JPH04320458A - Production of copper phthalocyanine pigment - Google Patents

Abstract

PURPOSE:To provide a new process for producing a pigment which is freed from the disadvantage of the conventional solvent salt milling process which requires large amounts of a grinding aid and an organic liquid and excessive energy to effect grinding for a long time. CONSTITUTION:A process for producing a copper phthalocyanine pigment comprising dry-crushing crude copper phthalocyanine together with a phthalocyanine derivative and wet-grinding the product in the presence of a grinding aid and an organic liquid.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION The present invention relates to a method for producing copper phthalocyanine pigments by wet milling. More specifically, it relates to a method for producing a copper phthalocyanine pigment, characterized in that the crude copper phthalocyanine is dry-milled together with a phthalocyanine derivative in advance in a method of wet-milling the crude copper phthalocyanine in the presence of a milling aid and an organic liquid.

0002

[Prior Art] Finely divided copper phthalocyanine pigments are used in large quantities in the color material industry because of their beautiful color tone, high coloring power, and good performance such as weather resistance and heat resistance. Widely used.

Crude copper phthalocyanine is usually prepared using phthalic anhydride or its derivatives, urea and a copper source, or phthalodinitrile or its derivatives and a copper source, in the presence or absence of a catalyst such as ammonium molybdate or titanium tetrachloride. It is produced by reacting in an organic solvent such as alkylbenzene, trichlorobenzene or nitrobenzene under normal pressure or increased pressure. However, the synthesized phthalocyanine molecules undergo crystal growth one after another in the synthesis solvent, and the major axis of the phthalocyanine molecules is 10~
It can only be obtained in the form of coarsely acicular crystals of about 200 μm, and its value as a coloring pigment for inks, paints, plastics, etc. is very low or non-existent.

[0004] Therefore, the crude copper phthalocyanine is a particle with high color utility value, that is, 0.01 to 0.5
It is necessary to refine the particles to about μm (hereinafter, this operation will be referred to as pigmentation).

As an industrial method, crude copper phthalocyanine is dry-milled with a grinding aid such as anhydrous sodium ferrocyanide or anhydrous barium chloride at a high temperature of 100 to 150° C. for a long time, the so-called dry salt milling method. The so-called solvent salt milling method, in which crude copper phthalocyanine is charged into a dual-arm dispersion mixer together with a milling aid such as a water-soluble inorganic salt such as sodium chloride and an organic liquid such as alcohol, polyol, or amine, and wet-milled, is used. There is a so-called dry milling method in which crude copper phthalocyanine is dry-milled in the absence of a chemical agent or an organic liquid, and then treated with an organic solvent or the like.

[0006]

[Problems to be Solved by the Invention] However, in the conventional method of producing pigments by solvent salt milling, a large amount of grinding aids and organic liquids are used, and there are restrictions on the drainage of water used during subsequent separation from pigments. It takes a lot of time and effort to collect and process the process, and it also requires a lot of energy for long grinding.There are many problems that need to be resolved.

[0007]

[Means for Solving the Problems] The present inventors have conducted extensive research to solve the above problems, and have finally accomplished the present invention.

The present invention provides a method for producing copper phthalocyanine pigments, which comprises dry-milling crude copper phthalocyanine together with a phthalocyanine derivative, and then wet-milling in the presence of a milling aid and an organic liquid. .

[0009] The production method for the crude copper phthalocyanine is not particularly limited, but phthalic anhydride or its derivatives, urea and a copper source, or phthalodinitrile or its derivatives and a copper source are used in the presence or absence of a catalyst. It is produced by reacting in an organic solvent at 120 to 270°C, preferably 170 to 230°C, for 2 to 15 hours, preferably 3 to 7 hours, under normal pressure or increased pressure. Note that the crude copper phthalocyanine may be a low chlorinated copper phthalocyanine.

Examples of the phthalocyanine derivatives according to the present invention include the following. These can be used alone or in combination of two or more.

Cu-Pc-(Cl)n
n=1 to 16Cu-Pc-[(Cl
) n1, (Br)n2] n2=1
~15, n2=1~6, n1+n2≦16 Al-Pc-(Cl)n
n= 1 ~ 16Cu-Pc-[CH2N
(C2H5)2] n n= 0.5
~4

[Formula 1] Cu-Pc-[CH2NHCOCH2NH(CH2)
3(C4H9)2] n n= 0.5 ~
4

[Chemical formula 2] Cu-Pc-[CH2NH(CH2)5N(C2H5
)2] n n= 0.5~4

[Chemical formula 3] Cu-Pc-[CH2N(C4H9)2] n
n=0.5~4

[C4
] Cu-Pc-(SO3H)n
n=0.5 ~
4 Cu-Pc-[SO2NH(CH2)3N(C2H5
)2] n n= 0.5 ~
4 Cu-Pc-[CH2NHCOCH2N(C2H5)
2] n n = 0.5 ~
4 Cu-Pc −[SO3− ・NH3 + (CH2)
11CH3] n n= 0.5 ~ 4 Cu-Pc - [SO3- ・NH3 + (CH2
)8CH3] n n= 0.5 ~4 Cu-Pc −[SO3− ・NH3 + (CH3)
3(CH2)11CH3] n n= 0.5 ~4 Cu-Pc -[SO3- ・NH+ NH((CH2
)11CH3)3 ] n n= 0.5 ~4 Cu-Pc -[SO3- ・NH+ ((CH2)1
1CH3)2 ] n n = 0.5 to 4 (Pc in the formula is a phthalocyanine residue, and n indicates the average number of substitutions.)

The amount of the phthalocyanine derivative added is 0.5 to 15% by weight based on the crude copper phthalocyanine, but if it is less than 0.5% by weight, sufficient effect cannot be obtained, and if it exceeds 15% by weight, It is not economical to add it. The preferred amount is 1 to 12% by weight, more preferably 2% by weight.
~10% by weight. Moreover, one or more of the above derivatives can be further mixed after the pigment is formed.

[0013] Examples of the organic liquid in the present invention include alcohols and polyols. Specifically, the 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, and these may be used alone or in combination of two or more thereof. Specific examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol. The amount of organic liquid used is
Although it varies depending on the amount of the grinding aid used, it is 0.1 to 2.0 times the weight of crude copper phthalocyanine, preferably 0.3
~1.5 times the weight.

[0014] 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. Furthermore, it is better to use a grinding aid that has been ground in advance. The amount used varies depending on the quality of the pigment to be obtained, but is 1 to 10 times the weight of crude copper phthalocyanine, preferably 2 to 8 times the weight of the crude copper phthalocyanine.

[0015] These grinding aids may also be added during dry grinding, and they work as grinding aids in dry grinding to increase grinding efficiency, and in the subsequent wet grinding, they are the same as the grinding aids added at that time. do the work. The amount of grinding aid added during dry grinding is 5.
Up to 3 times the weight, and more than this will result in poor efficiency, and preferably up to 3 times the weight.

[0016] For dry pulverization in the process, for example, a ball mill, a vibration mill, an attritor, or other pulverizers can be used. The grinding temperature can be freely set within the range of 20 to 130°C. The present invention will be specifically explained below with reference to Examples, but the present invention is not limited by the Examples. In the examples, "part" means part by weight, and "%" means % by weight.

Comparative Example 1 250 parts of crude copper phthalocyanine (halogen-free) produced by a conventional method, 1000 parts of dried sodium chloride and 250 parts of polyethylene glycol were placed in a 2 liter test kneader and kneaded at 100 to 110°C for 4 hours. The resulting mass was poured into 5 liters of warm water containing 25 g of 10% diluted sulfuric acid, stirred to completely dissolve the sodium chloride and polyethylene glycol, filtered, washed with water until acid-free, and filtered out the pigment. is dried at 90-100°C.

Example 1 95 parts of crude copper phthalocyanine (halogen-free) produced by a conventional method and 5 parts of the following phthalocyanine derivative were charged into an attritor and dry-pulverized for 5 minutes at a pulverization temperature of 50°C. The power consumption was 0.32 KWH/kg-pigment, the crystal form contained 9% α type, and the volume was 2.5 l/kg. The same operation (kneading) was performed except that this dry-pulverized product was replaced with the crude copper phthalocyanine of Comparative Example 1.

[Chemical formula 5] (Cu-Pc in the formula is a copper phthalocyanine residue) An offset ink was prepared using the obtained pigment and the pigment obtained in Comparative Example 1, and as a result of a comparative test, the coloring strength of this example was 115 %
(The coloring strength of the ink of the comparative example was set as 100% and was determined by a comparative judgment method. The same applies hereinafter.) It was also transparent and clear.

Examples 2 to 4 Comparative evaluation with Comparative Example 1 was carried out in the same manner as in Example 1 except that the phthalocyanine derivative added during the dry grinding was replaced with the following one. (Example 2) Cu-Pc-[SO3- ・NH3 +
(CH2)11CH3]1.5 (Example 3) Cu-Pc
-[SO2NH(CH2)3N(C2H5)2]1.5
(Example 4) Cu-Pc-Cl4 (Cu-Pc in the formula is a copper phthalocyanine residue) Example 2
Compared to Comparative Example 1, the pigments obtained in ~4 had a coloring strength of 1
05%, 109%, and 107%, the hue was clear and transparent.

Example 5 A pigment obtained in the same manner as in Example 1 but with a kneading time of 2 hours had the same coloring power, sharpness, and transparency as Comparative Example 1.

Example 6 In the same manner as in Example 1, dry pulverized product, sodium chloride,
The pigments obtained by adding 500 parts, 1250 parts, and 300 parts of polyethylene glycol had the same coloring power, sharpness, and transparency as Comparative Example 1.

Example 7 The sodium chloride dried during the dry grinding in Example 1 was
The same operation was performed using 500 parts of the obtained pulverized product and 750 parts of sodium chloride. The resulting pigment had a coloring strength of 110% compared to Comparative Example 1, and was clear and transparent.

Example 8 The same operation as in Example 1 was carried out except that the amounts of sodium chloride and polyethylene glycol added were halved to 500 parts and 125 parts, respectively. The resulting pigment had the same coloring power, sharpness, and transparency as Comparative Example 1.

[0024]

[Effects of the Invention] The advantages of the method for producing copper phthalocyanine according to the present invention are as follows. (1) Less milling time is required to obtain pigments of the same quality. (2) As a result, the total required energy including dry grinding can be reduced. (3) High-quality pigments can be obtained using the same energy as in conventional methods. (4) The throughput per unit capacity of the kneader is increased, resulting in high productivity. (5) Since fewer grinding aids and organic liquids are used, wastewater treatment can be reduced. It has extremely high utility value as an industrial pigment manufacturing method.

Claims (1)

[Claims] 1. A method for producing a copper phthalocyanine pigment, which comprises dry grinding crude copper phthalocyanine together with a phthalocyanine derivative, and then wet grinding in the presence of a grinding aid and an organic liquid.