JPS6361348B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing copper phthalocyanine pigments by wet milling. More specifically, the method is characterized in that crude copper phthalocyanine is wet-milled in the presence of a milling aid selected from sodium chloride, sodium sulfate, etc. and an organic liquid, with the addition of phthalimidomethyl phthalocyanine. This is a method for producing copper phthalocyanine pigments. It is well known in the art that crude copper phthalocyanine obtained by conventional synthetic reactions lacks pigmentary properties in terms of tinting strength, hue, and the like.
Therefore, various methods have been used to convert crude copper phthalocyanine into useful pigment forms. Conventional industrial methods include a method in which crude copper phthalocyanine is ground in a ball mill in the presence of a grinding aid and a very small amount of aromatic hydrocarbon (dry milling method);
Alternatively, it is broadly classified into a method (wet milling method) in which crude copper phthalocyanine is milled in a kneader in the coexistence of a milling aid and an organic solvent to form a viscous mass that is neither powder nor gruel. Conventionally, the latter milling method (wet milling) has been carried out using a large amount of milling aids such as sodium chloride and sodium sulfate. However, if a large amount of the grinding aid is used, it is necessary to increase the amount of organic solvent to form a sticky mass in proportion to the amount of the grinding aid. Moreover, in order to separate the pigment, the grinding aid, and the organic solvent after the grinding is completed, water is required to sufficiently dissolve the grinding aid, and as the amount of the grinding aid increases, the amount of water used also increases. In addition, the wastewater from which pigments are separated is collected and reused due to wastewater regulations, but if there is a large amount of grinding aid, the amount of wastewater will be large, and a lot of thermal energy is required for recovery, so it is not economically viable. Very disadvantageous. For this reason, how to reduce the amount of the grinding aid has been a major issue in the wet grinding method. The inventors of the present invention have arrived at the method of the present invention as a result of intensive research and study on methods to improve the drawbacks of these conventional methods. That is, the method of the present invention is a method of wet-milling crude copper phthalocyanine in the coexistence of a milling aid and an organic liquid. (In the formula, Pc represents a metal or a metal-free phthalocyanine residue, and n represents a number from 1 to 4.) Production of a copper phthalocyanine pigment characterized by adding and grinding phthalimidomethyl phthalocyanine represented by It is the law. In the present invention, in the phthalimidomethyl phthalocyanine represented by the general formula (), metals include Fe, Ni, and especially Cu, which can be produced by known methods. Phthalimidomethyl copper phthalocyanine can be used with particular advantage. The crude copper phthalocyanine used in the present invention is, for example, JP-A-52-38536, JP-A-57-87465.
It can be obtained by the method described in et al. Examples of the grinding aid include water-soluble ones such as sodium chloride, sodium sulfate, and calcium chloride, and these may be used alone or in combination of two or more. Further, it is preferable to use a grinding aid that has been ground in advance using a grinder. The amount used varies depending on the desired pigment quality, but is 2 to 10 times the weight of crude copper phthalocyanine, preferably ~7 times the weight of crude copper phthalocyanine. In the present invention, the organic liquid preferably has at least some water solubility, such as alcohols and polyols. Specific examples of alcohols include n-propyl alcohol, n-butyl alcohol, isopropyl alcohol, and isobutyl alcohol. Examples of polyols include polyols, polyol ethers, polyol esters, and chlorinated derivatives thereof. These may be used singly or in combination. Specifically, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol,
These include dipropylene glycol, tripropylene glycol, and tetrapropylene glycol. The amount of organic liquid used varies depending on the amount of grinding aid used, but it is
An amount of -50% by weight combined with 10 to 30% by weight, based on the grinding aid, is advantageous. The amount of phthalimidomethyl phthalocyanine pigment used, which characterizes the invention, is from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, based on the crude copper phthalocyanine.
is preferable. As for when to add it, there are two methods: adding it from the beginning or adding it during the grinding process, but adding it from the beginning is effective. In the present invention, crystal form stabilizing agents may be added depending on the case, and examples thereof include aliphatic and aromatic hydrocarbons such as acetone, trichlene, perchlorene, xylene, and toluene. The amount used is 5-100% by weight, preferably 8-50% by weight, based on the crude copper phthalocyanine. Two or more of these may be used in combination. After grinding, the copper phthalocyanine pigment is removed by a conventional method. That is, the milled contents are treated with water or dilute acid to dissolve the milling aid and organic liquid, the treated solution is filtered to separate the pigment, and the desired copper phthalocyanine pigment is obtained by washing, drying, and pulverizing. be able to. The copper phthalocyanine pigment obtained by the method of the present invention has the same quality or higher coloring power than the pigment obtained by the conventional method, and also has a grinding aid and an organic liquid. 20～ compared to conventional method
Can be reduced by 40%. The following table summarizes the effect of adding phthalimidomethyl copper phthalocyanine and the relationship between the amount of copper phthalocyanine as a grinding aid and the coloring strength.

