JPS63130672A - Preparation of organic pigment - Google Patents

Abstract

PURPOSE:To obtain an organic pigment having high tinting power and versatility, by dry grinding a crude organic pigment and an inorganic salt that will generate a gas by addition of an inorganic acid, treating the ground material with a crystallization solvent (an aqueous emulsion) and then adding an inorganic acid thereto for further treatment. CONSTITUTION:A crude organic pigment (e.g., a crude copper phthalocyanine) is dry ground together with an inorganic salt that will generate a gas by addition of an inorganic acid (e.g., sodium carbonate), the amount of the inorganic salt being 0.5-800wt% based on this pigment, and a chemical (e.g., calcium stearate) added if required for preventing the agglomeration of the organic pigment. The ground material is dispersed in a crystallization solvent (e.g., toluene or nitrobenzene) or an aqueous emulsion of this solvent to be treated therewith. An inorganic acid (e.g., hydrochloric acid) is added to this dispersion to decompose the inorganic salt to generate a gas (e.g., carbon dioxide gas) therefrom for further treatment. The treated material is separated by filtration, washed with water, and dried to give an objective pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION OBJECTS OF THE INVENTION Field of Industrial Application The present invention relates to a process for converting crude organic pigments into pigment form. Roughly in detail, 1. The present invention involves dry-pulverizing crude organic pigments with an inorganic salt and, if necessary, an anti-aggregating agent, reslurrying them in an aqueous system if necessary, and subjecting them to solvent or emulsion treatment and acid treatment. The present invention relates to a method for converting crude organic pigments into pigment form by.

(Prior art) Conventionally, crude organic pigments obtained by synthesis in organic solvents generally have coarse primary particles, so even when dispersed in various vehicles, they are indistinct and exhibit only low tinting power, and cannot be used as a single coloring material. value is small. Therefore, for use in various applications, it is necessary to refine the particles to nine particles.

When this crude organic pigment is ground in a ball mill or vibration mill without using a grinding aid, etc., it gradually becomes amorphous. Due to its strong cohesive force, it shows only low coloring power when crushed. However, this highly agglomerated pigment cannot be washed with a crystallization solvent such as xylene.

Alternatively, when treated in an aqueous emulsion, crystal transition occurs and conversion to the R material form is seen in Japanese Patent Publication No. 69435/1983. Methods in which crude organic pigments are ground in the absence of grinding aids and converted into pigment form by immersing them in crystallization solvents or water-based emulsions use a large amount of solvent, resulting in solvent recovery problems and fire hazards. In addition, there are difficulties in workability.

(Problems to be Solved by the Invention) The present invention provides a method for reducing or eliminating the above-mentioned problems as a method for conversion into a pigment form.

[Structure of the invention]

(Means for solving the problem) The present invention provides crude organic pigments and
800% by weight of an inorganic salt that generates gas with an inorganic acid;
Furthermore, the method for producing an organic pigment is characterized in that, if necessary, an anti-aggregation agent for the organic pigment is dry-pulverized, and then the second steps (a) and (b) are carried out.

(a) Adding an inorganic acid.

(b) Treatment with a crystallization solvent or an aqueous emulsion of the five agents.

That is, crude organic pigment, additives that suppress pulverization and agglomeration,
As a result of repeated research on the milling of inorganic salts, we added 0.5 to 800% by weight of an inorganic salt that generates gas with an inorganic acid as a grinding aid to the crude organic pigment, and added 0.1 to 800% by weight as a grinding aid if necessary. Add 200% by weight (milling) anti-agglomeration agent and perform dry milling. After dry pulverization, the pulverized material is reslurried in water as necessary, a crystallization solvent or its aqueous emulsion is added, and acid treatment is performed with an inorganic acid such as hydrochloric acid or sulfuric acid. It was discovered that an organic pigment can be obtained, and the present invention was completed.

