JPS63207858A - Production of copper phthalocyanine pigment - Google Patents

Abstract

PURPOSE:To directly produce the titled pigment only by a synthetic reaction without using pigmentation process, by adding a specific component in addition to a catalyst to a reaction system in the synthesis of copper phthalocyanine from phthalic acid, copper, etc., in an organic solvent. CONSTITUTION:The objective pigment is produced by reacting phthalic acid and/or its derivative with urea and copper (compound) in an organic solvent (e.g. nitrobenzene) in he presence of a catalyst (e.g. titanium tetrachloride) and a compound of formula (A and B are H, alkyl, allyl, etc.) usually at 150-250 deg.C. The compound of formula is e.g. pyromellitic acid anhydride diimide. The amount of the compound of formula I is usually 1-30wt.% based on the phthalic acid, etc.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to the production of a copper phthalocyanine pigment, which is widely used as a coloring agent for inks, paints, plastics, etc. as a blue pigment with a clear hue and great coloring power. It is about the method.

<Prior Art> Copper phthalocyanine pigments are generally produced through the following steps of synthesizing crude copper phthalocyanine and turning the crude copper phthalocyanine into fine particles.

(1) Synthesis Step Crude copper phthalocyanine is obtained 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.

(2) Pigment formation step Since the copper phthalocyanine obtained by the above synthesis step is a lump of coarse particles, the color tone is unclear 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 chemical 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 steel 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 (Japanese Patent Application Laid-open No. 48-32919,
-1135, Japanese Patent Publication No. 52-19217). However, these proposals were not fully satisfactory in terms of reaction performance and pigment suitability.

<Means for Solving the Problems> As a result of various studies by the present inventors in order to eliminate the various drawbacks of these conventional methods for producing copper phthalocyanine pigments, the present inventors have found that:
In the crude copper phthalocyanine synthesis reaction system described above,
The present invention was achieved by discovering that by reacting in the presence of a specific substance in an organic solvent, it is possible to directly use synthesized copper phthalocyanine particles as a pigment without going through a pigmentation process. It is.

That is, the present invention provides phthalic acid and/or its derivatives,
A method for producing a copper phthalocyanine pigment, which comprises coexisting a compound represented by the following general formula when producing copper phthalocyanine by reacting urea, copper, or a compound thereof in an organic solvent in the presence of a catalyst. be.

[In the formula, A and B are a hydrogen atom, an alkyl group, a hydroxylalkyl group, an alkoxylalkyl group, a cycloalkyl group, an allyl group, an aralkyl group or -C1l, a Y group (Y is a phenyl group or a derivative thereof, a naphthalene ring or A and B may be the same or different. ] The phthalic acid and/or its derivatives used in the present invention can form a copper phthalocyanine ring, such as phthalate, phthalic anhydride, phthalimide, phthalamic acid and its salt or its ester, phthalic acid ester,
Examples include phtronitrile and the like.

Copper and/or its compounds used in the present invention include, for example, metallic steel, cupric or cupric halides, copper oxide, copper cyanide, copper sulfate, copper nitrate, copper phosphate, copper acetate. , copper sulfide, copper hydroxide, etc. Furthermore, when using hydroxide steel or copper oxide, which have poor reactivity, a halide such as ammonium chloride may be allowed to coexist. The amount of the copper compound etc. to be used is about 1 to 1.3 mol per 4 mol of phthalic acid and/or its derivative.

Further, the amount of urea used in the present invention is about 4 to 40 moles per 4 moles of phthalic acid and/or its derivative.

Catalysts used in the present invention include, for example, ammonium molybdate, molybdenum oxide, molybdenum compounds such as phosphomolybdic acid, titanium compounds such as titanium tetrachloride and titanate esters, zirconium compounds such as zirconium chloride and zirconium carbonate, antimony oxide, Examples include arsenic oxide and boric acid.

Next, the organic solvents used in the present invention include aromatic hydrocarbons such as alkylbenzene, alkylnaphthalene, and tetralin; alicyclic hydrocarbons such as alkylcyclohexane and decalin; aliphatic hydrocarbons such as decane and dodecane; nitrobenzene, -Nitrotoluene, trichlorobenzene, dichlorobenzene, chloronaphthalene, diphenyl ether, sulfolane, dimethylsulfoxide, methylsulfolane, dimethylsulfolane, N-methylpyrrolidone, dimethylimidazolidinone, etc., and mixtures of two or more of these It's okay.

In the present invention, the substances shown in the above-mentioned general formula (r) can be used as the substances that can coexist during the production of phthalocyanine.

Specific examples of these include the following compounds.

4, Not, and N02. (RSR' represents an alkyl group, an allyl group, an aralkyl group, a cycloalkyl group, etc.)] [R is water 9-
It represents an atom, an alkyl group, a hydroxylalkyl group, a cycloalkyl group, an allyl group, an aralkyl group, a CIL-Y group, or the like.

