JP2577219B2 - Method for producing copper phthalocyanine pigment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention is a production of a copper phthalocyanine pigment widely used as a colorant for inks, paints, plastics, and the like as a blue pigment having a clear hue and a great coloring power. It is about the method.

<Prior Art> A copper phthalocyanine pigment is generally produced through a synthesis step of crude copper phthalocyanine and a pigmentation step of atomizing the crude copper phthalocyanine as described below.

(1). Synthesis Step A crude copper phthalocyanine is obtained by heating phthalic anhydride or a derivative thereof, copper or a compound thereof, a nitrogen source such as urea, and a small amount of a catalyst in an inert high boiling point solvent.

(2). Pigmentation 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 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 a solution dissolved in high-concentration sulfuric acid and pours it into a large amount of water to obtain fine particles and a machine using a ball mill, a kneader, or the like. There is a physical atomization method by mechanical grinding.

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

(1) The process is long and uneconomical.

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

(3) In the case of pigmentation by mechanical attrition, the treatment is complicated, requires a large amount of power for a long time, the throughput per batch is small, and the productivity is extremely low. Also high CO
D Wastewater treatment is a major problem.

As a method for solving these problems, development of a direct production method of a copper phthalocyanine pigment which does not require a pigmentation step is expected. Against this background, various methods have been proposed (JP-A-48-32919, JP-B-50-1135).
No., JP-B-52-19217, JP-A-61-203175).
However, these proposals have not been satisfactory methods in terms of reaction operation and pigment suitability.

<Means for Solving the Problems> The present inventors have conducted various studies to eliminate various drawbacks in the conventional method for producing a copper phthalocyanine pigment, and as a result, have found that in the above-described crude copper phthalocyanine synthesis reaction system, an organic solvent is used. Among them, it has been found that by reacting in the presence of a specific substance, copper phthalocyanine particles produced by synthesis can be directly used as a pigment without going through a pigmentation treatment step, thereby completing the present invention.

That is, the present invention provides a method for producing a copper phthalocyanine pigment by reacting an unsubstituted phthalic acid and / or a derivative thereof, urea, and copper or a compound thereof in an organic solvent in the presence of a catalyst. The following general formula (1) is based on 100 parts by weight of the acid and / or its derivative. [In the formula, M represents hydrogen or an alkali metal. A and B
Represents a carboxyl group or a group derived from a carboxyl group, and A and B may be the same or different, and may be further closed to form an imide or an acid anhydride. ] The reaction is carried out in the co-presence of 1 to 15 parts by weight of the compound represented by the formula (1), wherein the copper phthalocyanine skeleton has substantially no substituent.

The phthalic acid and / or derivative thereof used in the present invention is capable of forming a copper phthalocyanine ring, and examples thereof include phthalic acid salts, phthalic anhydride, phthalimide, phthalamic acid and salts or esters thereof, phthalic acid esters, phthalonitrile Can be mentioned.

Copper and / or a compound thereof used in the present invention include, for example, metal copper, cuprous or cupric halide, copper oxide, copper cyanide, copper sulfate, copper nitrate, copper phosphate, copper acetate , Copper sulfide, copper hydroxide and the like. Further, when copper hydroxide or copper oxide having low reactivity is used, a halide such as ammonium chloride may coexist. The amount of the copper compound used is about 1 to 1.3 mol per 4 mol of phthalic acid and / or its derivative.

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

Examples of the catalyst used in the present invention include ammonium molybdate, molybdenum oxide, molybdenum compounds such as phosphomolybdic acid, titanium tetrachloride, titanium compounds such as titanate, zirconium chloride, zirconium compounds such as zirconium carbonate, antimony oxide, and the like. Arsenic oxide, boric acid and the like.

