JPH0959531A - Production of alpha type copper phthalocyanine pigment composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject composition, excellent in dispersibility, capable of assuming a bright hue of a reddish blue color, having a high tinting strength, further excellent in suitability such as weather and heat and solvent resistances and especially useful as a colorant for coating materials and plastics. SOLUTION: This method for producing an α type copper phthalocyanine pigment composition comprises the first step for grinding (1) a mixture of a crude of a monochlorocopper phthalocyanine with a crude of copper phthalocyanine or (2) a crude of a semichlorocopper phthalocyanine synthesized from a monochlorophthalic acid or its alkali metallic salt and phthalic acid and the second step for treating the dry ground crude in a 65-75% sulfuric acid in an amount of 3-10 times based on the whole crude at 20-80 deg.C temperature, then diluting the resultant treated crude in water and separating the produced pigment.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has excellent dispersibility, has a clear reddish blue hue and high tinting strength, and is superior in weather resistance, heat resistance and heat resistance to pigments obtained by conventional pigmentation methods. The present invention relates to a method for producing an α-type copper phthalocyanine pigment which is excellent in suitability such as solvent property and is particularly useful as a coloring agent for paints and plastics.

[0002]

2. Description of the Related Art Conventionally, α-type copper phthalocyanine pigment has been used as a coloring pigment for paints, plastics and the like because it has a high pigmenting power and high transparency because of its fine pigment particle size.

Generally, α-type copper phthalocyanine pigments include chloro-free copper phthalocyanine in which one molecule of copper phthalocyanine has an average number of chlorine atoms of 0, semecrole copper phthalocyanine having 0 or more and less than 1 and monochloro copper phthalocyanine having one. In some cases, it is classified and called. Among these, the cemicrole copper phthalocyanine pigment is known to have improved solvent resistance and heat resistance as compared with the chlor-free copper phthalocyanine pigment because a part of the copper phthalocyanine molecule is replaced with a chlorine atom. . Also,
Since the number of chlorine atoms substituted is small, it is possible to maintain the original reddish blue color of the fluoro-free copper phthalocyanine pigment. Therefore, as a pigment for coloring paints, plastics and the like, the semi-microl copper phthalocyanine pigment is useful.

As a method of producing a semi-micro copper phthalocyanine pigment, a method of dissolving monochloro copper phthalocyanine crude and copper phthalocyanine crude in sulfuric acid and then taking out into water to form a pigment (acid paste method);
A method is known in which monochloro copper phthalocyanine and copper phthalocyanine are slurried in a sulfuric acid aqueous solution and then water is added to form a pigment (acid slurry method). Further, a method is known in which monochlorophthalic acid or a salt thereof and phthalic anhydride, or phthalodinitrile and cuprous chloride are used as raw materials to synthesize a crude salt of cemicrole copper phthalocyanine, which is then pigmented by an acid paste method or an acid slurry method. ing.

The acid slurry method is 50 to 90
% Of copper phthalocyanine in a sulfuric acid aqueous solution to form a slurry of copper phthalocyanine sulfate,
A method of adding water to form a pigment is generally used.

As a method for producing a pigment having a high tinting strength and high transparency, Japanese Patent Laid-Open No. 104104/1983 discloses that a crude of semikrole copper phthalocyanine is preliminarily dry-ground in a ball mill together with a steel rod or a steel ball. The crude was crushed and ground in a 50-60% sulfuric acid aqueous solution that is 4.5-5.5 times the sulfuric acid equivalent to the total crude to make a slurry, which was treated at 50-85 ° C and then water was added. A method of pigmentation is disclosed.

However, while the resulting pigment is very transparent, it is a very fine pigment particle, so that the paint,
When used for applications such as plastics, the pigment dispersibility, weather resistance, heat resistance, and solvent resistance are slightly insufficient, and when the slurry is treated at a temperature of 80 ° C or higher, the pigment particles become too large, It has a problem that high coloring power cannot be obtained.

As a method for producing a highly vivid pigment having a high tinting strength and capable of reducing the amount of sulfuric acid used, JP-A-1-7
According to Japanese Patent No. 0568, a crude product of cemicrole copper phthalocyanine is subjected to dry grinding in the presence of a crystal growth inhibitor, and a 50 to 90% sulfuric acid aqueous solution equivalent to 2.0 to 7.5 times the total amount of the crude product in terms of sulfuric acid. In the presence of a crystal growth inhibitor, dry-milled crude was slurried to 50-85
A method is disclosed in which water is added to the mixture to form a pigment after the treatment at ℃.

