JPS5850263B2 - Doufthalocyaninno Seizouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing copper phthalocyanine.

More specifically, the present invention involves reacting fucuric anhydride, phthalimide or derivatives thereof, a urea compound, and a small amount of catalytic copper oxide or copper hydroxide as a copper source in the presence of a halogen compound in an inert solvent. This is a method for producing copper fucrocyanine, which is characterized by the following.

Copper phthalocyanine is among the phthalocyanine pigments, and has a clear blue color and excellent pigment suitability.

For example, it has unique heat resistance, weather resistance, and chemical resistance that are not found in other organic pigments.

For this reason, it is widely used in the color material industry.

This copper phthalocyanine is produced by conventional methods.

(1) In the presence or absence of an aromatic inert high-boiling solvent,
A method for producing from phthalic anhydride, phthalimide, or a derivative thereof, urea, a copper compound, and a small amount of a catalyst.

(2) in the presence or absence of an aromatic inert high-boiling solvent;
A method of manufacturing from phthalodinitrile and a copper compound.

Among these conventional production methods, in the method of producing copper phthalocyanine from phthalic anhydride or phthalimide, the method using copper chloride as the copper compound used as the copper source is the most industrially common production method.

By the way, when copper phthalocyanine is produced using copper chloride, the remaining copper source is used to extract the target copper phthalocyanine through a post-processing step, and then is finally converted into copper hydroxide or copper phthalocyanine.
It is recovered as copper oxide, which is not reused as a source of copper for copper phthalocyanine.

When copper phthalocyanine is produced from phthalic anhydride or phthalimide using copper hydroxide or copper oxide as a copper source, the reaction rate is extremely low (approximately 40φ at most) and cannot be adopted at all practically or industrially. That's because there isn't.

If this could be reused as a copper source in the production of copper phthalocyanine, it would be extremely advantageous in various respects.

The present inventors conducted extensive research on a method for producing copper phthalocyanine using copper hydroxide or copper oxide, which was known conceptually but was considered difficult to use in actual industrial use. As a result of investigation, the present invention as described above was finally discovered.

Although it is possible to regenerate copper chloride from copper oxide or hydroxide and reuse it, this regeneration process is complicated and industrially expensive.

The present invention is extremely unique in that it can be carried out without such complicated steps.

The halogen compound used in the present invention is a compound that releases halogen during the reaction for producing copper phthalocyanine and preferably reacts with ammonia generated during the reaction to produce ammonium halide, and is suitable for this purpose. Examples include nonmetal halides, alkali metal or alkaline earth metal halides, and the like.

Specifically, sodium chloride, sodium fluoride, sodium bromide, potassium chloride, potassium iodo, ammonium chloride, ammonium bromide, ammonium fluoride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride, sulfonyl chloride, chlorine. , hydrogen chloride, etc., among which ammonium chloride is most preferred.

The amount used is 0.00% per mole of copper oxide or copper hydroxide.
The molar ratio is greater than or equal to 1, advantageously greater than or equal to 0.5.

Copper hydroxide or copper oxide as a copper source used in the present invention is most advantageously used as a reuse of recovered products obtained by producing copper phthalocyanine using copper chloride as described above.

However, the present invention is not limited thereto, and may also use copper hydroxide or copper oxide obtained from copper sources discarded from various industries, including copper smelting factories, electric wire factories, and copper rolling factories.

The amount used is 0.25 mol or more, preferably 0.251 to 1.0 mol, per 1 mol of phthalic anhydride or phthalimide.
It is a molar ratio.

Copper oxide and copper hydroxide may be used in combination.

The phthalic anhydride or phthalimide used in the present invention may be commercially available commercially available phthalic anhydride or phthalimide.

As the urea compound as a nitrogen donor used in the present invention, in addition to urea, biuret, guanidine, guanidylurea, dicyandiamide or cyanuric acid, and mixtures of these and urea can also be used.

Urea may be in the form of granules or powder for fertilizer or general industrial use, and the amount used is at least 1 mole, preferably from 2 to 6 moles, per mole of phthalic anhydride or phthalimide.

In the present invention, the catalysts added in small amounts include ammonium molybdate, ammonium varadate, molybdenum oxide, molybdic acid, phosphomolybdic acid, arsenic pentoxide,
Ammonium oxide, boric acid, etc. are mentioned, and the amount used varies depending on the catalyst, but for example, in the case of ammonium molybdate, it is 0.00% per mole of phthalic anhydride or phthalimide.
00001 molar ratio or more, advantageously 0.0001 to o, o
i molar ratio.

These may be used in combination.

Examples of inert solvents used in the present invention include xylene, monochlorobenzene, ortho-dichlorobenzene, trichlorobenzene, nitrobenzene, dodecylbenzene, naphthalene, anthracene, kerosene, chlornaphthalene, kerosene, diisopropyltoluene, and mixtures thereof. A high boiling point solvent is used.

The amount used is preferably equal to or more than 3 to phthalic anhydride.
Use ~10 times the amount.

The method of the present invention is carried out, for example, as follows.

