JPS61190566A - Production of copper phthalocyanine pigment - Google Patents

Abstract

PURPOSE:To obtain the titled pigment having excellent coloring power and clarity, by grinding a crude copper phthalocyanine together with a water-soluble inorganic salt and a organic liquid in a state of a viscous lump in nitrogen atmosphere sealed in the grinding system. CONSTITUTION:1pt. of a crude copper phthalocyanine is added with preferably 0.01-0.1pt. of preferably an alkali metal or alkaline earth metal hydroxide, and the grinding system is sealed with nitrogen. The copper phthalocyanine is then ground together with a water-soluble inorganic salt (preferably NaCl) and an organic liquid [preferably (di)ethylene glycol, triethylene glycol and/or polyethylene glycol] in a state of a viscous lump.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing copper phthalocyanine pigments.

Crude copper phthalocyanines obtained from various synthetic methods are not suitable for direct use as pigments. Conditioning (pigmentation) is required to impart properties as a pigment.

A known pigmentation method includes a method of dry milling using a ball mill using a water-soluble inorganic salt such as sodium chloride, sodium sulfate, calcium chloride, etc. as a milling aid. [“Dye and Medicine” Vol. 23, p. 221 (
1978)) LJ)LzNaka6's method has drawbacks such as long grinding time and the use of a large amount of inorganic salt and balls, resulting in a low production amount per unit volume.

Alternatively, an organic liquid such as ethylene glycol is added to a mixture of crude copper phthalocyanine and a water-soluble inorganic salt to form a viscous mass, which is then subjected to high shear such as a Banbury mixer or Nigu mixer. There is a method of wet milling that can be used. (U.S. Patent No. 2982666)
This method makes effective use of mechanical energy,
The milling time is considerably reduced compared to dry milling such as a ball mill. However, in order to obtain the desired pigment particles, 1
The disadvantage is that the productivity is low because of the long grinding time of 0 to 20 hours and the use of a large amount of water-soluble inorganic salt of 10 to 20 parts per 1 part of crude copper phthalocyanine.

Therefore, in order to improve these drawbacks, the inventors of the present invention have conducted intensive studies to increase the production amount per unit time and volume.

As a result, 0.0 of alkali metal hydroxide or alkaline earth metal hydroxide was added to 1 part of crude copper phthalocyanine.
It has previously been found that productivity can be significantly improved by adding 1 part or more and less than 0.1 part.

However, although this method attempted to shorten the milling time and reduce the amount of water-soluble inorganic salts, the coloring power and sharpness of the resulting copper phthalocyanine pigment were the same as those of the conventional method.

Therefore, the inventors of the present invention have conducted extensive studies on a method for obtaining a colored car with even better clarity.

As a result, when producing a copper phthalocyanine pigment by grinding crude copper phthalocyanine together with a water-soluble inorganic salt and an organic liquid into a viscous mass, the coloring power is improved by sealing the grinding system with nitrogen. It has been discovered that a pigment with excellent sharpness can be obtained, leading to the present invention.

The method of nitrogen sealing is to replace the inside of the grinding device with nitrogen,
There are methods to perform the grinding in a closed state or to keep nitrogen flowing into the apparatus during the grinding. Further, it is sufficient if nitrogen sealing is completely performed, and excessive nitrogen has no adverse effects, but is disadvantageous without improving quality.

In the present invention, examples of the alkali metal hydroxide or alkaline earth metal hydroxide include sodium, potassium, and lithium hydroxides, and magnesium and calcium hydroxides. Preferably used is sodium hydroxide.

The amount of these hydroxides added is 0.01 part or more and less than 0.1 part with respect to 1 part of crude copper phthalocyanine.

In the present invention, examples of water-soluble inorganic salts include sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, and the like. Particularly industrially, finely powdered sodium chloride is advantageous. The amount used is crude copper phthalocyanine 1
2 to 10 parts is preferable.

In addition, organic liquids for holding crude copper phthalocyanine and water-soluble inorganic salts as a viscous mass include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol, jetanolamine, and triethanol. amine,
Included are amines such as aniline, and mixtures thereof. Among these, those soluble in water and acids are preferred, and polyhydric alcohols are particularly advantageous for industrial purposes.