Next, the organic solvent used in the present invention includes: aromatic hydrocarbons such as alkylbenzene, alkylnaphthalene and tetralin; alicyclic hydrocarbons such as alkylcyclohexane and decalin; aliphatic hydrocarbons such as decane and dodecane;
Nitrobenzene, o-nitrotoluene, trichlorobenzene, dichlorobenzene, chloronaphthalene, diphenylether, sulfolane, dimethylsulfoxide, methylsulfolane, dimethylsulfolane, N-methylpyrrolidone, dimethylimidazolidinone, and the like;
A mixture of two or more of these may be used.

Specific examples of the compound represented by the general formula (1) used in the present invention include 4-sulfophthalic acid,
Examples thereof include -sulfophthalimide, 3-sulfophthalimide and alkali metal salts thereof, and particularly preferred is 4-sulfophthalic acid.

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

The reaction temperature in the range of usually 150 to 250 ° C. is sufficient. The compound represented by the above general formula may be added at any time before the phthalocyanine ring is formed.

For removal of the copper phthalocyanine obtained in the reaction, the solvent is distilled off under reduced pressure of the reaction mass, and then the powder is washed with hot water or a mineral acid aqueous solution and filtered, or the reaction mass is mixed and diluted with hot water or the like. Then, there is a method of filtering.

<Effect of the Invention> According to the method of the present invention, a copper phthalocyanine pigment can be obtained only by a synthesis reaction step using phthalic acids or the like without passing through a pigmentation step, as compared with the conventional method for producing a copper phthalocyanine pigment. That's amazing.

By dispersing the obtained copper phthalocyanine pigment in a medium such as a resin, a varnish, and a plastic according to the purpose, a paint, an ink, a plastic colorant, and the like can be produced.

<Examples> Examples, comparative examples, and reference examples will be described below.

The parts and percentages in the examples are by weight, and the specific surface area is BET.
It adopted the N ₂ gas phase adsorption method by law.

Example 1 592 parts of phthalic anhydride, 960 parts of urea, 105 parts of cuprous chloride,
80 parts of titanium tetrachloride and 30 parts of 4-sulfophthalic acid were added to 6000 parts of sulfolane, the temperature was increased to 180 to 190 ° C. with stirring, and the mixture was heated at the same temperature for 5 hours. Next, the mixture is cooled down to 100 ° C., and 5,000 parts of warm water previously kept at 60 ° C. are added. Next, the reaction mass is filtered, and after the filtration is completed, it is washed with 5000 parts of hot water at 80 ° C. Thereafter, the removed wet cake is subjected to 2% hydrochloric acid 10,000
After stirring at 60 ° C. for 1 hour, the mixture was filtered. Next, it was washed with 10,000 parts of hot water at 80 ° C. and dried to obtain 578 parts of copper phthalocyanine. The specific surface area of the obtained compound was 102 m ² / g.

Example 2 592 parts of phthalic anhydride, 800 parts of urea, 100 parts of cuprous chloride,
80 parts of titanium tetrachloride and 15 parts of 4-sulfophthalic acid were added to 4500 parts of sulfolane, the temperature was increased to 180 to 190 ° C. with stirring, and the mixture was heated at the same temperature for 5 hours. Next, the mixture is cooled down to 100 ° C., and 5,000 parts of warm water previously kept at 60 ° C. are added. Next, the reaction mass is filtered, and after the filtration is completed, it is washed with 5000 parts of hot water at 80 ° C. Thereafter, the removed wet cake is subjected to 2% hydrochloric acid 10,000
After stirring at 60 ° C. for 1 hour, the mixture was filtered. Next, it was washed with 10,000 parts of hot water at 80 ° C. and dried to obtain 565 parts of copper phthalocyanine. The specific surface area of the obtained compound was 100 m ² / g.

Example 3 592 parts of phthalic anhydride, 960 parts of urea, 140 parts of cuprous bromide,
90 parts of titanium tetrachloride and 60 parts of 4-sulfophthalic acid were added to 6000 parts of sulfolane, heated to 170 to 180 ° C. with stirring, and heated at the same temperature for 7 hours. Next, the mixture is cooled down to 100 ° C., and 5,000 parts of warm water previously kept at 60 ° C. are added. Next, the reaction mass is filtered, and after the filtration is completed, it is washed with 5000 parts of hot water at 80 ° C. Thereafter, the removed wet cake is subjected to 2% hydrochloric acid 10,000
After stirring at 60 ° C. for 1 hour, the mixture was filtered. Then, it was washed with 10,000 parts of hot water at 80 ° C. and dried to obtain 575 parts of copper phthalocyanine. The specific surface area of the obtained compound was 110 m ² / g.

Example 4 592 parts of phthalic anhydride, 960 parts of urea, 105 parts of cuprous chloride,
80 parts of titanium tetrachloride and 30 parts of 4-sulfophthalimide were added to 6000 parts of sulfolane, and the temperature was increased to 180 to 190 ° C. with stirring,
Heated at the same temperature for 5 hours. Next, the mixture is cooled down to 100 ° C., and 5,000 parts of warm water previously kept at 60 ° C. are added. Then
The reaction mass is filtered, and after the completion of the filtration, washed with 5000 parts of 80 ° C. hot water. After that, remove the wet cake with 2% hydrochloric acid 10
After stirring at 60 ° C. for 1 hour, the mixture was filtered. Next, it was washed with 10,000 parts of hot water at 80 ° C. and dried to obtain 573 parts of copper phthalocyanine. The specific surface area of the obtained compound was 100 m ² / g.

Example 5 592 parts of phthalic anhydride, 960 parts of urea, 105 parts of cuprous chloride,
50 parts of titanium tetrachloride and 30 parts of 4-sulfophthalic acid were added to 6000 parts of dimethyl sulfoxide, the temperature was increased to 170 to 180 ° C. with stirring, and the mixture was heated at the same temperature for 5 hours. Next, the mixture is cooled to 100 ° C., and 5,000 parts of warm water kept at 70 ° C. in advance is added. Next, the reaction mass was filtered, and after the filtration was completed, warm water of 80 ° C. 5000
Wash in part. After that, the removed wet cake is 5%
The mixture was added to 10,000 parts of hydrochloric acid, stirred at 60 ° C. for 1 hour, and filtered. Next, it was washed with 1000 parts of hot water at 80 ° C. and dried to obtain 540 parts of copper phthalocyanine. The specific surface area of the obtained compound was 80 m ² / g.

Example 6 phthalic anhydride 592 parts, urea 740 parts, cuprous chloride 105 parts,
6 parts of ammonium molybdate and 4-sulfophthalic acid
Add 30 parts to 3000 parts of nitrobenzene and stir at 180-190 ° C
And heated at the same temperature for 5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was added to 10,000 parts of 2% hydrochloric acid.
After stirring at 0 ° C. for 1 hour, the mixture was filtered. Then, it was washed with 10,000 parts of hot water at 80 ° C. and dried to obtain 576 parts of copper phthalocyanine. The specific surface area of the obtained compound is 60 m ² /
g.

Example 7 592 parts of phthalic anhydride, 740 parts of urea, 105 parts of cuprous chloride,
4 parts of ammonium molybdate and 4-sulfophthalic acid
30 parts were added to 3000 parts of Hisol P, the temperature was increased to 180 to 190 ° C. with stirring, and the mixture was heated at the same temperature for 5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was added to 10,000 parts of 5% hydrochloric acid.
After stirring at 1 ° C. for 1 hour, the mixture was filtered. Next, warm water at 80 ° C
After washing with 10,000 parts and drying, 575 parts of copper phthalocyanine was obtained. The specific surface area of the obtained compound is 68 m ² / g
Met.

Example 8 592 parts of phthalic anhydride, 960 parts of urea, 105 parts of cuprous chloride,
80 parts of titanium tetrachloride and 50% aqueous solution of 4-sulfophthalic acid 60
The mixture was added to 6000 parts of sulfolane, heated to 180 to 190 ° C. with stirring, and heated at the same temperature for 5 hours. Next, the mixture is cooled down to 100 ° C., and 5,000 parts of warm water previously kept at 60 ° C. are added. Next, the reaction mass was filtered, and after the filtration was completed, warm water of 80 ° C. 5000
Wash in part. After that, the removed wet cake is 2%
The mixture was added to 10,000 parts of hydrochloric acid, stirred at 60 ° C. for 1 hour, and filtered. Next, it was washed with 10,000 parts of hot water at 80 ° C. and dried to obtain 580 parts of copper phthalocyanine. The specific surface area of the obtained compound was 103 m ² / g.

Example 9 592 parts of phthalic anhydride, 1000 parts of urea, 100 parts of cuprous chloride,
50 parts of titanium tetrachloride and 60 parts of 4-sulfophthalimide are added to 6000 parts of sulfolane, and the temperature is increased to 210 to 220 ° C. with stirring,
Heated at the same temperature for 3 hours. Next, the mixture is cooled down to 100 ° C., and 5,000 parts of warm water previously kept at 60 ° C. are added. Then
The reaction mass is filtered, and after the completion of the filtration, washed with 5000 parts of 80 ° C. hot water. After that, remove the wet cake with 2% hydrochloric acid 10
After stirring at 60 ° C. for 1 hour, the mixture was filtered. Next, the resultant was washed with 10,000 parts of hot water at 80 ° C. and dried to obtain 598 parts of copper phthalocyanine. The specific surface area of the obtained compound was 90 m ² / g.

Example 10 592 parts of phthalic anhydride, 740 parts of urea, 105 parts of cuprous chloride,
Add 80 parts of titanium tetrachloride and 10 parts of 4-sulfophthalic acid trisodium salt to 4500 parts of sulfolane, and stir at 180 to 190 ° C.
And heated at the same temperature for 5 hours. Next, the mixture is cooled down to 100 ° C., and 5,000 parts of warm water previously kept at 60 ° C. are added. Next, the reaction mass is filtered, and after the filtration is completed, it is washed with 5000 parts of hot water at 80 ° C. Thereafter, the removed wet cake was added to 10,000 parts of 2% hydrochloric acid, and stirred at 60 ° C. for 1 hour.
Filtered. Then, it was washed with 10,000 parts of hot water of 80 ° C. and dried to obtain 560 parts of copper phthalocyanine. The specific surface area of the obtained compound was 105 m ² / g.

Example 11 phthalic anhydride 592 parts, urea 960 parts, cuprous chloride 105 parts,
80 parts of titanium tetrachloride and 50% aqueous solution of 4-sulfophthalic acid 40
To 6000 parts of sulfolane, heated to 160 to 170 ° C. with stirring, and heated at the same temperature for 8 hours. Next, the mixture is cooled down to 100 ° C., and 5,000 parts of warm water previously kept at 60 ° C. are added. Next, the reaction mass was filtered, and after the filtration was completed, warm water of 80 ° C. 5000
Wash in part. After that, the removed wet cake is 2%
The mixture was added to 10,000 parts of hydrochloric acid, stirred at 60 ° C. for 1 hour, and filtered. Next, it was washed with 10,000 parts of hot water at 80 ° C. and dried to obtain 570 parts of copper phthalocyanine. The specific surface area of the obtained compound was 110 m ² / g.