Y represents a phenyl group or a derivative thereof, a naphthalene ring or a derivative thereof, a phthalocyanine ring or a derivative thereof. ] Here, specific examples of -CI12Y include the following.

(n is an integer of 1 to 18, R represents an alkyl group, a phenyl group, etc.) The amount of the compound represented by these general formulas is not particularly limited, but usually, relative to phthalic acid, etc. 1-3
A weight ratio of 0% is preferred.

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 the above general formula may be added at any time before the phthalocyanine ring is formed.

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

<Effects of the Invention> By the method of the present invention, copper phthalocyanine pigments can be obtained only through a synthetic reaction step using phthalic acids, etc., without going through a pigmentation step, compared to the conventional method for producing copper phthalocyanine pigments. It's truly amazing what it can do.

Paints, inks, plastic colorants, etc. can be produced by dispersing the copper phthalocyanine pigment thus obtained into a medium depending on the purpose, such as a resin, varnish, or plastic.

<Example> Examples, comparative examples, and reference examples are listed below.

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, original form 740B, cuprous chloride 10
5 parts of ammonium molybdate, and 30 parts of pyromellitic anhydride diimide represented by
The temperature was raised to ℃ and heated at the same temperature for 4.0 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and the residue was dissolved in 2% hydrochloric acid (5.000 g).
After stirring at 70°C for 1 hour, the mixture was filtered under suction. The cake was thoroughly washed with hot water at 80°C and then dried to obtain 575 parts of copper phthalocyanine. The specific surface area of this product was 85 m'/g.

Example 2 586 parts of copper phthalocyanine was obtained in the same manner as in Example 1 except that 40 parts of the imide represented by the formula in Example 1 was used.

The specific surface area of this material was measured and found to be 80 m''/g.

Example 3 Copper phthalocyanine 570 was prepared in the same manner as in Example 1 except that nitrobenzene was used as the solvent instead of Hysol P.
I got the department. The specific surface area of this product was 78 m'/g.

Examples 4 to 9 Copper phthalocyanate was prepared by changing the imide and Noizole P used in Example 1 to other imides and solvents.
ff111'A I, f-The following table summarizes its support nests.

Example 10 592 parts of phthalic anhydride, 960 parts of urea, 10 parts of cuprous chloride
5 parts of titanium tetrachloride, and 30 parts of an imide represented by the following formula were added to 4.500 parts of sulfolane, and the temperature was raised to 180 to 190°C with stirring, and heated at the same temperature for 5 hours. Next, cool to 100°C and add 5,000 parts of warm water kept at 60°C in advance.

Next, the reaction mass is filtered, and after the filtration is completed, it is washed with 5,000 parts of 80°C warm water. Then, remove the wet
The cake was added to 5.000 parts of 2% hydrochloric acid, stirred at 60°C for 1 hour, and then filtered. Then 80℃ warm water 5.00
By washing with 0 parts and drying, 575 parts of copper phthalocyanine were obtained. The specific surface area of the obtained compound is 90 m'
/g.

Example 11 592 parts of phthalic anhydride, 960 parts of urea, 10 parts of cuprous chloride
5 parts of titanium tetrachloride, 80 parts of titanium tetrachloride, and 45 parts of an imidomethylol derivative represented by the following structural formula were added to 6,000 parts of sulfolane, and the temperature was raised to 180 to 190°C with stirring, and heated at the same temperature for 5 hours. Next, cool to 100°C and add 5,000 parts of warm water kept at 60°C in advance. Next, the reaction mass is filtered to complete the filtration.

Afterwards, it is washed with 5,000 parts of 80°C warm water. Thereafter, the wet cake taken out was added to 5.000 parts of 2% hydrochloric acid, stirred at 60°C for 1 hour, and then filtered. Then 80
By washing with 5,000 parts of warm water at °C and drying,
590 parts of copper phthalocyanine were obtained. The specific surface area of the obtained compound was 90 m'/g.

Example 12 592 parts of phthalic anhydride, 960 parts of urea, 10 parts of cuprous chloride
5 parts of titanium tetrachloride, 80 parts of titanium tetrachloride, and 60 parts of a phthalocyanine derivative represented by the following structural formula were added to 6,000 parts of sulfolane, and the temperature was raised to 185° C. with stirring, and heated at the same temperature for 5 hours. Then cool to 100℃ and preheat to 60℃
Add 5,000 parts of warm water to the solution. Next, the reaction mass is filtered, and after the filtration is completed, it is washed with 5,000 parts of 80°C warm water. Thereafter, the removed wet cake was added to 10.000 parts of 2% hydrochloric acid, and after stirring at 60°C for 1 hour,
Filtered. Next, 600 parts of copper phthalocyanine was obtained by washing with 10,000 parts of 80°C warm water and drying. The specific surface area of the obtained compound was 88 m'/g.