Trichlorobenzene is charged as an inert solvent, and while stirring is started, phthalic anhydride or phthalimide, urea, ammonium molybdate, copper oxide or copper hydroxide, and ammonium chloride are charged and the temperature begins to rise.

The reaction is completed by stirring at a temperature of 110° C. or higher, preferably 120° C. or higher, for 2 to 6 hours.

After the reaction is complete, the contents are transferred to a filter to separate the copper phthalocyanine.

After thoroughly washing with alcohol to remove trichlorobenzene, it is treated with, for example, 5% hydrochloric acid to dissolve impurities, separated by F, washed with water, and dried to obtain copper phthalocyanine in a high yield of 85% or more.

In addition, in the method of the present invention, if an alkaline agent such as caustic soda or caustic potash is added to the reaction system, the objective can be achieved at a relatively low reaction temperature.

According to the present invention, it is possible to produce the desired copper phthalocyanine in an extremely high yield using copper oxide or copper hydroxide, which has conventionally been completely impractical as a copper source for producing copper phthalocyanine, Its industrial value is immeasurable.

In the present invention, it is clear that the halogen compound acts as a promoter of the reaction for producing copper phthalocyanine, and thereby the desired copper phthalocyanine can be obtained at a high yield equivalent to or higher than when conventional copper chloride is used. This is truly remarkable.

Hereinafter, the unique effects brought about by the present invention will be explained through experiments.

As an example, when copper phthalocyanine is synthesized using cupric oxide, the relationship between the molar ratio of ammonium chloride added as a reaction accelerator and the yield of copper phthalocyanine is as shown in the experimental data in the following table.

(The experimental operations were carried out under the same conditions as in Example 1).

From Table 1, the effect of adding ammonium chloride is clear.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.

Also, parts in the example sentences represent parts by weight.

Example 1 230 parts of trichlorobenzene was charged into a 500 volume reaction vessel, and while stirring, 74 parts of phthalic anhydride, 90 parts of urea, 15.8 parts of cupric oxide (purity 99.8%), and 0.0 parts of ammonium molybdate were added. Add 3 parts and 22 parts of ammonium chloride and start heating.

Raise the temperature to 180℃ in 3 to 4 hours, then 180 to 200℃
Stir and keep warm for 3 hours.

After the reaction is completed, the contents are filtered to remove trichlorobenzene, the trichlorobenzene adhering to the copper phthalocyanine is thoroughly washed with methanol, and the separated copper phthalocyanine is charged into a 2000 volume reaction vessel.

Next, add 1000 parts of 5 polyhydrochloric acid solution and add 8 parts while stirring.
After incubating at 0 to 90°C for 1 hour to dissolve impurities, it was filtered, washed with water, and dried to yield 67.7 parts (purity 96.8% pure yield 9
1.3%) of copper phthalocyanine was obtained.

Example 2 Cupric hydroxide (purity 99) was used instead of cupric oxide in Example 1.
．． 5%) and otherwise operated in the same manner as in Example 1 to obtain 67.5 parts (purity: 95.7%, pure yield: 90.1%).
%) of copper phthalocyanine was obtained.

Example 3 Phthalimide 73.5 instead of phthalic anhydride in Example 1
67.
9 parts (purity 95.6 ml, pure yield 90.4%) of copper phthalocyanine were obtained.

Example 4 Salt 13 was used instead of ammonium chloride prepared in Example 1.
．． Using 7 parts, the other parts were prepared in the same manner as in Example 1, and the same operations and treatments were performed to obtain 68.0 parts (purity: 96, o%, pure yield: 90.7%) of copper phthalocyanine.

Example 5 19.2 parts of potassium chloride was used instead of the ammonium chloride charged in Example 1, and the other ingredients were prepared in the same manner as in Example 1.
The same operations and treatments were performed to obtain 68 parts of copper phthalocyanine.

Example 6 The same procedure as in Example 1 was repeated except that 13.1 parts of sodium bromide was used in place of the ammonium chloride charged in Example 1, to obtain 67.9 parts of copper phthalocyanine.

Example 7 Orthodichlorobenzene 230 in a 500 volume reaction vessel
74 parts of phthalic anhydride and 9 parts of urea while stirring.
0 parts, cupric oxide (purity 99.8) 15.8 parts, ammonium molybdate 0.3 parts, ammonium chloride 22 parts
Prepare the ingredients and start heating.

The temperature is raised to 140°C in 1 to 2 hours, 10.5 parts of caustic soda (solid purity 92.3) is added, and the reaction is completed by stirring at 140 to 150°C for 3 to 4 hours.

Thereafter, the same operations and treatments as in Example 1 were carried out to obtain 67.6 parts of copper phthalocyanine.

Claims (1)

[Claims] 1. A method of producing copper phthalocyanine, which is characterized by reacting phthalic anhydride, phthalimide or a derivative thereof, a urea compound, a small amount of a catalyst, and copper oxide or copper hydroxide as a copper source in the presence of a halogen compound in an inert solvent. Manufacturing method.