Example 12 592 parts of phthalic anhydride, 960 parts of urea, 105 parts of cuprous chloride,
10 parts of titanium tetrachloride and 30 parts of 4-sulfophthalimide
-Methylpyrrolidone was added to 5,000 parts, the temperature was increased to 180 to 190 ° C with stirring, and the mixture was heated at the same temperature for 5 hours. Next, the mixture is cooled down to 100 ° C., and 5,000 parts of warm water previously kept at 60 ° C. are added. Next, the reaction mass is filtered, and after the filtration is completed, it is washed with 5000 parts of hot water at 80 ° C. Thereafter, the removed wet cake was added to 10,000 parts of 2% hydrochloric acid, and stirred at 60 ° C. for 1 hour.
Filtered. Next, it was washed with 10,000 parts of hot water at 80 ° C. and dried to obtain 550 parts of copper phthalocyanine. The specific surface area of the obtained compound was 80 m ² / g.

Example 13 phthalic anhydride 592 parts, urea 1000 parts, cuprous chloride 100 parts,
6 parts of ammonium molybdate and 30 parts of trisodium 4-sulfophthalate were added to 4500 parts of sulfolane, heated to 180 to 190 ° C. with stirring, and heated at the same temperature for 5 hours. Then cool to 100 ° C and warm water 5
Add 000 parts. Next, the reaction mass is filtered, and after the filtration is completed, it is washed with 5000 parts of hot water at 80 ° C. Thereafter, the removed wet cake was added to 10,000 parts of 2% hydrochloric acid, stirred at 60 ° C. for 1 hour, and filtered. Next, it was washed with 10,000 parts of hot water at 80 ° C. and dried to obtain 565 parts of copper phthalocyanine. The specific surface area of the obtained compound was 98 m ² / g.

Reference Example-1 In Example-1, the reaction was carried out in the same manner as in Example-1, except that 4-sulfophthalic acid was not present, to obtain 570 parts of copper phthalocyanine. When the specific surface area of this product was measured, it was 25 m ² / g.

Comparative Example-1 Commercially available crude copper phthalocyanine (100 parts), common salt (400 parts) and ethylene glycol (100 parts) were mixed in an experimental double-arm kneader to obtain 80 parts.
Milling for 5 hours while maintaining ~ 85 ° C. The mixture was washed with warm water at 80 ° C., and dried to obtain 98 parts of a copper phthalocyanine pigment. The purity was 96%, and the specific surface area was 70 m ² / 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. The coloring power was measured, and the result was set as 100. The results obtained by similarly forming the copper phthalocyanine obtained in Examples and Reference Examples into inks and measuring the coloring power are shown in Table 1.

Comparative Example 2 4 parts of the copper phthalocyanine pigment obtained in Comparative Example 1 was 3 m in diameter.
m in a glass bottle containing 90 parts of glass beads, add 12 parts of melamine alkyd paint varnish and 14 parts of xylene,
After driving in a paint shaker for 1 hour, the same melamine alkyd varnish (50 parts) was added and the operation was continued for another 10 minutes. Thereafter, the glass beads were rubbed off with a wire net to obtain a blue primary color paint. 3 parts of this primary color paint and 5 parts of similar white paint containing 30% titanium white were mixed well with a glass rod to prepare a blue paint.

Next, paints were prepared in the same manner for the copper phthalocyanines obtained in Example-1 and Reference Example-1.

As a result of comparing these coloring powers, the results were as follows.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-19392 (JP, A) JP-A-53-6332 (JP, A) JP-A-53-66938 (JP, A) JP-A 48-48 91130 (JP, A)

Claims (1)

(57) [Claims] An unsubstituted phthalic acid and / or a derivative thereof,
When producing a copper phthalocyanine pigment by reacting urea and copper or a compound thereof in an organic solvent in the presence of a catalyst,
For 100 parts by weight of unsubstituted phthalic acid and / or its derivative, the following general formula [In the formula, M represents hydrogen or an alkali metal. A and B represent a carboxyl group or a group derived from a carboxyl group, and A and B may be the same or different, and may further form a ring to form an imide or an acid anhydride. ] A method for producing a pigment having substantially no substituent on the copper phthalocyanine skeleton, wherein the reaction is carried out in the presence of 1 to 15 parts by weight of the compound represented by the formula (1).