JPH07310024A - Production of beta-type copper phthalocyanine pigment - Google Patents

Abstract

PURPOSE:To industrially advantageously produce the subject pigment having a green-based hue and excellent in dispersibility, etc., by grinding a crude copper phthalocyanine pigment according to the dry method to prepare a mixture of alpha-form copper phthalocyanine and beta-form copper phthalocyanine and transferring it thoroughly to beta-form using an organic solvent. CONSTITUTION:This pigment is produced by (A) grinding a crude copper phthalocyanine according to the dry method to prepare a mixture of alpha-form copper phthalocyanine and beta-form copper phthalocyanine, subsequently (B) conducting transformation of the crystal form thoroughly to beta-type copper phthalocyanine in an organic solvent (preferably a three component mixture solvent composed of isopropyl alcohol, xylene and water) and then dispersing it under application of a mechanical energy (e.g. ball mill or oscillating mill). In addition, the weight ratio (alpha/beta) of alpha-form copper phthalocyanine to beta-form copper phthalocyanine in the above-mentioned mixture is preferably 40/60 to 80/20 and a copper phthalocyanine derivative {e.g. a compound of the formula [CuPc is copper phthalocyanine residue; (n) is an integer of 1 to 6]} is preferably added during the course of the process (A) or (B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a β-type copper phthalocyanine pigment, and more particularly to a method for industrially producing a greenish β-phthalocyanine pigment.

[0002]

2. Description of the Related Art Conventionally, a greenish β-type phthalocyanine pigment is industrially produced by a method in which a crude copper phthalocyanine is ground with an apparatus such as a kneader using an inorganic salt and a binder such as ethylene glycol. Has been done. This method
Since this is a method of using a grinding aid other than the pulverized material at the time of grinding, the cost for collecting and reusing these is high, which causes a high cost.

In order to solve these drawbacks, Japanese Unexamined Patent Publication No.
No. 0-157419 and Japanese Patent Laid-Open No. 52-69435 disclose that a crude copper phthalocyanine is dry pulverized to prepare a mixture of α-type copper phthalocyanine and β-type copper phthalocyanine, which is used as a crystallization solvent such as xylene. A method for obtaining a β-type copper phthalocyanine pigment by immersing it and converting it into a β-type crystal form is disclosed.

However, the β-type copper phthalocyanine pigment obtained by this method is compared with the conventional method in which crude copper phthalocyanine is ground by a kneader or the like using an inorganic salt and a binder such as ethylene glycol. Since the hue is reddish, the dispersion of the pigment in the vehicle is poor, and the coloring power is poor, substitution is difficult.

The reason why the hue becomes reddish is (1) when a mixture of α and β type is crystallized into β type in an organic solvent, it grows into large needle-like crystals. It is considered that the α-type crystal remains because the mixture is not sufficiently loosened during the apparent conversion to. In addition, the cause of poor dispersibility is, when dry-milling the crude copper phthalocyanine pigment, the primary crystals are a mixture of strongly agglomerated α and β-type copper phthalocyanine of several millimicrons, and to the extent of being immersed in an organic solvent, This is probably because it cannot be loosened enough.

In order to solve these drawbacks, Japanese Patent Application Laid-Open No.
No. 9-155467 discloses that when a crude copper phthalocyanine is dry-milled, a derivative of cyanine, for example, phthalimidomethyl copper phthalocyanine is added to form a mixture of α and β types, and a range in which a dry state can be maintained. Discloses a method of transferring an α-type component to a β-type composition by adding an organic solvent to form a β-type composition, and then dispersing the β-type composition in a solvent in the presence of mechanical energy.

However, according to this method, although the hue is certainly improved, there is a problem in dispersibility, it is not easily dispersed even in the presence of mechanical energy in a solvent, and the coloring power is inferior to the conventional manufacturing method. There was a problem. In this method, after the crude copper phthalocyanine is dry-milled to form a mixture of α and β-type copper phthalocyanine, it is converted to β-type by adding an organic solvent in the dry-milled state, so that needle-like large crystals are obtained. It is thought that this is because it is hard to generate, but on the other hand, the ground material is a loosely aggregated material.

[0008]

The problem to be solved by the present invention is to dry pulverize a crude copper phthalocyanine pigment to obtain a mixture of α and β type copper phthalocyanine, and then to add α type component to β type with an organic solvent. In order to provide a method for producing a β-type copper phthalocyanine pigment, a pigment having a green hue, excellent dispersibility, and easily mechanically dispersible is provided.

