JP2002114924A - Process for producing halogenated metal phthalocyanine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a pigment-quality halogenated metal phthalocyanine pigment in high yields without the necessity for a treatment for conversion into a pigment. SOLUTION: In the process for producing a halogenated metal phthalocyanine pigment by thermally reacting a halogenated phthalodinitrile (A) with a metal salt (B) of an aliphatic or alicyclic monocarboxylic acid in the presence of ammonia (C), optionally an ammonia donor, in an organic solvent (D), the reaction is effected by using as the organic solvent (D) an aromatic organic solvent having a boiling point of 373-423 K and capable of dissolving both the halogenated phthalodinitrile (A) and the metal salt (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a metal phthalocyanine halide suitable as an organic pigment.

[0002]

2. Description of the Related Art Japanese Patent Publication No. 45-8101 discloses that a halogenated phthalodinitrile and a metal salt of an aliphatic monocarboxylic acid are prepared in a hydrophilic organic solvent such as an alcohol in the presence of an alkaline substance. A method for producing a metal halide phthalocyanine pigment to be reacted is described.

[0003]

However, according to the above-mentioned production method, the main raw materials, that is, the halogenated phthalodinitrile and the metal salt of the aliphatic monocarboxylic acid, have low solubility in the reaction solvent. There is a disadvantage that the reaction system is heterogeneous, and as a result, the yield of the metal halide phthalocyanine is low.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above-mentioned situation, and found that a specific metal salt of a monocarboxylic acid and a specific reaction solvent are mixed so that the main raw materials are uniformly dissolved in the reaction system. By performing the reaction in combination with
It has been found that metal halide phthalocyanines can be obtained in high yields even at relatively low reaction temperatures.

[0005] In addition, the reaction can be carried out at a relatively low temperature, and as a result, crystals do not grow too much and have an appropriate particle shape. Thus, a pigment suitable for a colorant can be prepared without performing a conventionally required pigmentation treatment. Found that metal halide phthalocyanine that can also be used as is obtained with good productivity,
The present invention has been completed.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Terms used in the present invention are defined below. The halogenated phthalodinitrile (A) refers to phthalodinitrile in which 1 to 4 hydrogen atoms on a benzene ring are substituted with a halogen atom. The halogenated phthalodinitrile (A) was reacted with the halogenated phthalodinitrile and ammonia or alcohol in equimolar amounts.
Ammonia adducts and alcohol adducts of halogenated phthalodinitrile are also included. The ammonia donor (C) refers to one that generates ammonia by heating.

Hereinafter, the present invention will be described in detail. The present invention relates to a method for converting a halogenated phthalodinitrile (A) and a metal salt of an aliphatic or alicyclic monocarboxylic acid (B) into an organic solvent (D) in the presence of ammonia or an ammonia donor (C). In the method for producing a metal halide phthalocyanine pigment which is heated and reacted in an air, the organic solvent (D) is a metal salt (B) of the halogenated phthalodinitrile (A) and the aliphatic or alicyclic monocarboxylic acid. Characterized by using an aromatic organic solvent having a boiling point of 373 to 423 K which dissolves both of these, and provides a method for producing a metal halide phthalocyanine in high yield which can be used as a pigment without requiring a pigmentation treatment. It is.

[0008] The halogenated metal phthalocyanine obtained in the present invention is a metal phthalocyanine in which a hydrogen atom on a phthalocyanine ring is substituted by a halogen atom.

The halogenated phthalodinitrile (A) used in the present invention includes phthalodinitrile, which is known per se, and the above-mentioned adduct, 1,3-
Mono-, di-, tri- or tetra-substituted halides such as diiminoisoindoline and 1-alkoxy-3-iminoisoindolenine can be mentioned, and these can be used alone or in combination. As the halogen atom, any halogen atom can be used, but industrially, chlorine or bromine is generally used.

As the metal salt (B) of the aliphatic or alicyclic monocarboxylic acid used in the present invention, known ones can be used. Specifically, aliphatic or alicyclic monocarboxylic acid, For example, it can be obtained by reacting with a metal sulfate or the like.