In the present invention, the crude 18R material is one synthesized by a known method.9 For example, the production method for the crude phthalocyanine is not particularly limited, but phthalic anhydride or its derivatives, urea, and a copper source are used.

Alternatively, phthalodinetolyl or its derivatives and a copper source can be used as a catalyst (e.g. ammonium molybdate).

120 to 270°C, preferably 170 to 23°C in an organic solvent in the presence or absence of titanium tetrachloride, boron, etc.
It is produced by reacting at 0°C for 2 to 10 hours under normal pressure or increased pressure.

As with crude phthalocyanine, there are no particular restrictions on the manufacturing method for crude quinacridone. Dialkyl dianilinodihydroterephthalate is prepared from aniline and dialkyl succinate and cyclized to dihydroquinacridone by heating in an inert solvent. Pure quinacridone is then produced by oxidation of dihydroquinacridone. Alternatively, dialkyl dianilinoderephthalate is produced by oxidizing dialkyl dianilinodihydroterephthalate, which is then hydrolyzed to produce dianilinoterephthalic acid. Further cyclization of dianilinoterephthalic acid produces crude quinacridone.

Crude anthraquinone is also a crude phthalocyanine.

As with crude quinacridone, there are no particular restrictions on the manufacturing method. In addition, organic pigments such as perinone-based or dioxazine-based pigments can also be applied.

In the dry grinding process, carbonates such as sodium carbonate, sodium bicarbonate, and calcium carbonate and inorganic salts such as sodium oxalate not only act as grinding aids, but also remove inorganic substances between pigment particles when an inorganic acid is added. Salt generates gas such as carbon dioxide gas, and is thought to have the effect of deflocculating the agglomeration of crushed and agglomerated particles. However, if these salts are less than 0.5% by weight based on the crude organic pigment, they have little effect as a grinding aid, and pigments with high tinting strength cannot be obtained by a single method. Moreover, if it is added in an amount exceeding 5ooi%.

Although pulverization progresses, the productivity of the target pigment decreases due to its addition, and it is difficult to say that the manufacturing method is necessarily economical. The preferred amount added is 0.5 to 80% by weight.

More preferred is 1 to 50% by weight. Inorganic salts include sodium carbonate, sodium hydrogen carbonate, and calcium carbonate, which generate carbon dioxide gas with inorganic acids.

Sodium oxalate is preferred. Inorganic salts that generate gases other than carbon dioxide can also be used in some cases, but generally require more consideration than carbon dioxide from the viewpoint of the working environment.

The anti-aggregation agent is one selected from surfactants, resins, plasticizers, metal salts of fatty acids, etc. For example, fatty acid salts, higher alkyl sulfates (Na salts).

amine salt), alkylbenzene sulfonate (Na salt), alkyl phosphate, dialkyl sulfosuccinate, alkyl amine salt, quaternary ammonium salt,
Alkylpyridinium halide, alkylpyridinium chloride, alkylpicolium halide, alkyldimethylbenzylammonium chloride, alkyloxymethylpyridium chloride, polyoxyethylene alkylamine, polyoxyethylene alkyl ether,
Polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amide, sorbitan alkyl ester, polyoxyethylene soldavin alkyl ester, rosin gum rosin, wood rosin, hydrogenated rosin, polymerized rosin, oxidized rosin, tall oil rosin, xylene Resin, coumaron resin, ketone resin, maleic acid resin, phthalic acid resin, fatty acids (lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, caprylic acid, caproic acid), fatty acid barium, magnesium, zinc or These include aluminum salts, phthalic acid derivatives, and liquid paraffin. Further, as an anti-agglomeration agent, an organic solvent can be used in an amount within a range that does not inhibit the effect of dry grinding. These solvents include benzene, toluene, xylene, chlorobenzene, nitrobenzene, tetrahydrofuran, ethanolamine, aniline, pyridine, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, trichlorethylene, and tetrachlorethylene.

Examples include cellosolve acetate and butyl acetate.

The amount of the anti-aggregation agent added is 0.1 to 200% by weight based on the pigment. When added in excess of 200% by weight.

This suppresses pulverization and also contributes to adhesion or sticking during milling. Furthermore, metal salts of fatty acids such as calcium stearate themselves act as a predisposition and cause a decrease in coloring power. The amount added is preferably 0.1 to 100% by weight, more preferably 0.5 to 30% by weight. 20-80 finely agglomerated by adding an anti-aggregation agent and an inorganic acid.
% of the organic pigment in an unstable crystal form transforms into an unstable crystal form of 0 to 40%. This is the main fact in the present invention, that the deflocculation of flocculation is progressing, although it cannot be said to be sufficient due to the transfer.

Increase in specific surface area 1. Increase in tinting strength was avoided. In this case, it was found that the dispersion of the anti-aggregation agent occurred whether it was added during or after the dry grinding.

Dry pulverization is carried out, for example, in a vibrating mill, attritor, ball mill, or other pulverizer. The grinding temperature is 20
~130°C is preferred, and keeping the grinding temperature below 20°C is not advantageous in terms of cooling costs.

If the temperature exceeds 130°C, fine peptization will not occur when treated with a crystallization solvent or an aqueous emulsion, which is not desirable. What is the general relationship between grinding temperature and pigment quality?

The lower the grinding temperature, the more unstable crystals the ground product contains.

Crystals (when using HF4 agent or its aqueous emulsion, use a solvent of 0.1 to 500% by weight, preferably 0.1 to 50% by weight, more preferably 0.5 to 30% by weight based on #4 agent) Types include benzene, toluene, xylene, chlorobenzene, nitrobenzene, tetrahydrofuran, ethanolamine, aniline, pyridine, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, trichlorethylene, tetrachlorethylene, and cellosolve acetate.

Use butyl acetate. There are also resins in these solvents.

Activators, plasticizers, or derivatives of each pigment can be included.

Re-slurrying may be carried out by simply stirring at any temperature that maintains a liquid phase, or by dispersing in the presence of mechanical energy such as a mill.

There is no difference in quality whether the inorganic acid added is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc., but the amount added depends on the pH of the system.
It is desirable to add so that the amount is 5 or less, preferably 3 or less. If the pH exceeds 5, crystal transition is not sufficient and peptization is difficult to proceed. Furthermore, higher coloring power was obtained when the crystallization solvent treatment or aqueous emulsion treatment was performed and the 5th order was an inorganic acid.

Each pigment treated slurry is isolated as a pigment by filtration, drying or distillation. Of course, it is also possible to use it as it is in a wet state for paints, printing inks, plastics, etc. without isolation.

(Examples) The present invention will be explained below with reference to Examples. In the examples, 1 part means part by weight, and 1% means % by weight.

Example 1 80 parts of crude copper phthalocyanine produced by the urea method.

15 parts of sodium carbonate and 5 parts of calcium stearate were dry-pulverized for 11 hours at a grinding temperature of 45 to 55°C using an Attrike. The obtained pulverized material is reslurried in water,
The mixture is heated and stirred at 85 to 95°C, and a xylene emulsion having the composition described below is added thereto. Then, sulfuric acid was added until the pH reached 1 to generate carbon dioxide gas, and at the same time, the slurry production was carried out. The mixture was filtered, washed with water, and dried to obtain 82 parts of pigment.

This pigment showed 100% β-type crystal form in the X-ray diffraction diagram and had a specific surface area of 42 rrr/g. When this ink was dispersed in a rosin-modified phenol resin type face, it became a slightly reddish, clear ink with high coloring power.

"Preparation of emulsion" The following composition was stirred for 1 minute using a homomixer.

