materials may be conventionally known conditions.
The temperature is 220°C, and the preferred time is about 3 to 10 hours.

(Operation/Effect) According to the present invention as described above, in the urea method using phthalic acids, high purity copper phthalocyanine can be produced in a high yield even though the amount of solvent used is extremely small. be able to. Therefore, even in the urea method, the production amount of copper phthalocyanine per lot has been significantly improved, and the problems of the prior art have been solved.

Next, the present invention will be further explained with reference to Examples. In addition, parts and percentages in the text are based on weight unless otherwise specified.

Example 1 60 parts of phthalic anhydride, 74 parts of urea, 10.5 parts of cuprous chloride
While stirring 0.4 parts of ammonium molybdate and 170 parts of trichlorobenzene, 3 parts of alkylbenzenesulfonic acid isopropylamine salt was added.
The temperature was raised to 190-200°C, and the mixture was reacted for 5 hours. After the reaction is complete, the solvent is removed by vacuum distillation,
Thereafter, a blue crude copper phthalocyanine was obtained by hot water treatment, dilute acid treatment, filtration, water washing, and drying. When the product was further purified according to a conventional method, 54.4 parts of a copper phthalocyanine blue pigment with a clear color (yield 94.9) was obtained.
%) was obtained.

For comparison, the yield was obtained when the above-mentioned surfactant was not added and the other operations were performed in the same manner as in Example 1.
At 91.4% (52.4 parts), the color tone of the product was extremely unclear.

Example 2 60 parts of phthalimide, 49 parts of urea, 10.5 parts of cuprous chloride
1 part, 4 parts of ammonium molybdate, and 3 parts of naphthalene sulfonic acid formalin condensate were added to 150 parts of trichlorobenzene, and the mixture was reacted at 180 to 200°C for 4 hours.

The following procedure was carried out in the same manner as in Example 1 to obtain 55.9 parts of blue copper phthalocyanine with a clear color tone (yield: 95.8 parts).
%) was obtained.

For comparison, when the above surfactant was not added and the other operations were performed in the same manner as in Example 2, the yield of copper phthalocyanine obtained was 91.9% (51.5 parts).
The color tone was extremely unclear.

Example 3 23.2 parts of phthalic acid, 58 parts of urea, 5.1 parts of cupric chloride,
6.4 parts of antimony trichloride, 2.8 parts of sodium lauryl sulfate and 65 parts of nitrobenzene at 180-200℃
19.2 parts of bright blue copper phthalocyanine (yield 95.3) was prepared in the same manner as in Example 1.
%) was obtained.

For comparison, the yield when no surfactant was added was 92.4% (18.6 parts), which was extremely unclear.

Example 4 23.2 parts of phthalic acid, 58 parts of urea, 5.1 parts of cupric chloride,
0.2 parts ammonium molybdate, 3.2 parts N-alkyltrimethyldiamine and nitrobenzene
60 parts were heated and stirred at 180-200°C for 4 hours. A clear blue copper phthalocyanine was prepared in the same manner as in Example 1.
19.3 parts (yield 96.1%) were obtained.

For comparison, the yield when no surfactant was added was 18.6 parts (92.7%), which was extremely unclear.

Claims (1)

[Claims] 1 In a method for producing copper phthalocyanine by heating a reaction mixture consisting of a nitrogen source such as phthalic acids and urea, a catalyst, and a solvent, an anionic surfactant is added to the reaction mixture, and the amount of the solvent is adjusted to A method for producing copper phthalocyanine, characterized in that the amount is 2 to 3 times the weight of copper phthalocyanine.