[0009]

Means for Solving the Problems The inventors of the present invention dry-milled a crude copper phthalocyanine pigment in the absence of a grinding aid,
By the method of solvent treatment, hue greenish, as a result of intensive research on a method of obtaining good dispersibility, after dry pulverizing the crude copper phthalocyanine pigment, while suppressing the growth of crystals in a crystallization solvent, A β-type copper phthalocyanine pigment, which has a green hue, good dispersibility, and excellent coloring power and is comparable to the conventional kneader method, is obtained by crystal conversion into β type and then dispersing in the presence of mechanical energy. They have found that they can be obtained and have completed the present invention.

That is, in order to solve the above problems, the present invention is a first step of producing a mixture of α-type copper phthalocyanine and β-type copper phthalocyanine by dry crushing crude copper phthalocyanine, the mixture in an organic solvent. Provided is a method for producing a β-type copper phthalocyanine pigment, which comprises a second step of completely converting the crystal form into β-type copper phthalocyanine and then dispersing the same in the presence of mechanical energy.

In the first stage, when the peak heights of the X-ray diffraction diagram showing the α-type and β-type crystal forms of the crude copper phthalocyanine pigment are Lα and Lβ, the α-type is determined from the calibration curve of Lα / Lβ and the content ratio. Dry pulverize until the content is ≧ 40%.
The most industrially advantageous one is that the content of α-type is about 60%. In the X-ray diffraction pattern, Lα had a peak height of 6.8 ° and Lβ had a peak height of 9.2 °.

In the second step, the pulverized product is immersed in an organic solvent to completely convert the α-type copper phthalocyanine into β-type copper phthalocyanine. This step is the most important. That is, it is desirable that the crystallinity is good and the crystal size is at least smaller than that used as a pigment. As a method of suppressing the growth of crystals, the type of solvent, the temperature of solvent immersion,
Time etc. Further, it is more preferable to add a derivative of a copper phthalocyanine pigment in this step.

As the derivative of the copper phthalocyanine pigment,
For example, the general formula (I)

[0014]

[Chemical 1]

(Wherein CuPc represents a copper phthalocyanine residue, and n represents an integer of 1 to 6), the general formula (II)

[0016]

[Chemical 2]

[In the formula, CuPc represents a copper phthalocyanine residue, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ each independently have 1 to 20 carbon atoms. An alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 6 to 8 carbon atoms, or a cycloalkyl group having 6 to 8 carbon atoms, or a 4-membered, 6-membered or 7-membered heterocyclic ring containing a nitrogen atom by R ² and R ³ ( As a ring-forming atom, one oxygen atom, a sulfur atom or another nitrogen atom may be contained). ] The compound represented by the general formula (III)

[0018]

[Chemical 3]

(In the formula, CuPc represents a copper phthalocyanine residue, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ each independently have 1 carbon atom. ˜20 alkyl group, alkoxyalkyl group having 3 to 12 carbon atoms, cycloalkyl group having 6 to 8 carbon atoms, or 5 member containing a nitrogen atom by R ² and R ³ , 6
Member or a 7-membered heterocyclic ring (which may contain one oxygen atom, a sulfur atom or another nitrogen atom as a ring-constituting atom), and n represents an integer of 1 to 6 . ) A compound represented by the general formula (IV)

[0020]

[Chemical 4]

(Wherein CuPc represents a copper phthalocyanine residue, Q represents a benzene ring or naphthalene ring which may have a substituent, and n represents an integer of 1 to 6). , General formula (V)

[0022]

[Chemical 5]

(In the formula, CuPc represents a copper phthalocyanine residue, and R ² and R ³ each independently have 1 to 2 carbon atoms.
0 alkyl group, alkoxyalkyl group having 3 to 12 carbon atoms, cycloalkyl group having 6 to 8 carbon atoms, or R
A 5-membered, 6-membered or 7-membered heterocyclic ring containing a nitrogen atom by ² and R ³ (even if it contains one oxygen atom, a sulfur atom or another nitrogen atom as an atom constituting the ring) Good)
And n represents an integer of 1 to 6. ).

When the derivatives of these copper phthalocyanine pigments are added, the addition amount is preferably in the range of 1 to 10% by weight based on the copper phthalocyanine pigment, and industrially 3 to 5%.
A weight% range is particularly preferred. Further, the same effect can be obtained by adding these copper phthalocyanine derivatives when dry-milling the crude copper phthalocyanine pigment.

Any organic solvent can be used as long as it has a crystal conversion capability for the copper phthalocyanine pigment.
Examples thereof include hydrocarbons such as benzene, toluene, xylene and mineral spirit, halogenated hydrocarbons such as trichloroethane, trichloroethylene and chlorobenzene, propanol, n-butanol, isobutanol, isopropyl alcohol, methyl cellosolve and ethyl. Alcohols such as cellosolve, butyl cellosolve, cyclohexanol, etc., Tetones such as methyl ethyl ketone, cyclohexanone, etc., ethyl acetate, propyl acetate, butyl acetate, esters such as cellosolve acetate, butyl cellosolve acetate, methyl benzoate, etc., dimethylformamide, N-methyl Examples thereof include amides such as pyrrolidone. Two or more kinds of these organic solvents can be mixed and used. Above all, it is preferable to use a mixed solvent of three kinds of isopropyl alcohol, xylene, and water in terms of the ability of crystal conversion from α type to β type, the ease of solvent recovery, and the quality of the obtained pigment. In this case, it is preferable to add a copper phthalocyanine derivative.

Examples of the mechanical energy device for dispersing the crystal conversion composition obtained as described above include a ball mill, a vibration mill, an attritor, a sand mill and a bead mill.

[0027]

EXAMPLES The present invention will be described in more detail with reference to production examples, examples and comparative examples. In the following description, “part” and “%” represent “part by weight” and “% by weight”, respectively.

<Production Example 1> (Production of crude copper phthalocyanine pigment) 1218 parts of phthalic anhydride, 1540 parts of urea, 200 parts of anhydrous cuprous chloride, 5 parts of ammonium molybdate and 5 to 8 carbon atoms as a solvent. 4000 parts of a mixture of alkylbenzene having an alkyl group was charged into a reactor, heated with stirring to raise the temperature to 200 ° C., and then reacted at the same temperature for 2.5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, the remaining reaction product was added to 8000 parts of 2% hydrochloric acid, and the mixture was stirred at 70 ° C. for 1 hour and then suction filtered. After thoroughly washing the cake thus obtained with warm water at 80 ° C.,
It was dried to obtain crude copper phthalocyanine.

<Production Example 2> (Production of dry pulverized product of crude copper phthalocyanine pigment) 500 parts of the crude copper phthalocyanine pigment obtained in Production Example 1 was mixed with an attritor having a volume of 5 liters (13 kg of steel balls having a diameter of 3/8 inch). Including), the internal temperature of 80 ℃ to 90 ℃
After crushing for 60 minutes, a mixture of 60% α-type copper phthalocyanine and 40% β-type copper phthalocyanine was obtained. α
The weight ratio of α-type copper phthalocyanine to β-type copper phthalocyanine (α / β) is the peak height Sα at the diffraction angle (2θ) = 6.8 ° that represents the α-type crystal form in the X-ray diffraction diagram shown in FIG. , Β-type crystal form diffraction angle (2θ) = 9.2
Was calculated from the peak height Sβ.

The X-ray diffraction conditions at this time are as follows: target: Cu, filter: Ni, voltage: 40 KV, current:
It is 30 mA.

<Comparative Example 1> (Kneader method) 500 parts of the mixture obtained in Production Example 2 was pulverized into 2500 parts of salt.
The mixture was kneaded together with 500 parts of diethylene glycol and 30 parts of xylene at 80 ° C. for 6 hours using a kneader having a capacity of 8 liters. 100 parts of the obtained kneaded material was added to a 1% hydrochloric acid aqueous solution 2
After dispersing with 000 parts at 80 ° C. for 2 hours, filtration,
It was washed with water and dried to obtain a pigment. The crystal form of the copper phthalocyanine thus obtained was analyzed by X-ray diffraction,
It was β type.

<Comparative Example 2> (Solvent method) 50 parts of the mixture obtained in Production Example 2 was added to 200 parts of isobutanol.
After heating at azeotropic temperature for 4 hours in a flask with a volume of 1 liter together with 100 parts of water and 400 parts of water, the solvent was completely recovered, and the solid content was filtered and dried to obtain a pigment. The crystal form of the copper phthalocyanine pigment thus obtained was analyzed by X-ray diffractometry and found to be β-type.

<Comparative Example 3> Mixture 4,0 obtained in Production Example 2
00 parts was added to 36,000 parts of isopropyl alcohol, and the mixture was stirred at room temperature for 4 hours to give α-type copper phthalocyanine 40
% And β-type copper phthalocyanine 60%.

Further, this mixture was passed through a pearl mill (model: PM-DCP3-45) manufactured by Drais. The α-type content of the composition thus obtained was 27%. This was further heated at boiling point for 3 hours. Thereafter, water was added to collect the solvent. The crystal form of the copper phthalocyanine pigment obtained by filtering and drying the solid substance was analyzed by X-ray diffractometry and found to be β type.