Xylene 1.6 parts Activator 0.1 part Water 98.3 parts Comparative Example 1 An example of the case where no components other than the crude phthalocyanine were added in Example 1, or when each additive was added to 0.1 part The one that was dry-milled and treated with xylene emulsion in the same way as No. 1 showed only low coloring strength when scratched with oil ink.

Example 2 85 parts of crude quinacridone, 12 parts of calcium carbonate, and 3 parts of calcium stearate were mixed using a vibration mill.

The pulverized product obtained by continuous dry pulverization at a pulverization temperature of 55 to 65°C is reslurried in water, heated and stirred at 85 to 95°C, and the same amount of xylene emulsion having the same composition as in Example 1 is added. Next, hydrochloric acid is added until the pH becomes 1, and carbon dioxide gas is generated, and at the same time, a scattering process is performed. filtration, washing,
This pigment, which was dried to yield 86 parts of pigment, exhibited high tinting strength in alkyd resin paints.

Comparative Example 2 In Example 2, 100 parts of calcium stearate was added to 1 part of crude quinacridone.

Although the clarity improved, the coloring power decreased due to calcium stearate, and the oil ink had poor fluidity.

Example 3 Brominated anthraquinone orange (C,1,Pig+a
entRed 168), 25 parts of sodium oxalate, and 5 parts of hydrogenated rosin (stevelite resin) were dry-pulverized using a ball mill. Post-processing is Example 1
Xylene emulsion treatment was carried out in the same manner. The pigment obtained by this method showed high tinting strength in a plastic (polyvinyl chloride) test.

Example 4 Rough! lI! ! 80 parts of copper phthalocyanine, 17 parts of sodium bicarbonate, and 3 parts of alkylbenzene sulfonic acid sorter (trade name: Neoperex 205) were dry-pulverized using an attritor to form a xylene emulsion (0.
8 parts of activator, 0.1 part of activator, and 99.1 parts of water), and hydrochloric acid was added until the pH reached 1. filtration.

It was washed with water and dried to obtain 80 parts of pigment. A rosin-modified phenolic resin type face showed high tinting strength.

Example 5 Perylene Red (C, 1, Pigment Red 1
23), 17 parts of calcium carbonate, and 3 parts of calcium stearate were subjected to the same treatment as in Example 1. The pigment obtained by this method showed high tinting power in paint and plastic tests.

Example 6 Dioxazine violet (C,1, Pigment
The same treatment as in Example 1 was performed using 80 parts of Violet 23), 15 parts of soda carbonate, and 5 parts of barium laurate. The pigment obtained by this method showed clear plastic coloration and high tinting power.

Claims (1)

[Claims] 1. Crude organic pigment and 0.5 to 800
An organic pigment characterized by dry-pulverizing % by weight of an inorganic salt that generates a gas with an inorganic acid, and optionally an anti-aggregation agent for organic pigments, and then carrying out the following (a) and (b). manufacturing method. (a) Add inorganic acid. (b) Treat with a crystallization solvent or an aqueous emulsion of the relevant agent. 2. The method for producing an organic pigment according to claim 1, wherein the inorganic salt is used in an amount of 1 to 50% by weight based on the pigment. 3. 0.1 to 200% by weight of anti-aggregation agent to the pigment
A method for producing an organic pigment according to claim 1 or 2. 4. The method for producing an organic pigment according to any one of claims 1 to 3, wherein the organic pigment is one selected from phthalocyanine, quinacridone, and anthraquinone. 5. The method for producing an organic pigment according to claim 4, wherein the organic pigment is copper phthalocyanine. 6. Any one of claims 1 to 5, wherein the inorganic salt is one selected from sodium carbonate, sodium bicarbonate, calcium carbonate, and sodium oxalate, and the inorganic acid is one selected from hydrochloric acid and sulfuric acid. The method for producing the organic pigment described in 7. The method for producing an organic pigment according to any one of claims 1 to 6, wherein the agglomeration inhibitor for the organic pigment is a metal salt of a fatty acid.