JPS6166757A - Production of halogenated copper phthalocyanine pigment for gravure printing ink - Google Patents

Abstract

PURPOSE:To obtain the titled pigment having high coloring value and giving an ink having excellent fluidity, by adding a beta-naphthol compound to a halogenated copper phthalocyanine pigment, and kneading the mixture with a kneader in the presence of water under heating. CONSTITUTION:Crude halogenated copper phthalocyanine prepared by the halogenation of copper phthalocyanine is mixed with beta-naphthol. The mixture is kneaded with a kneader in the presence of water under heating to obtain the objective pigment. The kneading is carried out preferably at 90-110 deg.C under normal or positive pressure for 2-5hr. The ratio of the halogenated copper phthalocyanine pigment to the beta-naphthol is preferably 100:30-100.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a halogenated copper phthalocyanine pigment for intaglio printing ink. As halogen-substituted copper phthalocyanines in which a halogen atom is substituted in the benzene nucleus of copper phthalocyanine, chloro-substituted copper phthalocyanines, bromine-substituted copper phthalocyanines, and chloro-bromo copper phthalocyanine in which chromium and bromine are substituted in the same molecule are generally known. .

Halogenated copper phthalocyanine pigments are bright green pigments with good heat resistance, weather resistance, and chemical resistance, and are therefore used in many practical applications as pigments for printing inks.

In particular, intaglio inks are required to have good fluidity.

Since the above-mentioned halogen-substituted copper phthalocyanine is produced in a form unsuitable for use as a pigment during synthesis, various processing methods are known for converting the obtained crude halogen-substituted copper phthalocyanine into a form suitable for use as a pigment.

For example, a method in which crude phthalocyanine is dissolved or suspended in sulfuric acid and poured into water to precipitate it again as fine particles, or a method in which crude phthalocyanine is mixed with an inorganic salt such as common salt and ground to form a pigment. Furthermore, a method of converting crude halogenated phthalocyanine into a pigment by heating it with β-naphthol (Japanese Patent Publication No. 45-14
No. 425 (1ll1) and the like are known.

However, the particles of the pigment itself are so fine that when used in ink, the ink has poor fluidity, resulting in poor wiping properties and poor coloring power.

With the aim of eliminating the above-mentioned defects, the present inventors have conducted various studies to obtain a halogenated copper phthalocyanine pigment that does not reduce coloring power and has excellent fluidity for ink. We discovered that by mixing the crude halogenated copper phthalocyanine obtained by β-naphtholate and milling it in a kneader under heating, a pigment with coloring power and excellent fluidity when made into ink could be obtained. invention has been achieved.

That is, the present invention provides a method for producing a halogenated copper phthalocyanine pigment for intaglio printing ink, which comprises adding β-naphthols to a halogenated copper phthalocyanine pigment and heat-milling this mixture in a kneader in the presence of water. It is.

The halogenated copper phthalocyanine used in the present invention includes:
Examples include those having 10-16 chlorine atoms, bromine atoms and chlorine-bromine atoms.

Further, as the halogenated copper phthalocyanine pigment used in the present invention, both a crude halogenated copper phthalocyanine pigment and a halogenated copper phthalocyanine pigment pigmented by a conventional method can be used.

When a dry halogenated copper phthalocyanine pigment is used in the practice of the present invention, the pigment is predispersed in water and an organic solvent such as butyl cellosolve to form a paste, and then mixed with β-naphthol. However, when a wet press cake of halogenated copper phthalocyanine is used, water is added in an amount to peptize the press cake, and β-naphthol is further blended therein.

The halogenated copper phthalocyanine pigment mixture containing β-naphthol was placed in a kneader at a temperature of 80°C to 150°C.
°C, preferably 90 to 110 °C, 2 to 2 °C under normal pressure or increased pressure
Kneaded for 5 hours.

The amount of β-naphthol added in the above kneading is preferably the minimum necessary amount, for example, 20 to 300 parts by weight of β-naphthol to 100 parts by weight of the halogenated copper phthalocyanine pigment.
Preferably, 30 to 100 parts by weight of Geo is preferred.

After the kneading is completed, an aqueous solution of caustic soda equivalent to β-naphthol is added to dissolve the β-naphthol, and the pigment is separated by filtration, and the β-naphthol in the filtrate is recovered by acid precipitation.

The halogenated copper phthalocyanine pigment obtained by the present invention has a clearer color tone, a smaller specific surface area of particles, and a coloring power of 1
Improved by 0% or more.

Further, the halogenated copper phthalocyanine pigment according to the present invention is
It has extremely excellent fluidity when used not only in intaglio printing inks, but also in offset printing inks, gravure inks, and paints.

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Crude chlorinated copper phthalocyanine pigment presscake obtained by conventional methods (pigment bone 40%, chlorine content approx. 47
．． 5%) in a pure amount of 250 parts by weight to a kneader 11)
and further added 250 parts of water and 250 parts by weight of β-naphthol, and kneaded at 95 to 100° C. for 3 hours with stirring.