When the hue of the copper phthalocyanine pigment obtained in Comparative Example 3 was compared with that of the pigment of Comparative Example 1 by the lithographic ink test, the color difference Δa was 1.1, and the color was reddish. A spectrophotometer ACX-1400STC was used for color measurement.

Comparative Example 4 Mixture 4,0 obtained in Production Example 2
00 parts was added to 3,600 parts of isopropyl alcohol and 400 parts of xylene, and immersed at room temperature for 24 hours to obtain α
Type copper phthalocyanine 15% and β type copper phthalocyanine 8
A mixture consisting of 5% was obtained. 32,000 parts of isopropyl alcohol was further added to this mixture, and the solid content concentration was adjusted in the same manner as in Comparative Example 3. This mixture was passed through a pearl mill as in Comparative Example 3. The content of α-type copper phthalocyanine in the composition thus obtained was 5%. This was further heated at boiling point for 3 hours. After that, add water,
The solvent was recovered. The crystal form of the copper phthalocyanine pigment obtained by filtering and drying the solid substance was analyzed by X-ray diffractometry and found to be β type.

When the hue of the copper phthalocyanine pigment obtained in Comparative Example 4 was compared with that of the pigment of Comparative Example 1 in the same manner as in Comparative Example 3, it was reddish with a color difference Δa = 0.7.

Example 1 Mixture 4,0 obtained in Preparation Example 2
00 parts and 120 parts of phthalimidomethylcopper phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) were added to 2,000 parts of isopropyl alcohol and 2,000 parts of xylene, and the mixture was immersed at 5 ° C. for 24 hours for complete β-form. To obtain copper phthalocyanine.

The crystal form of the copper phthalocyanine pigment obtained by diluting the copper phthalocyanine thus obtained with isopropyl alcohol to adjust the pigment concentration and then treating in the same manner as in Comparative Example 3 was determined by an X-ray diffraction pattern. As a result of analysis, it was β type.

When the hue of the copper phthalocyanine pigment obtained in Example 1 was compared with that of the pigment of Comparative Example 1 in the same manner as in Comparative Example 3, the color difference Δa was 0.1. This hue was a greenish β-type copper phthalocyanine pigment which was almost similar to that of a kneader method product. Further, the coloring power was equal to or higher than that, and the dispersibility was excellent when the ink was observed under a microscope.

<Example 2> The mixture obtained in Production Example 2 was mixed with 4,
2,000 parts and phthalimidomethylcopper phthalocyanine pigment 200 parts, isopropyl alcohol 20,000
Parts, xylene 2,000 parts and water 13,800 parts, and stirred at 40 to 45 ° C. for 6 hours to obtain copper phthalocyanine completely converted to β type.

The crystal form of the copper phthalocyanine pigment obtained by treating this in the same manner as in Comparative Example 1 was analyzed by X-ray diffraction and the result was β type.

When the hue of the copper phthalocyanine pigment obtained in Example 2 was compared with that of the pigment of Comparative Example 1 in the same manner as in Comparative Example 3, the color difference Δa was 0.3.

A comparison of hues (Δa value) between the production method of the present invention and the kneader method is summarized in Table 1 below.

[0045]

[Table 1]

The smaller the value of Δa, the greener the hue.

[0047]

INDUSTRIAL APPLICABILITY The production method of the present invention is, in the production of a greenish β-type copper phthalocyanine pigment, compared with the conventional milling method using diethylene glycol and salt with a kneader.
This is an industrially excellent method because the cost of recovering the auxiliary raw material is extremely small and continuous production is possible.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction diagram of the ground product obtained in Production Example 2.

FIG. 2 is an X-ray diffraction pattern of an α-type copper phthalocyanine pigment.

FIG. 3 is an X-ray diffraction pattern of β-type copper phthalocyanine pigment.

Claims (4)

[Claims] 1. Crude copper phthalocyanine is dry-milled,
From the first step of producing a mixture of α-type copper phthalocyanine and β-type copper phthalocyanine, from the second step of completely crystallizing the mixture into β-type copper phthalocyanine in an organic solvent, and then dispersing in the presence of mechanical energy A method for producing a β-type copper phthalocyanine pigment, which comprises: 2. The weight ratio (α-type copper phthalocyanine and β-type copper phthalocyanine in the mixture after dry grinding in the first step (α
/ Β) is in the range of 40/60 to 80/20.
The manufacturing method described. 3. The production method according to claim 1, wherein a derivative of a copper phthalocyanine pigment is added during dry pulverization or during crystal conversion of the dry pulverized product with an organic solvent. 4. The method according to claim 1, 2 or 3, wherein the crystal conversion composition is dispersed in the presence of mechanical energy.