[0009]

However, since the crystal growth inhibitor is added during the production of the slurry, only very fine pigment particles can be obtained, and the pigment dispersibility, weather resistance, and
It has a problem that its heat resistance and solvent resistance are slightly insufficient.

In any of the production methods, in order to produce pigments having different average number of chlorine atoms, it is necessary to produce a crude product of semimicrol copper phthalocyanine each time, which causes a problem that productivity is not so good. are doing.

The problems to be solved by the present invention are excellent in dispersibility, have a clear reddish blue hue and high tinting strength, and are also excellent in weather resistance, heat resistance, solvent resistance and the like. Another object of the present invention is to provide a method for producing an α-type copper phthalocyanine pigment which is particularly useful as a colorant for paints and plastics.

[0012]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a mixture of monochloro copper phthalocyanine crude and a mixture of copper phthalocyanine crude, or a mixture of semimicrol copper phthalocyanine crude is dry-processed. By grinding and pigmenting by the acid slurry method, it has excellent dispersibility, has a clear reddish blue hue and high coloring power, and has excellent suitability for weather resistance, heat resistance, solvent resistance, etc. Therefore, the inventors have found a method for producing an α-type copper phthalocyanine pigment composition which is particularly useful as a colorant for paints and plastics, and completed the present invention.

That is, in order to solve the above-mentioned problems, the present invention was synthesized from (1) a mixture of monochloro copper phthalocyanine and a crude mixture of copper phthalocyanine, or (2) monochlorophthalic acid or its alkali metal and phthalic acid. The first step of dry milling the crude crude of semimicrol copper phthalocyanine, and the crude mill that was dry milled,
A) a second step in which the pigment is separated by treating it in 65 to 75% sulfuric acid in an amount of 3 to 10 times the total amount of the crude at a temperature of 20 to 80 ° C., and then diluting it in water to separate the pigment. Provided is a method for producing a type copper phthalocyanine pigment composition.

The manufacturing method of the present invention will be described in more detail below.

The crude of copper phthalocyanine and the crude of monochloro copper phthalocyanine used in the production method of the present invention may be those synthesized by a known method, and the production method is not particularly limited. In the case of crude, a method of reacting phthalic anhydride or a salt thereof, a copper source and urea in an organic solvent, or a method of reacting phthalodinitrile and a copper source in the presence or absence of a catalyst in an organic solvent, etc. In the case of crude monochlorocopper phthalocyanine, a method of reacting 3/4 mol of phthalic anhydride or a salt thereof, 1/4 mol of monochlorophthalic acid or a salt thereof, a copper source and urea in an organic solvent, Phthalodinitrile 3/4 mol, monochlorophthalodinitrile 1/4 mol and copper source in organic solvent in the presence or absence of catalyst Method of response, and a method of reacting the cupric chloride and phthalonitrile in the presence or absence of a catalyst in organic solvents. In addition, a crude of semelic copper phthalocyanine obtained by changing the use ratio of phthalic anhydride or its salt and monochlorophthalic anhydride or its salt may be used.

The first step in the production method of the present invention is to process the crude of cemicrole copper phthalocyanine in the absence of a grinding aid and an organic solvent, for example, in a ball mill, a sand grinder, a vibration mill, an attritor, or other grinders. This is a dry grinding step, and a method using an attritor is preferable from the viewpoint of grinding efficiency.

In the dry grinding step, if the grinding temperature becomes higher, the β-type copper phthalocyanine in the ground material is less likely to decrease, so the grinding temperature is 100 ° C. or less, preferably 80 ° C.
It is controlled as follows.

When a crude copper phthalocyanine crude and a copper phthalocyanine crude are used in this step, it is essential to mix them in advance and then dry mill them. Even if the second step described below is performed, α having the desired performance is obtained.
No type copper phthalocyanine pigment composition is obtained.

