JPH011766A - Method for producing copper phthalocyanine pigment - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to the development of copper phthalocyanine pigments, which are widely used as coloring agents for inks, paints, plastics, etc., as blue pigments with a clear hue and greatly improved tinting power. This relates to a manufacturing method.

<Prior art> Copper phthalocyanine pigments are manufactured using the following synthetic process for crude copper phthalocyanine pigments. ! It is generally manufactured through a pigmentation process in which copper phthalocyanine is made into fine particles.

(1) Synthesis process Crude steel phthalocyanine ring 19 is produced by heating phthalic anhydride or its derivatives, copper or its compound, a nitrogen source such as urea, and a small amount of catalyst in an inert high-boiling solvent.
p le.

(2) Pigment formation step Since the copper phthalocyanine obtained by the above synthesis step is a lump of coarse particles, the color tone is dull and the coloring power is poor, and it cannot be put to practical use in this state. Therefore, a pigmentation step is required to impart tinting strength, sharpness and pigment suitability. This process mainly uses sulfuric acid to form a salt with sulfuric acid or dissolves it in high concentration sulfuric acid and pours it into a large amount of water to obtain fine particles using a scientific atomization method and a ball mill, kneader, etc. There is a physical atomization method using mechanical grinding.

<Problems to be Solved by the Invention> However, the method of synthesizing crude copper phthalocyanine and then converting it into a pigment has the following unsatisfactory points in terms of the process.

(1) The process is long and uneconomical.

(2) When sulfuric acid is used in the pigmentation process, there are important problems related to pollution, such as corrosion of equipment and disposal of waste acid generated in large quantities.

(3) In the case of pigment formation by mechanical grinding, the process is complicated, requires a large amount of power over a long period of time, and the throughput per batch is small, resulting in very low productivity. Also high COD
Wastewater treatment has become a major issue.

As a method to solve these problems, it is expected to develop a method for directly producing copper phthalocyanine pigments that does not require a pigmentation step. Against this background, various methods have been proposed (JP-A-48-32919, JP-A-61-
No. 203175, Special Publication No. 1135, Special Publication No. 50-1135, Special Publication No. 1135
2-19217).

However, these proposals were not fully satisfactory in terms of reaction operation and pigment suitability.

On the other hand, copper phthalocyanine has homologous types, and the α type, which has a reddish characteristic, and the β type, which has a greenish characteristic, are popular as pigments. Furthermore, there is also the ε type, which has a brighter red color and better solvent stability than the α type, but it is rarely used because it is expensive. A method for producing ε-type copper phthalo/anine having two extremely favorable properties is disclosed in Japanese Patent Publication No. 52-6300 and Japanese Patent Publication No. 52-6300.
As proposed in Publication No. 6301, it was inevitable that the cost would be extremely high. Therefore, various manufacturing methods were studied, and Japanese Patent Application Laid-Open Nos. 53-39325 and 57-141 were found to have industrial value.
The method described in No. 453 and Japanese Unexamined Patent Publication No. 57-149358 has been proposed. These methods are
In both cases, when synthesizing copper phthalocyanine, ε-type copper phthalocyanine is obtained by adding a copper phthalocyanine derivative, which is a manufacturing method that has extremely industrial value from a conventional perspective, but the complexity of the compound to be added, It was not satisfactory due to the complicated addition conditions. Furthermore, the ε-type copper phthalocyanine obtained by these production methods is then
It required a pigmentation process such as kneader grinding.

Means for Solving the Problems The present inventors have conducted various studies to eliminate the various drawbacks of the conventional copper phthalocyanine pigment production methods, and have found that:
The coarseness mentioned above! ! ! In the copper phthalocyanine synthesis reaction system, by using a specific solvent and carrying out the synthesis reaction in the coexistence of 'M790 cyanine sulfonic acids, preferable ε-type copper phthalocyanine particles can be directly produced without going through a pigmentation treatment step. The present invention was completed by discovering that it is possible to manufacture the same.

That is, the present invention is a method for producing a copper phthalocyanine pigment, which is characterized by reacting a compound capable of forming a phthalocyanine ring, urea, a copper compound, and a catalyst in a sulfolane solvent in the coexistence of a copper phthalocyanine sulfonic acid. .

The method of the present invention will be explained in more detail below.

Compounds capable of forming a phthalocyanine ring used in the present invention include phthalic acid, phthalic anhydride, phthalimide, phthalamic acid and its salts or esters,
Examples include phthalic acid esters and phthalnitrile. Particularly preferred are phthalic acid, phthalic anhydride, and phthalimide.

Further, examples of the copper compound used in the present invention include metallic copper, cupric or cupric halide, copper oxide, copper sulfate, copper acetate, copper cyanide, copper nitrate, copper sulfide, copper hydroxide. Examples include. The amount of the copper compound used is about 1 to 1.2 moles per 4 moles of the phthalocyanine ring-forming compound.

The amount of urea used in the present invention is about 4 to 30 moles per 4 moles of the phthalocyanine ring-forming compound.