The monocarboxylic acid used for the aliphatic or alicyclic monocarboxylic acid metal salt (B) used in the present invention may be any of those known and commonly used. There are up to 30 aliphatic or cycloaliphatic monocarboxylic acids. For example, propionic acid, valeric acid, enanthic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, naphthenic acid, arachinic acid, lignoceric acid, heptacosanoic acid, melisic acid and the like. Preferably 10 total carbon atoms
~ 30 aliphatic or alicyclic monocarboxylic acids. For example, naphthenic acid, oleic acid, stearic acid, palmitic acid, lauric acid and the like can be mentioned, and naphthenic acid is particularly preferred.

In the present invention, naphthenic acid is a general term for carboxylic acid derivatives derived from petroleum, such as cyclopentane, cyclohexane, cycloheptane, and other homologs of naphthene, and has a molecular weight of 170 to 350.

The metal used for the metal salt of the aliphatic or alicyclic monocarboxylic acid (B) used in the present invention may be any of those known and used, for example, copper, titanium, vanadium, chromium, and the like. Aluminum, iron, cobalt, manganese, lead and zinc. These can be used, for example, as metal sulfates, as described above.

As the metal salt of the aliphatic or alicyclic monocarboxylic acid (B), those which have been produced and isolated in advance by a known method can be used, but the organic metal used for the synthesis of the metal halide phthalocyanine can be used. It is also possible to produce the halogenated metal phthalocyanine in the solvent (D) in advance and to produce the metal halide phthalocyanine without isolation, without any isolation. Can be.

The amount of the metal salt of aliphatic or alicyclic monocarboxylic acid (B) to be used is 0.1 to 4 mol of the halogenated phthalodinitrile (A) in any of the above-mentioned methods. 95 to 1.05 mol is preferred.

When the metal salt (B) of the aliphatic or alicyclic monocarboxylic acid used in the present invention is produced in the organic solvent (D) used for the synthesis of the metal phthalocyanine halide, the aliphatic or alicyclic metal is used. By heating a formula monocarboxylic acid and a metal salt such as a metal sulfate or a metal chloride in the presence of a basic substance, an aliphatic or alicyclic monocarboxylic acid metal salt (B) is converted into an organic solvent ( It is produced during D) and can be continuously supplied to the production of metal halide phthalocyanine without isolation.

The amount of the aliphatic or alicyclic monocarboxylic acid used in this case is such that the stoichiometric amount of the metal salt such as a metal sulfate or a metal chloride reacts without excess or deficiency. It is not always necessary, for example, 0.1 to 1 equivalent may be used. That is, even if the amount used is less than the stoichiometric amount, the monocarboxylic acid is converted from the aliphatic or alicyclic monocarboxylic acid metal salt (B) consumed by the reaction with the halogenated phthalodinitrile (A). Is liberated, reacts with an unreacted metal salt in the presence of a basic substance, again forms an aliphatic or alicyclic monocarboxylic acid metal salt (B), and is supplied to the reaction. However, the reaction proceeds continuously.

Therefore, even if the amount of the aliphatic or alicyclic monocarboxylic acid used is less than the stoichiometric amount, it does not hinder the progress of the reaction at all. This is preferable in that the same yield as in the above case can be obtained.

The basic substance used for the production of the metal salt of aliphatic or alicyclic monocarboxylic acid (B) in the organic solvent (D) includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, Potassium carbonate and the like are used, and the amount of use is generally 0.5 to 2 equivalents per 1 mol of a metal salt such as a metal sulfate or a metal chloride.

Organic solvent (D) used in the present invention
Is an aromatic organic solvent having a boiling point of 373 to 423 K (Kelvin temperature), and is a main raw material of the halogenated phthalodinitrile (A) and the metal salt of the aliphatic or alicyclic monocarboxylic acid ( B) need to be dissolved.

As such an organic solvent (D), an alkylbenzene having a total of 7 to 8 carbon atoms can be obtained by mixing a raw material phthalodinitrile (A) with an aliphatic or alicyclic monocarboxylic acid metal salt (B). ) Is preferable because of excellent solubility in both. For example, toluene, xylene and ethylbenzene are mentioned, and xylene is particularly preferred.

The amount of the organic solvent (D) used may be any amount as long as the reaction proceeds smoothly. Usually, the organic solvent (D) is used in an amount of 3 to 1 based on 1 part by weight of the halogenated phthalodinitrile (A).
0 parts by weight are used. Particularly preferably, it is 4 to 6 parts by weight.

Both the above-mentioned metal salt of an aliphatic or alicyclic monocarboxylic acid (B) and the halogenated phthalonitrile (A) are uniformly dissolved in the above-mentioned aromatic organic solvent, so that the reaction proceeds smoothly. As the process proceeds, a metal halide phthalocyanine can be synthesized in a high yield.

Aromatic hydrocarbons such as naphthalene or methylnaphthalene or nitrated or halogenated aromatic hydrocarbons such as nitrobenzene, di and trichlorobenzene are highly toxic and have a high boiling point, so that evaporation of the solvent may occur. The recovery requires a large amount of heat or requires measures such as reducing the pressure, and is not suitable for industrial mass production, and the use of a suitable organic solvent in the present invention has lower toxicity. In addition, since the solvent has a low boiling point, the solvent can be easily recovered, which is advantageous.

In the present invention, in order to make the reaction proceed smoothly, ammonia or ammonia donor (C) is added to the reaction system.
Need to be supplied. As the ammonia donor (C) used therefor, for example, ammonium acetate, ammonium hydrogen carbonate, urea, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium citrate,
Examples thereof include compounds such as ammonium oxalate, and one or more of them can be used.

The amount used is, for example, generally 1 to 2 mol per 1 mol of the metal salt (B) of the aliphatic or alicyclic monocarboxylic acid as the starting material.

In the present invention, the heating temperature of the system at the time of carrying out the reaction is suitably at least 363 K and at most the boiling point of the solvent used, and the highest yield can be obtained especially at a temperature close to the boiling point. The reaction time is appropriately set to 1 to 7 hours,
Particularly preferably, it is 3 to 5 hours.

According to the method of the present invention, a clear and high coloring power colorant can be obtained immediately after the completion of the reaction by filtration, washing with water, and drying. Washing with an aqueous solution is also possible.

The metal phthalocyanine halide thus obtained can be reacted at a relatively low temperature of 363 to 423 K. As a result, crystals do not grow too much and have an appropriate particle shape, and are suitable for a colorant. It can be used as it is as a pigment. Since it is not necessary to carry out a pigmentation treatment such as a known solvent salt milling which has been conventionally required, a pigmentation equipment such as a kneader is not required, so that capital investment can be reduced, and energy saving and productivity are high.

[0030]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. In the following, “%” means “% by weight” unless otherwise specified.

EXAMPLE 1 220 g of xylene, 44.1 g (0.16 mol) of tetrachlorophthalodinitrile, copper naphthenate (copper content: 500 g) were placed in a 500-ml glass reactor equipped with a stirrer, thermometer and cooling tube. 25.4 g (0.04 mol) and 6.2 g (0.08 mol) of ammonium acetate were charged and reacted at 408 K for 4 hours with stirring.

After the completion of the reaction, the mixture was cooled to 323 K, and the product was separated by filtration.
And washed. Then, the mixture was peptized in the order of 1000 g of 1% hydrochloric acid and 1000 g of 1% caustic soda, and each was washed at 363 K for 1 hour. After sufficiently washing the obtained wet cake with water, it was dried at 363 K to obtain 43.4 g of green hexadecachlorocopper phthalocyanine (yield 98.2%).

After preparing a lithographic ink in accordance with the test examples described below, the coloring power was evaluated according to the coloring power evaluation method. Even if a pigmentation treatment such as conventionally known solvent salt milling was not carried out, the solvent could be used. The coloring power was almost equivalent to the pigment obtained by salt milling.

Example 2 220 g of xylene and 10.2 g of naphthenic acid were placed in a 500 ml-capacity glass reactor equipped with a stirrer, thermometer and cooling tube.
(0.04 mol), 3.2 g of sodium hydroxide (0.0
8 mol), and the mixture was reacted at 343 K for 1 hour with stirring. Then, 6.4 g (0.04 mol) of copper sulfate was added, and the mixture was further reacted at 343 K with stirring for 2 hours. Then, 44.1 g (0.16 mol) of tetrachlorophthalodinitrile and 6.2 g (0.08 mol) of ammonium acetate were added, and the mixture was reacted at 408 K for 4 hours with stirring.