The end point of the dry grinding is the time when the content of β-type crystals is ground to 40% or less.
The smaller the content of the β-type crystal is, the more preferable from the viewpoint of causing the crystal transition to the crystal form. The β-type crystal content can be obtained using a calibration curve prepared based on X-ray diffraction patterns of samples having different blending ratios of the β-type copper phthalocyanine pigment and the α-type copper phthalocyanine pigment.

The grinding time in the case of using an attritor depends on the kind of the crusher, the shape and filling amount of the crushing medium (steel balls, etc.), and the rotation speed of the crusher. When using 3/8 inch steel balls in an amount 30 times the crude weight of phthalocyanine and grinding at 300 rpm, the content of β-type crystals is 40% or less in about 2 hours. However,
The milling time and the like are slightly different depending on the mixing ratio of the crude of copper phthalocyanine and the crude of monochloro copper phthalocyanine used as a raw material and the β crystal content in the crude of the semi-micro copper phthalocyanine. If the crude product with a β-type crystal content after dry milling of 40% or more in the X-ray diffraction pattern is pigmented, the pigment particles tend to become large and the desired high coloring power is obtained. It is not possible to obtain pigments with

The second step in the manufacturing method of the present invention is the first step.
This is a so-called acid slurry method of pigmenting the dry-milled crude obtained in the step in dilute sulfuric acid. In this step, the sulfuric acid concentration, the treatment temperature, and the weight ratio of sulfuric acid to copper phthalocyanine in producing the copper phthalocyanine sulfate slurry are important factors. When the dry-milled crude is pigmented by the acid slurry method, the sulfuric acid concentration is preferably 65 to 75%. When the sulfuric acid concentration is less than 65%, it is not preferable because a uniform sulfate slurry cannot be obtained and a part of the dry-milled crude remains as it is, and the sulfuric acid concentration is 80%. If the concentration is higher than the above, the viscosity of the slurry becomes too high, so that a large load tends to be applied to stirring.
It is not preferable in production.

The amount of sulfuric acid used in the dry-milled crude is preferably in the range of 3 to 10 times by weight, preferably 4.
The range of 5 to 5.5 times is more preferable from the viewpoint of properties of the obtained pigment and treatment of waste acid. Crude amount of sulfuric acid used
When the amount used is more than 0 times, it is the same as the pigmenting method using only the acid paste method, so that there is no effect of dry milling, the hue becomes yellow, and the obtained pigment particles are finer. And the aggregation of the pigment particles is further promoted and the dispersibility tends to be lowered, which is not preferable. Further, it is not preferable to use a large amount of sulfuric acid from the viewpoint of increasing raw material cost and treating wastewater.

The temperature for treating the sulfate slurry is 20 to 20.
The range of 80 ° C is preferable, and the range of 55 to 75 ° C is particularly preferable. When the sulfate slurry is treated at a high temperature exceeding 80 ° C., the obtained pigment particles become large and a high tinting strength tends not to be obtained, which is not preferable.

In the general acid slurry method, water is added to the sulfate slurry, but in the case of the production method of the present invention, a pigment having similar performance can be obtained by adding the sulfate slurry to water.

[0025]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the scope of these examples. In the following examples and comparative examples, "part" and "%" represent "part by weight" and "% by weight", respectively.

<Example 1> Phthalic anhydride, cuprous chloride,
160 parts of copper phthalocyanine crude produced by a solvent method using urea and a catalyst, 1 mol% sodium monochlorophthalate and 3 mol% phthalic anhydride, cuprous chloride,
Mix with 240 parts of monochloro copper phthalocyanine crude produced by solvent method using urea and catalyst,
Dry milling was performed with an attritor for 2 hours together with 12,000 parts of 3/8 inch steel balls to obtain a dry milled crude crude of semikrole copper phthalocyanine having an average number of chlorine atoms in one molecule of about 0.6. . The X-ray diffractogram of this grind showed that it did not contain β-type crystals.

50 parts of a dry-milled crude of semikrole copper phthalocyanine was mixed with 294 parts of 68% sulfuric acid (4 parts of the crude).
(Corresponding to twice the amount of sulfuric acid) and stirred at 60 ° C. for 2 hours, the slurry was taken out into 1600 parts of water at 30 ° C., heated and stirred at 80 to 85 ° C. for 2 hours, and then filtered. The residue was washed with water at 50 to 60 ° C., dried and pulverized to obtain an α-type copper phthalocyanine pigment composition having an average number of chlorine atoms in one molecule of about 0.6.