Any conventionally known catalyst can be used, but examples include molybdenum compounds such as ammonium molybdate and molybdenum oxide, and titanium compounds such as titanium tetrachloride and titanate esters. The amount is 0.01 to 4 moles of phthalocyanine ring-forming compound.
It is about 1.0 mol.

In the method of the present invention, it is important to use sulfolane as a solvent. Specific examples of the sulfolane solvent used here include sulfolane, methylsulfolane, dimethylsulfolane, etc.
It may be at least 3.0 times the weight of the compound capable of forming a phthalocyanine ring, but preferably about 4.5 to 10.0 times. Although the sulfolane solvent is used in the present invention, other solvents such as dimethyl sulfoxide (DMS○) can also be used in combination if necessary.

Further, the copper butalone anine sulfonic acids coexisting in the method of the present invention are preferably those represented by the following general formula (1) (wherein 'J represents a hydrogen atom or an alkali gold atom, and n is 0.2 to 3 ) is a compound represented by Specific examples include mixtures of and, and mixtures of mixtures of.

That is, the compound represented by the general formula (1) used in the present invention includes both a single compound and a mixture, and n in the formula represents all the sulfones with respect to the gold copper phthalocyanine nucleus in the single compound or mixture. It represents the number of acid groups.

The present inventors believe that the synthesis of the preferable ε-type copper phthalocyanine does not require a further pigmentation step (-9 formula M)
In the compound, n is 0.2 to 3, preferably 0
．． We have found that compounds with a ratio of 5 to 2 are particularly preferred.

In addition, the amount of the compound represented by -9 formula (1) is:
Although not particularly limited, it is usually 1 to 20% by weight, particularly preferably 1 to 10% by weight, based on the phthalocyanine ring-forming compound.

According to the production method of the present invention, the desired copper phthalocyanine pigment can be easily obtained by essentially the same reaction operation as in the production of ordinary crude copper phthalocyanine.

As the reaction temperature, a range of 150 to 250°C is sufficient. Further, the compound represented by formula -9 may be added at any time before the phthalocyanine ring is formed.

Regarding the extraction of copper phthalocyanine obtained by the reaction,
There is a method in which the solvent is distilled off from the reaction mass under reduced pressure, and then the powder is washed with warm water or a mineral acid solution and filtered, or a method in which the reaction mass is mixed and diluted with warm water and then filtered.

<Effects of the Invention> According to the method of the present invention, compared to conventional methods for producing copper phthalocyanine pigments, copper phthalocyanine pigments, Among them, it is possible to obtain an ε-type copper phthalocyanine pigment that is reddish in color, vivid, and has high coloring power.
These words are truly astonishing.

Paints, inks, and plastic colorants can be produced by dispersing the obtained ε-type copper phthalocyanine pigment in a medium depending on the purpose, such as a resin, varnish, or plastic.

<Examples> The present invention will be described in more detail below by giving Examples, Comparative Examples, and Reference Examples.

In addition, parts and % in the examples are based on weight, and specific surface area values are BET.
The N2 gas phase adsorption method was adopted.

Example-1 592 parts of phthalic anhydride, 960 parts of urea, 10 parts of cuprous chloride
5 parts, 80 parts of titanium tetrachloride, and 30 parts of copper phthalocyanine sulfonic acid (n=0.9 in -9 formula (I)) were added to 4500 parts of sulfolane, and while stirring,
The temperature was raised to 0°C and heated at the same temperature for 5 hours. then 10
Warm water cooled to 0°C and kept at 60°C in advance
Add 00 copies. Next, the reaction mass is filtered, and after the filtration is completed, it is washed with 5000 parts of 80°C warm water. Thereafter, the removed wet cake was added to 10,000 parts of 2% hydrochloric acid, stirred at 60°C for 1 hour, and then filtered. Next, 80
By washing with 10,000 parts of warm water at °C and drying,
590 parts of the desired copper phthalocyanine pigment were obtained. The purity of the obtained compound was 95%, and the specific surface area was 65 m''/g.The crystal type was ε type.

Example-2 592 parts of phthalic anhydride, 960 parts of urea, 10 parts of cuprous chloride
5 parts, titanium tetrachloride 50 parts and sodium copper phthalocyanine sulfonate (n-1,9 in general formula (I)) 3
Add 0 part to 4500 parts of sulfolane and add 180 to 1 part while stirring.
The temperature was raised to 90°C and heated at the same temperature for 5 hours. then 1
Warm water 5 cooled to 00℃ and kept at 60℃ in advance
Add 000 copies. Next, the reaction mass is filtered, and after the filtration is completed, it is washed with 5000 parts of 80°C warm water. Thereafter, the wet cake taken out was added to 10,000 parts of 2% hydrochloric acid, stirred at 60°C for 1 hour, and then filtered.

Next, the mixture was washed with 10,000 parts of 80°C warm water and dried to obtain 585 parts of copper phthalocyanine pigment. The purity of the obtained compound was 96%, and the specific surface area was 70 m'/g. Moreover, the crystal type showed ε type.