After the completion of the reaction, the same post-treatment as in Example 1 was carried out to give green hexadecachlorocopper phthalocyanine 42.6.
g was obtained (yield 94.5%). When the coloring power was evaluated in the same manner as in Example 1, the coloring power was almost the same as that of the pigment obtained by solvent salt milling without performing a conventionally known pigmentation treatment such as solvent salt milling.

Example 3 The procedure of Example 1 was repeated, except that 23.6 g of cobalt naphthenate (cobalt content: 10%) was used instead of 25.4 g of copper naphthenate. 40.9 g of chlorocobalt phthalocyanine was obtained (91.1% yield).

When the coloring power was evaluated in the same manner as in Example 1, the coloring power was almost the same as that of the pigment obtained by the solvent salt milling without performing the conventionally known pigmentation treatment such as solvent salt milling. there were.

Comparative Example 1 In place of 220 g of xylene of Example 1, ethanol 2 was used.
In the same manner as in Example 1 except that 20 g was used, 7.3 g of cupric acetic anhydride was used instead of 25.4 g of copper naphthenate, and the reaction temperature was changed to 348 K instead of 408 K,
3.7 g of green hexadecachloro copper phthalocyanine was obtained (8.1% yield).

In this example, the yield was extremely low due to the low solubility of cupric acetic anhydride in ethanol at 348K. When the coloring power was evaluated in the same manner as in Example 1, the coloring power was slightly inferior to the pigment obtained by solvent salt milling.

Test Example: Method for preparing lithographic inks The following methods were used to obtain lithographic inks obtained in Examples and Comparative Examples.
A lithographic ink was prepared using a halogenated metal phthalocyanine. 0.3 g pigment, resin varnish for lithographic ink 1.2
g was dispersed with a Hoover muller to produce a dark ink.
A light-colored ink was prepared by mixing 0.1 g of the dark-colored ink obtained above and 2.0 g of a white ink containing 30% of white pigment. Each of the obtained inks was used as a test ink, and the coloring power was evaluated by the following method.

Evaluation Method of Coloring Power Each metal phthalocyanine halide obtained in Examples and Comparative Examples was evaluated according to the following method. Commercially available hexadecachloro copper phthalocyanine green pigment (“FASTOGEN GREEN” manufactured by Dainippon Ink and Chemicals, Inc.)
S ") and the pigments obtained in Examples and Comparative Examples,
Dark and light color inks were prepared according to the above lithographic ink preparation method. The light-colored ink obtained from FASTOGEN GREEN S was used as a standard light-colored ink. The light-colored inks obtained in Examples and Comparative Examples were arranged side by side with a spatula on a color-developed paper to evaluate the coloring power.

[0042]

According to the present invention, a metal phthalocyanine halide can be obtained in a high yield by performing a reaction in a specific aromatic organic solvent using a metal salt of an aliphatic or alicyclic monocarboxylic acid. I can do it. In addition, the productivity can be improved because a metal halide phthalocyanine of pigment quality can be directly produced in high yield without performing a conventionally known pigmentation treatment such as solvent salt milling. Further, since a pigmentation treatment step is not required, there is an advantage that a pigmentation facility is not required, raw materials and energy required for the pigmentation treatment are not required, and productivity of a colorant is more improved.

Claims (4)

[Claims] 1. A halogenated phthalodinitrile (A),
In the method for producing a metal phthalocyanine halide, the metal salt (B) of an aliphatic or alicyclic monocarboxylic acid is heated and reacted in an organic solvent (D) in the presence of ammonia or an ammonia donor (C). As the organic solvent (D), an aromatic organic solvent having a boiling point of 373 to 423K that dissolves both the halogenated phthalodinitrile (A) and the metal salt of the aliphatic or alicyclic monocarboxylic acid (B) is used. A method for producing a metal halide phthalocyanine. 2. The method according to claim 1, wherein the aromatic organic solvent having a boiling point of 373 to 423 K is an alkylbenzene having a total of 7 to 8 carbon atoms. 3. The method according to claim 1, wherein the aliphatic or alicyclic monocarboxylic acid is a monocarboxylic acid having 3 to 30 carbon atoms in total. 4. The aliphatic or alicyclic monocarboxylic acid is a monocarboxylic acid having 10 to 30 carbon atoms in total.
Or the production method according to 2.