Comparative Example 1 5 parts of N, N-dimethylamino-1,3-propanediaminosulfonyl copper phthalocyanine was mixed with 45 parts of the dry-milled crude crude semocyanol phthalocyanine used in Example 1. Next, the mixture was added to 237 parts of a 60% aqueous sulfuric acid solution at 68 to 72 ° C. (corresponding to 2.84 times the amount of sulfuric acid in all crudes), stirred at the same temperature for 1.5 hours, and added with 410 parts of water. 70-75
After stirring at ℃ for 1.5 hours, it was filtered. 50 to 6 residues
It was washed with water at 0 ° C., dried and pulverized to obtain an α-type copper phthalocyanine pigment composition having an average number of chlorine atoms per molecule of about 0.6.

Comparative Example 2 Monochloro copper phthalocyanine and copper phthalocyanine crude were dry-milled under the same conditions as in Example 1. From the X-ray diffraction pattern, the crude product obtained by dry-grinding copper phthalocyanine contained about 40% of β-type crystals, but no β-form crystals were found in the crude product obtained by dry-milling monochloro copper phthalocyanine.

20 parts of dry milled copper phthalocyanine crude and 30 parts of dry milled monochloro copper phthalocyanine were mixed and a mixture containing 16% β-type crystals was used in the same manner as in Example 1. To obtain an α-type copper phthalocyanine pigment composition.

Comparative Example 3 50 parts of the dry-milled crude used in Example 1 was replaced with 294 parts of 68% sulfuric acid (4 parts of crude).
It was added to a double amount of sulfuric acid) and stirred at 100 ° C. for 2 hours, then this slurry was taken out into 1600 parts of water at 30 ° C., heated and stirred at 80 to 85 ° C. for 2 hours, and then filtered. The residue was washed with water at 50 to 60 ° C., dried and pulverized to obtain an α-type copper phthalocyanine pigment having about 0.6 chlorine atoms in one molecule.

Comparative Example 4 Pigmentation was carried out in the same manner as in Example 1 except that the step of dry grinding with an attritor for 2 hours together with 12,000 parts of 3/8 inch steel balls was omitted. Then, α-type copper phthalocyanine pigment was obtained.

Example 2 Sodium monochlorophthalate 1
Semimicrol copper having an average number of chlorine atoms in one molecule obtained by synthesizing 00 parts and 32 parts of phthalic anhydride together with cuprous chloride by a solvent method and having a β-type crystal content of about 0.6. 100 parts of the crude phthalocyanine was dry-milled in the same manner as in Example 1. From the X-ray diffractogram, the crude product of the crude of semecrole copper phthalocyanine contained 10% of β type crystals.
Contained.

The dry-milled crude silica phthalocyanine thus obtained was pigmented in the same manner as in Example 1 to obtain an α-type copper phthalocyanine pigment composition.

Comparative Example 5 50 parts of the dry-milled crude used in Example 2 was added to 237 parts of a 60% sulfuric acid aqueous solution (corresponding to 2.84 times the amount of sulfuric acid of the crude), and the same procedure as in Example 2 was carried out. Pigmentation was carried out to obtain an α-type copper phthalocyanine pigment composition.

Example 3 The same as Example 2 except that 267 parts of 75% sulfuric acid (corresponding to 4 times the amount of sulfuric acid of crude) was used in place of 294 parts of 68% sulfuric acid. Pigmentation was carried out to obtain an α-type copper phthalocyanine pigment composition.

<Comparative Example 6> The procedure of Example 2 was repeated, except that 294 parts of 68% sulfuric acid was replaced with 235 parts of 85% sulfuric acid (corresponding to 4 times the amount of crude sulfuric acid). Pigmentation was carried out, but at the time of stirring for about 40 minutes, the slurry viscosity increased and stirring became impossible, so the slurry with increased viscosity was taken out into 1600 parts of water at 30 ° C.,
After heating and stirring at 80 to 85 ° C for 2 hours, the mixture was filtered. The residue was washed with water at 50 to 60 ° C., dried and pulverized to obtain an α-type copper phthalocyanine pigment composition having an average number of chlorine atoms in one molecule of about 0.6.