Example 13 592 parts of phthalic anhydride, 800 parts of urea, 10 parts of cuprous chloride
0 parts, ammonium molybdate, 4 parts, and 40 parts of an imide represented by the following formula were added to 4.500 parts of sulfolane, and the temperature was raised to 180 to 190°C with stirring, and heated at the same temperature for 5 hours. Next, cool to 100℃ and preheat to 60℃.
Add 5,000 parts of warm water kept at ℃.

Next, the reaction mass is filtered, and after the filtration is completed, it is washed with 5,000 parts of 80°C warm water. Then, remove the wet
The cake was added to 8.000 parts of 2% hydrochloric acid, stirred at 60°C for 1 hour, and then filtered. Then 80℃ warm water 10.0
By washing with 0.00 parts and drying, 550 parts of copper phthalocyanine was obtained. The specific surface area of the obtained compound is 85 m
″/g.

Example 14 592 parts of phthalic anhydride, 800 parts of urea, 10 parts of cuprous chloride
0 parts, ammonium molybdate 4 parts, and 30 parts of the imide represented by the following formula in dimethyl sulfoxide (DMSO)
The mixture was added to 6.000 parts, heated to 200 to 210°C with stirring, and heated at the same temperature for 4 hours. Then cooled to 100℃ and heated water previously kept at 60℃ for 10,000 seconds.
Add. Next, the reaction mass was filtered, and after the filtration was completed, 8
Wash with 5,000 parts of warm water at 0°C. Then, add the removed wet cake to 10.000 parts of 1% hydrochloric acid and
After stirring at 0°C for 1 hour, it was filtered. Next, 530 parts of copper phthalocyanine was obtained by washing with 10,000 parts of 80°C warm water and drying. The specific surface area of the obtained compound was 85 m'/g.

Example 15 592 parts of phthalic anhydride, 800 parts of urea, 14 parts of cuprous bromide
0 parts, titanium tetrachloride 10 parts, and 30 parts of an imide compound represented by the following formula were added to 5.500 parts of sulfolane, and 180 parts of titanium tetrachloride was added under stirring.
The temperature was raised to ~190°C and heated at the same temperature for 5 hours. Next, cool to 100°C and add 5,000 parts of warm water kept at 60°C in advance. The reaction mass is then filtered,
After filtration, wash with 10,000 parts of 80°C warm water.

After that, the removed wet cake was mixed with 2% hydrochloric acid 10.0
00 parts, stirred at 60°C for 1 hour, and then filtered.

Next, 580 parts of copper phthalocyanine was obtained by washing with 10,000 parts of 80°C warm water and drying. The specific surface area of the obtained compound was 85 m'/g.

Reference Example-1 In Example-1, the reaction was carried out in the absence of the pyromellitic anhydride diimide used, and copper phthalocyanine 57
I got 0 copies. When the specific surface area of this material was measured, it was 24
m'/g.

Reference Example-2 In Example-10, the reaction was carried out in the absence of the pyromellitic anhydride diimide used, and copper phthalocyanaf 5
Got 60 copies. When the specific surface area of this material was measured, it was found that 2
It was 5 m'/g.

Comparative Example-1 100 parts of commercially available crude copper phthalocyanine, 400 parts of common salt,
100 parts of ethylene glycol was ground for 5 hours while maintaining a temperature of 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. The specific surface area was 70 m'/g.

An ink was prepared from 4 parts of the copper phthalocyanine pigment thus obtained, 80 parts of titanium white, and 160 parts of linseed oil. This coloring power was measured, and using this value as 100, the copper phthalocyanine obtained in Examples and Reference Examples was also formed into ink and the coloring power was measured.

Comparative Example-2 4 parts of the copper phthalocyanine pigment obtained in Comparative Example-1 was directly added (?4 parts).
Place it in a plastic bottle containing 90 parts of 3 mm glass beads.
Melamine alkyd paint festival 12 parts and xylene 14 parts
ffr! , and the paint shaker was run for 1 hour, then 50 parts of the same melamine alkyd varnish was added and the run was run for an additional 10 minutes. 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 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 10 and Reference Example 1 in the same manner.

The results of comparing these coloring powers were as follows.

Comparative example - 2100% Example-10110% Reference example - 130% I l

Claims (1)

[Claims] When producing copper phthalocyanine by reacting phthalic acid and/or its derivatives, urea, copper, or its compounds in an organic solvent in the presence of a catalyst, the coexistence of a compound represented by the following general formula A method for producing a copper phthalocyanine pigment, characterized by carrying out the following reaction. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A and B are hydrogen atoms, alkyl groups, hydroxylalkyl groups, alkoxylalkyl groups, cycloalkyl groups, allyl groups, aralkyl groups, or represents a phenyl group or its derivatives, a naphthalene ring or its derivatives, a phthalocyanine ring or its derivatives)
, but A and B may be the same or different. ]