Next, 70 parts by weight of caustic soda was added in the form of an approximately 10% aqueous solution, β-naphthol was dissolved, the pigment was separated, the pigment was washed with water and dried, and the resulting pigment had a higher coloring power than the pigment obtained in the comparative example. has increased by 10%.

Furthermore, after thoroughly kneading 10 parts by weight of the obtained chlorinated copper phthalocyanine pigment and 20 parts by weight of modified linseed oil with a test roll, the ink flow measurement (JIS 5701) was performed, and the result was 3.50. The surface area was 51 rrr/g, and the fluidity was excellent.

Example 2 300 parts by weight of crude chlorinated copper phthalocyanine pigment presscake (pigment bone 40%, chlorine content approximately 47.5%) was placed in a kneader (m<IIl), and then 150 parts of water and β-naphthol were added. Add 150 parts by weight and add 95 to 100 parts by weight while stirring.
Kneading is carried out for 3 hours at °C.

Next, 42 parts of caustic Zoda was added in the form of an approximately 10% aqueous solution.
-The pigment obtained by dissolving the naphthol and separating the pigment, washing it with water and drying it had a clear color tone similar to Example 1, and β-
The density was increased by 15% compared to the pigment that was not treated with a kneader by adding naphthol.

After thoroughly kneading 10 parts by weight of the obtained chlorinated copper phthalocyanine pigment and 20 parts by weight of modified linseed oil with a test roll, the ink flow measurement (JIS K 5701) was performed and the result was 3.60, and the specific surface area was 481/g, and had excellent fluidity.

Example 3 300 parts by weight of a chlorinated copper phthalocyanine pigment (chlorine content: about 47.5%) obtained by the pigmentation method of the school was put into a kneader (II2 kneader), and 470 parts by weight of a 5% butyl cellosolve aqueous solution was added. Stir. Next, 99 parts by weight of β-naphthol was added to this mixture, and while stirring, 95 to 10 parts by weight of
Kneading is carried out for 3 hours at 0°C.

Next, 28 parts by weight of caustic soda was added in the form of an approximately 10% aqueous solution to separate the pigment, and when the pigment was washed with water and dried, the color tone was clear, and the concentration was increased by 15% compared to the pigment that was not treated with a kneader by adding β-naphthol. did.

After sufficiently kneading 10 parts by weight of the obtained chlorinated copper phthalocyanine pigment and 20 parts by weight of modified linseed oil using a test roll,
The result of ink flow measurement (JIS K5701) was 3.70, and the specific surface area was 42g/g.
It had excellent liquidity.

Example 4 Crude chloro-bromo copper phthalocyanine pigment (7% chlorine,
625 parts by weight of a press cake containing about 40% (58% bromine), 125 parts by weight of water and 125 parts by weight of β-naphthol are placed in a kneader (1-gu), and kneaded at 95-100° C. for 3 hours with stirring.

Next, 35 parts by weight of caustic soda was added in the form of an approximately 10% aqueous solution to separate the pigment, and when the pigment was washed with water and dried, the color tone was clear, and the coloring power was a comparative example compared to a pigment that was not treated with a kneader after adding β-naphthol. This is an increase of 15% compared to 2.

After sufficiently kneading 10 parts by weight of the obtained chloro-bromine copper phthalocyanine pigment and 20 parts by weight of modified linseed oil using a test roll, the ink flow ff111 constant (JIS K
5701), the result was 3.90, the specific surface area was 24 m/g, and the fluidity was excellent.

Comparative Example 1 400 parts by weight of crude chlorinated copper phthalocyanine pigment press cake (pigment bone 40%, chlorine content approximately 47.5%) was placed in an oven-shaped stainless steel container, and peptized in 4000 parts of water. Add 400 parts by weight of β-naphthol, bring the temperature of the contents to 100°C, and stir for 3 hours.

Next, 112 parts by weight of caustic soda was added in the form of an approximately 10% aqueous solution, β-naphthol was dissolved, the pigment was separated, the pigment was washed with water, and the resulting pigment was subjected to flow measurement in the same manner as in Example I. The result was 2.86, indicating poor fluidity. The specific surface area was 87 m/g.

Comparative Example 2゜crude chloro-bromine copper phthalocyanine pigment press cake (ill content 40%, chlorine content 7%, bromine content 58%)
A pure amount of 400 parts by weight was placed in an oven-shaped stainless steel container, peptized in 4000 parts of water, 400 parts by weight of β-naphthol was added, the temperature of the contents was brought to 100°C, and the mixture was stirred for 3 hours.

Next, a calculated amount of caustic soda was added in the form of an approximately 10% aqueous solution to separate the pigment, and the pigment was washed with water and dried. The ink flow was measured in the same manner as in Example 1, and the result was 2.92. Sex wasn't good. Specific surface area 61m/g
Met'.

Chapter 1 Table

Claims (1)

[Claims] A method for producing a halogenated copper phthalocyanine pigment for intaglio printing ink, which comprises adding β-naphthols to the halogenated copper phthalocyanine pigment and heat-milling the mixture in a kneader in the presence of water.