Example-3 592 parts of phthalic anhydride, 1000 parts of urea, 1 part of cuprous bromide
45 parts, titanium tetrachloride 90 parts, and copper phthalocyanine sulfonic acid (n=1.5 in general formula (1)) 15
of sulfolane was added to 5,000 parts of sulfolane, and while stirring, 180 to 19
The temperature was raised to 0°C and heated at the same temperature for 5 hours. then 10
Warm water cooled to 0℃ and kept at about 60℃
Add 00 copies. Next, the reaction mass is filtered, and after the filtration is completed, it is washed with 5000 parts of 80°C warm water. After that, the removed wet cake was added to 10,000 parts of 2% hydrochloric acid,
After stirring at 60°C for 1 hour, it was filtered. Then, 80℃
By washing with 10,000 parts of warm water and drying, 600 parts of copper phthalocyanine pigment was obtained. The purity of the obtained compound was 93%, and the specific surface area was 60 m2/g. Also,
The crystal type showed ε type.

Example-4 592 parts of phthalic anhydride, 800 parts of urea, 10 parts of cuprous chloride
0 parts, ammonium molybdate 15 parts, copper phthalocyanine sulfonic acid (n = 1.6 in general formula (■))2
Add 0 part to 4500 parts of sulfolane and add 180 to 1 part while stirring.
The temperature was raised to 90°C and heated at the same temperature for 5 hours. then 1
Warm water 5 cooled to 00℃ and kept at 60℃ in advance
Add 000 copies. Next, the reaction mass is filtered, and after the filtration is completed, it is washed with 5000 parts of 80°C warm water. After that, the removed wet cake was added to 8000 parts of 2% hydrochloric acid,
After stirring at 60°C for 1 hour, it was filtered. Then, 80℃
By washing with 10,000 parts of warm water and drying, 550 parts of copper phthalocyanine was obtained. The purity of the obtained compound was 95%, and the specific surface area was 60+n2/g. Moreover, the crystal type showed ε type.

Note that n of the copper phthalocyanine sulfonic acids used in Examples 1 to 4 above was determined from elemental analysis.

Reference Example-1 In Example-1, 560 parts of copper phthalocyanine was obtained by carrying out the same reaction without the presence of copper phthalocyanine sulfonic acid, and performing the other completely same post-treatments. Purity was 95%, and the specific surface area was 25 m2/g.

Reference Example 2 In Reference Example 1, 570 parts of copper phthalocyanine was obtained in the same manner as in Reference Example 1 except that 40 parts of the compound represented by the formula was used. The purity was 80% and the specific surface area was 30 m'/g.

Moreover, the crystal type showed β type.

Comparative Example-1 100 parts of commercially available crude copper phthalocyanine, 400 parts of common salt, and 100 parts of ethylene glycol were ground for 5 hours while maintaining the temperature at 80 to 85°C in a double-armed experimental Ni-Goo. The mixture was washed with warm water at 80°C and dried to obtain 98 parts of copper phthalocyanine pigment. Purity 96%, specific surface area 70m2/
It was g.

An ink was prepared from 4 parts of the thus obtained copper phthalocyanine pigment, 80 parts of titanium white, and 160 parts of linseed oil. This coloring power was measured, and using this value as 1oo, the copper phthalocyanine obtained in the Examples and Reference Examples was also made into an ink.
Coloring power and hue were measured.

*Hue evaluation was not possible because the tinting power was too low.

*The color tone was determined visually based on the JIS standard L-0804 gray scale for discoloration and fading.

R: means reddish.

Comparative Example-2 4 parts of the copper phthalocyanine pigment obtained in Comparative Example-1 was placed in a tube with a diameter of 3 m.
Add 12 parts of melamine alkyd paint varnish and 14 parts of xylene to a plastic bottle containing 90 parts of M glass beads, put in a paint shaker and run for 1 hour, then add 50 parts of the same melamine alkyd varnish and add 10 parts of the same melamine alkyd varnish.
I drove for a minute. He then strained the glass peas through a wire mesh to obtain blue primary color paint.

Three parts of this primary color paint and five parts of a white paint material of the same type containing 30% titanium white were thoroughly mixed with a glass rod to make a blue paint.

Next, paints were made using the copper phthalocyanine obtained in Example 2 and Reference Example 1 in the same manner.

The results of comparing these coloring powers were as follows.

Comparative example - 2100% Example-211O% Reference example - 130%

Claims (1)

[Claims] 1. A method for producing a copper phthalocyanine pigment, which comprises reacting a compound capable of forming a phthalocyanine ring, urea, a copper compound, and a catalyst in a sulfolane solvent in the coexistence of a copper phthalocyanine sulfonic acid. . 2. Copper phthalocyanine sulfonic acids have the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, M represents a hydrogen atom or an alkali metal atom,
n represents 0.2 to 3. ) The method according to claim 1, which is a compound represented by: