JPS63308074A - Production of copper phthalocyanine pigment - Google Patents

Abstract

PURPOSE:To obtain the titled pigment having clear color hue and high coloring power and useful as a blue pigment for ink, etc., by reacting phthalic acid (derivative) with urea and copper (compound) in an inert organic solvent in the presence of a catalyst and a specific aromatic polybasic acid (derivative). CONSTITUTION:The objective pigment is produced by reacting (A) phthalic acid and/or its derivative with (B) urea, (C) copper or its compound and (D) an aromatic polybasic acid and/or its derivative expressed by formula (R1-R3 are H, carboxyl or a group derived from carboxyl; when two or more groups of R1-R3 are adjacent to each other, they may form an imide or acid anhydride group by cyclization; X, Y and Z is carboxyl, a group derived from carboxyl, nitrile or X and Y or Y and Z together form an imide or acid anhydride group by cyclization) in an inert organic solvent in the presence of a catalyst.

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 phthalonanine and making 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 minimum 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 copper phthalocyanine and then converting it into a pigment has the following unsatisfactory points in the process.

(1) The process is long and extremely uneconomical.

(2) When sulfuric acid is used in the pigment forming 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 pigmentation by mechanical grinding, the processing is complicated, requires a large amount of power over a long period of time, and the amount of processing per batch is small, resulting in very low productivity. Also high CO
D Wastewater treatment has become a major problem.

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 proposals have been made (Japanese Patent Publication No. 48-3291'9,
(No. 1135, Special Publication No. 19217 of 1983)
.

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

<Means for Solving the Problems> As a result of various studies by the present inventors 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,
It was discovered that by reacting in an inert organic solvent in the presence of a specific aromatic polybasic acid, the copper phthalocyanif particles produced by the reaction can be used directly as a pigment without going through a pigmentation treatment step, and the present invention This is the completed version.

That is, the present invention provides phthalic acid and/or its derivatives,
When producing copper phthalocyanine by reacting urea and copper or its compound in an inert organic solvent in the presence of a catalyst, aromatic polybasic acids and/or derivatives thereof represented by the following general formula (I) are used. This is a method for producing a copper phthalocyanine pigment, which is characterized in that the reaction is carried out in the presence of coexistence.

B [In the formula, R1-R1 represents a hydrogen atom, a carboxyl group, or a group derived from a carboxyl group, but if two or more exist adjacently, the ring is closed to form an imide or an acid anhydride. Good too. X1Y and Z represent a carboxyl group, a group derived from a carboxyl group, or a nitrile group, and xSy.

Z may be the same or different, and furthermore, X and Y or Y and Z may be ring-closed to form an imide or an acid anhydride. ] As the aromatic polybasic acid represented by the above general formula (1) and/or its derivative used in the present invention, the following compounds can be specifically exemplified.

Benzene-1,2,3-tricarboxylic acid, benzene-hexacarboxylic acid, benzene-1,2,3°4- or l,2
, 3.5 tetracarboxylic acid.

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 ester, phthalate ester,
Examples include phthalonitrile.

Copper and/or its compounds used in the present invention include, for example, metallic copper, cupric or cupric halides, copper oxide, copper cyanide, copper sulfate, copper nitrate, copper phosphate,
Examples include copper acetate, copper sulfide, and copper hydroxide. Furthermore, when copper hydroxide or copper oxide, which has poor reactivity, is used, a halide such as ammonium chloride may be allowed to coexist. The amount of copper, etc. used is 1 to 4 moles of phthalic acid and/or its derivatives.
It is about 1°3 moles.

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.

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

Next, the inert organic solvents used in the present invention include aromatic hydrocarbons such as alkylbenzene, alkylnaphthalene, and tetralin; alicyclic hydrocarbons such as alkylcyclohexane and decalin; and aliphatic hydrocarbons such as decane and dodecane. Nitrobenzene, 0-nitrotoluene, trichlorobenzene, dichlorobenzene, chloronaphthalene, diphenyl ether, sulfolane, dimethyl sulfoxide, methylsulfolane, dimethylsulfolane, N-methylpyrrolidone, dimethylimidazolidinone, etc. can be mentioned, and two or more of these It may be a mixture.

The amount of the compound represented by the general formula (1) used in the present invention is not particularly limited, but is usually 1 to 30%, particularly 1 to 15% by weight, based on phthalic acid etc. is preferred.

In the production method of the present invention, a copper phthalocyanine pigment can be easily obtained by essentially the same reaction operations 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 with warm water, etc., diluted, and then filtered.

<Effects of the Invention> The present invention enables copper phthalocyanine pigments to be produced without the need for a pigmentation process, using only a synthetic reaction process using phthalic acids, etc. Phthalocyanine pigments can be obtained directly.

In this way, by dispersing the obtained copper phthalocyanine pigment into a medium depending on the purpose, such as a resin, a face, or a plastic, paints, inks, plastic colorants, etc. could be manufactured.

<Example> Examples, comparative examples, and reference examples are listed below. Note that parts and percentages in the examples are based on weight, and specific surface area values are determined using a gas phase adsorption method using the BET method.

Example-1 592 parts of phthalic anhydride, 960 parts of urea, 15 parts of cuprous chloride
0 parts, 80 parts of titanium tetrachloride and 30 parts of hemimellitic acid (benzene-1,2,3-tricarboxylic acid) were added to 4 parts of sulfolane.
Add to 500 parts and raise the temperature to 180-190°C while stirring,
It was heated at the same temperature for 5 hours. Then cooled to 100°C,
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 5000 parts of 80°C warm water. Thereafter, the wet cake taken out was added to 100,001 parts of 2% hydrochloric acid, stirred at 60°C for 1 hour, and then filtered. Next, 80℃ hot water 10,000
575 parts of the target copper phthalocyanine were obtained by washing with 1 part and drying. The specific surface area of this thing is 75m
'/g.

Example-2 592 parts of phthalic anhydride, 960 parts of urea, 15 parts of cuprous chloride
0 parts, 80 parts of titanium tetrachloride, and 40 parts of MeIJ) acid (benzene hexacarboxylic acid) 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 preheat at 6°C.
Add 5000 parts of warm water kept at 0°C. 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, wash with 10,000 parts of 80°C warm water,
By drying, 570 parts of copper phthalocyanine was obtained. The specific surface area of this product was 73 m27 g.

Example 3 592 parts of phthalic anhydride, 740 parts of urea, 15 parts of cuprous chloride
0 parts of ammonium molybdate, and 50 parts of hemimellic acid were added to 3,500 parts of Hysol P (manufactured by Nippon Oil Corporation), the temperature was raised to 180° C. with stirring, and the mixture was heated at the same temperature for 4 hours. After the reaction, the solvent was distilled off under reduced pressure and the residue was reduced to 2%
The mixture was added to 5.000 parts of hydrochloric acid, stirred at 70°C for 1 hour, and then filtered with suction. The cake was thoroughly washed with hot water at 80°C and then dried to obtain 580 parts of copper phthalocyanine. The specific surface area of this product was 70 m27 g.

Example 4 In Example 3, instead of hemime+J) acid, meiJ
) 570 parts of copper phthalocyanine was obtained in the same manner as in Example 3 except that 25 parts of acid were used. The specific surface area of this material is 7
It was 0 m2/g.

Example 5 570 parts of copper phthalocyanine was obtained in the same manner as in Example 3 except that nitrobenzene was used as a solvent instead of Hysol P. The specific surface area of this product was 70 m27 g.

Reference Example-1 Copper phthalocyanine was prepared in the same manner as in Example 1 except that 30 parts of trimellitic acid (benzene-1,2,4-tricarboxylic acid) was used in place of the hemimetic acid used in Example 1. 576 copies were obtained. The specific surface area of this material is 3
button”/g.

Reference Example 2 In Example 1, the reaction was carried out in the absence of the hemime IJ) acid used, and the same post-treatment was carried out to obtain 560 parts of copper phthalocyanine. The specific surface area of this thing is 25m
”/g.

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 80°C warm water and then dried to obtain 98 parts of copper phthalocyanine pigment. The purity was 96% and 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 placed in a tube with a diameter of 3 m.
Add 12 parts of melamine alkyd-based paint varnish and 14 parts of xylene to a pot containing 90 parts of glass beads of M.M, add 12 parts of melamine alkyd paint varnish and 14 parts of xylene, run in a paint shaker for 1 hour, then add 50 parts of the same melamine alkyd varnish and I drove for 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 2 and Reference Example 2 in the same manner.

The results of comparing these coloring powers were as follows.

Comparative example - 2100% Example-2105% Reference example - 230%

Claims (1)

[Claims] When copper phthalocyanine is produced by reacting phthalic acid and/or its derivatives, urea, and copper or its compound in an inert organic solvent in the presence of a catalyst, it is possible to produce copper phthalocyanine represented by the following general formula. A method for producing a copper phthalocyanine pigment, which comprises reacting in the coexistence of an aromatic polybasic acid and/or a derivative thereof. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 to R_3 represent a hydrogen atom, a carboxyl group, or a group derived from a carboxyl group, but if two or more exist adjacently, the ring is closed. may form an imide or an acid anhydride. X, Y, and Z represent a carboxyl group, a group derived from a carboxyl group, or a nitrile group, and X, Y, and Z may be the same or different, and furthermore, Imides or acid anhydrides may also be formed. ]