Apparatus for grinding the viscous mass obtained in this way under high shear forces include a Peka-Birkins sigma mixer, a Hoerner-Pfriederer sigma mixer, a Pambry mixer, or Beca Perkins M-
P or co-kneader type continuous efficiency mixers are mentioned.

The temperature during milling is possible within a wide range, but between 40 and 12
Preferably, it is carried out at 0°C. The milling time is continued until the desired pigment particles are obtained, but if it takes a long time, it is preferable to increase the amount of water-soluble inorganic salt and complete the milling in 4 to 12 hours.

After milling, the copper phthalocyanine pigment is processed by conventional methods.
Alkali metal or alkaline earth metal hydroxides (for those with low solubility in water, use mineral acids, especially hydrochloric acid), water-soluble inorganic salts, and organic liquids are dissolved in water, filtered, and isolated. .

The copper phthalocyanine pigment obtained by the present invention has higher coloring power and excellent clarity than the conventional method that does not seal with nitrogen. Particularly, when an alkali metal hydroxide or an alkaline earth metal hydroxide was added and a polyhydric alcohol was used as the organic liquid, a large effect was found.

Hereinafter, the present invention will be further explained in detail with reference to Examples.

In the examples, parts refer to parts by weight.

Example 1 1450 parts of sodium chloride, 18 parts of sodium hydroxide (90% purity), and crude copper phthalocyanine (95% purity) were added to a Baker Perkins Sigma type mixer having an internal volume of 4000 parts by volume while passing nitrogen gas. 265 parts of diethylene glycol and 340 parts of diethylene glycol were added and heated to 80 to 90°C under a nitrogen stream while keeping the contents in a viscous mass.
Grinding was carried out for 6 hours. During this time, an additional 50 parts of diethylene glycol was added in portions during the milling. Take out the contents into a 10,000 volume beaker and add 7,500 parts of water.
The mixture was stirred at 80 to 90°C for 2 hours, filtered and washed, and dried at 70 to 80°C. 248 parts of beta copper phthalocyanine pigment were obtained.

For comparison, a pigment was obtained by grinding according to this example except that nitrogen gas was not used.
It was observed that the coloring power obtained in this example was 5 inches higher and the clarity was excellent.

Example 2 1450 parts of sodium chloride was added to the mixer used in Example 1.
18 parts of sodium hydroxide (purity 90%), 265 parts of crude copper phthalocyanine (purity 95%), and 390 parts of diethylene glycol were charged, nitrogen gas was passed through at 20%, the inside of the apparatus was replaced with nitrogen, and then sealed, and heated at 80 to 90°C. Milling was carried out for 7 hours. The contents were treated according to Example 1 to obtain 248 parts of beta copper phthalocyanine pigment.

The resulting pigment had the same coloring power and sharpness as that of Example 1.

Example 3 Crude copper phthalocyanine 25 was added to the mixer used in Example 1.
6 parts (purity 97.5%) and 1750 parts of pulverized sodium chloride were charged and mixed uniformly while passing nitrogen gas. Then, 380 parts of ethylene glycol is injected and milled at 70-75°C for 10 hours. During this time, nitrogen gas was passed through the mixer, and 70 parts of ethylene glycol was added to keep the contents in a viscous mass.

The contents were treated according to Example 1 to obtain 248 parts of a beta copper phthalocyanine pigment with excellent clarity.

Example 4 A further addition of 5 parts of phthalimidomethyl copper phthalocyanine was carried out in the same manner as in Example 3, but the grinding time was for 7 hours), resulting in a beta-type copper phthalocyanine having the same color strength and brightness as in Example 3. 253 parts of pigment were obtained.

Claims (4)

[Claims] (1) Copper characterized in that when producing a copper phthalocyanine pigment by grinding crude copper phthalocyanine together with a water-soluble inorganic salt and an organic liquid into a viscous mass, the grinding system is sealed with nitrogen. Method for producing phthalocyanine pigments. (2) The method according to claim 1, wherein 0.01 part or more and less than 0.1 part of an alkali metal hydroxide or alkaline earth metal hydroxide is added to 1 part of crude copper phthalocyanine. (3) The method according to claim 1, wherein the organic liquid is a polyhydric alcohol. (4) The method according to claim 3, wherein the polyhydric alcohol is ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, or a mixture thereof.