【table】

[Table] Next, the present invention will be explained with reference to Examples and Comparative Examples, but is not limited thereto. Furthermore, in the examples, parts by weight represent parts by weight. Comparative Example 1 256 parts of crude β-type copper phthalocyanine (purity 97.5%) and 1750 parts of pulverized sodium chloride are charged into a 4000-volume double-arm mixer and mixed uniformly. Next, 380 parts of diethylene glycol was gradually injected, and while keeping the contents in the form of a dense lump that was neither powdery nor gruel-like, 15 parts of perklein was injected, and the mixture was kneaded and ground at 65 to 75°C for 8 hours. The ground contents are placed in a beaker, 7000 parts of 1% sulfuric acid is added, and the mixture is stirred at 80 to 90°C for 1 hour. The wet cake is then filtered and washed with water, and the resulting wet cake is dried at 70-80°C. 247.5 parts of copper phthalocyanine pigment were thus obtained. Example 1 256 parts of crude β-type copper phthalocyanine (purity 97.5%), 2.5 parts of phthalimidomethyl copper phthalocyanine pigment, and 1750 parts of ground sodium chloride are charged into a 4000-part double-arm mixer and mixed uniformly. Next, gradually inject 380 parts of diethylene glycol,
While keeping the contents in a dense lump that is neither powdery nor gruel-like, 15 parts of Perculen is poured into the mixture, and the mixture is kneaded and ground at 65-75°C for 8 hours. The ground contents are placed in a beaker, 7000 parts of 1% sulfuric acid is added, and the mixture is stirred at 80 to 90°C for 1 hour. The wet cake is then washed with water and dried at 70-80°C. 249.5 parts of copper phthalocyanine pigment are thus obtained. Pigment Handbook (edited by Japan Pigment Technology Association)
As a result of the coloring strength test described on page 85, when the pigment obtained in Comparative Example 1 was used as the standard (100), the pigment obtained in this example had a coloring strength of 110% and was excellent in transparency and sharpness. Ta. Example 2 The same procedure as in Example 1 was repeated except that the grinding aids, ie, pulverized sodium chloride, was changed to 1250 parts, and diethylene glycol was changed to 270 parts, and 250 parts of a copper phthalocyanine pigment was obtained. The color strength was compared with the pigment obtained in Example 2 using Comparative Example 1 as a standard (100) according to the color strength test method described in Example 1, and the color tone was the same and the color strength was 103%. Example 3 In Example 2, the amount of phthalimidomethyl copper phthalocyanine pigment was changed to 12.5 parts, and the other procedures were carried out in the same manner as in Example 2 to obtain 259.5 parts of copper phthalocyanine pigment. According to the color strength test method described in Example 1, the color strength was compared with the pigment obtained in Example 3 using the pigment obtained in Comparative Example 1 as a standard (100).The color strength was 107%, and the transparency was , and had excellent clarity. Example 4 The same procedure as in Example 1 was repeated except that the grinding aids, ie, pulverized sodium chloride, was changed to 1000 parts, and diethylene glycol was changed to 250 parts, and the process was repeated in the same manner as in Example 1 to obtain 248 parts of a copper phthalocyanine pigment. Example 4 was prepared according to the color strength test method described in Example 1, using the pigment obtained in Comparative Example 1 as the standard (100).
When the color strength was compared with that of the pigment obtained in , the color strength was 98%. Example 5 The same procedure as in Example 4 was repeated except that 5 parts of the phthalimidomethyl copper phthalocyanine pigment was used in Example 4 to obtain 251 parts of a copper phthalocyanine pigment. Example 5 was prepared according to the color strength test method described in Example 1, using the pigment obtained in Comparative Example 1 as the standard (100).
When comparing the coloring intensity with the pigment obtained in , the color tone and transparency were the same at 100% coloring intensity. Comparative Example 2 In Comparative Example 1, 1250 parts of crushed sodium chloride, which is a grinding aid, and diethylene glycol were added.
270 parts and otherwise treated in the same manner as in Comparative Example 1 to obtain 247.5 parts of copper phthalocyanine pigment. When the coloring strength of this product was compared using the pigment obtained in Comparative Example 1 as a standard (100), the coloring strength was 90% and the clarity and transparency were poor. Example 6 In Comparative Example 2, 1.25 parts of the phthalimidomethyl copper phthalocyanine pigment was added, and the other procedures were carried out in the same manner as in Comparative Example 2 to obtain 248 parts of the copper phthalocyanine pigment. The pigment obtained in Comparative Example 2 was used as the standard (100).
When comparing the coloring strength, it was found that the coloring strength
It was 107%, with excellent clarity and transparency.
Further, when the coloring strength was compared using the pigment obtained in Comparative Example 1 as a standard (100), it was 97%. Example 7 In Comparative Example 2, 875 parts of crushed sodium chloride, which is a grinding aid, and 230 parts of diethylene glycol were added.
Part, phthalimidomethyl copper phthalocyanine pigment
2.5 parts and otherwise treated in the same manner as in Comparative Example 2 to obtain 249 parts of copper phthalocyanine pigment. The pigment obtained in Comparative Example 2 was used as the standard (100).
When comparing the coloring strength, the coloring strength was 103%.
It had excellent clarity and transparency. Further, when the coloring strength was compared using the pigment obtained in Comparative Example 1 as a standard (100), it was 93%.

Claims (1)

[Scope of Claims] 1. In a method of wet-milling crude copper phthalocyanine in the presence of an organic liquid consisting of an inorganic salt as a milling aid and one or more alcohols or polyols, Te2~
Using 10 times the weight of the grinding aid, 20 to 50% by weight of the crude copper phthalocyanine and the grinding aid
Using a total amount of organic liquid of 10 to 30% by weight, further, general formula () (In the formula, Pc represents a metal or metal-free phthalocyanine residue, and n represents a number from 1 to 4.)
A method for producing a copper phthalocyanine pigment, which comprises adding % by weight and grinding. 2. The method according to claim 1, wherein the grinding aid is one or more selected from sodium chloride, sodium sulfate, and calcium chloride.