<Example 4> In the same manner as in Example 2 except that 534 parts of 75% sulfuric acid (corresponding to 8 times as much sulfuric acid as crude) was used instead of 294 parts of 68% sulfuric acid. Pigmentation was carried out to obtain an α-type copper phthalocyanine pigment composition having an average number of chlorine atoms in one molecule of about 0.6.

<Example 5> Pigmentation was carried out in the same manner as in Example 1 except that the operation of stirring at 60 ° C for 2 hours was replaced with the operation of stirring at 30 ° C for 2 hours. An α-type copper phthalocyanine pigment composition having an average number of chlorine atoms in one molecule of about 0.6 was obtained.

Example 6 The mixing ratio of the crude of copper phthalocyanine and the crude of monochloro copper phthalocyanine used in Example 1 was 280 parts / 120 parts, and 3/8 inch steel balls were used together with 12,000 parts in an attritor. Dry milling was carried out for an hour to obtain a crude dry crude crude of semimicrol copper phthalocyanine having an average number of chlorine atoms of about 0.3. The X-ray diffractogram of this dry-milled crude showed that it contained 8% β-type crystals.

50 parts of the dry-milled crude of the cemicrol copper phthalocyanine was added to 428 parts of 70% sulfuric acid (corresponding to 6 times the amount of sulfuric acid of the crude), and the mixture was stirred at 30 ° C. for 2 hours, and then the slurry was heated to 30 ° C. It was taken out in 2000 parts of water, heated and stirred at 80 to 85 ° C. for 2 hours, and then filtered. The residue was washed with water at 50 to 60 ° C., dried and ground to obtain an α-type copper phthalocyanine pigment composition having an average number of chlorine atoms in one molecule of about 0.3.

Table 1 shows a summary of the pigmenting methods carried out in Examples 1-6 and Comparative Examples 1-5.

[0043]

[Table 1]

<Evaluation> (Conditions for preparing paint) Pigments obtained in each of Examples and Comparative Examples.
6 parts and N, N-dimethylamino-used in Comparative Example 1
0.4 parts of 1,3-propanediaminosulfonyl copper phthalocyanine (however, in the case of the pigments obtained in Comparative Example 1 and Comparative Example 4, N, N-dimethylamino-1,3-propanediaminosulfonyl copper phthalocyanine was added. Without
Pigment (4.0 parts) was used as a melamine alkyd mixed varnish (manufactured by Dainippon Ink and Chemicals, Inc .; "Beccosol J-524-IM-60" / "Super Beckamine J-".
820-60 "solids weight ratio = 7/3 mixture) 1
3.0 parts, thinner (xylene / butanol = 3/1)
13.0 parts together with 80 g of glass beads (3 mmφ)
It was taken in a 100 ml glass bottle and dispersed for 15 minutes using a paint conditioner. To the dispersion thus obtained, add 50 parts of melamine alkyd mixed varnish,
It was further dispersed for 5 minutes to obtain a primary color paint.

Separately, "Taipeque R-930"
(Ishihara Sangyo, titanium dioxide) 150 parts, "Beckosol J-524-IM-60" (Dainippon Ink and Chemicals, Inc., alkyd varnish) 135 parts, thinner (xylene: butanol = 3: 1) 15 parts , 400 g of glass beads (3 mmφ) were placed in a 500 ml glass bottle, and dispersed for 60 minutes using a paint conditioner. Alkyd varnish 1 was added to the dispersion thus obtained.
00 parts, "Super Beckamine J-820-60" (Melamine alkyd manufactured by Dainippon Ink and Chemicals, Inc.) 10
0 part was added and the mixture was further dispersed for 5 minutes to obtain a white paint.

(Hue) The primary color paint and the white paint are mixed so that the ratio of the blue pigment and the white pigment is 1:10, and the mixture is 6 mils (6/1).
(000 inch) was applied onto the art paper using a film applicator, and then baked at 140 ° C. for 20 minutes.
Then, based on the article to be coated using the pigment of Comparative Example 1,
The color differences (ΔL ^* , Δa ^* , Δb ^* ) and the relative tinting strength of the articles to be coated using the pigments of Examples and Comparative Examples were measured using a spectrophotometer, and the results are shown in Tables 2 and 3. Are summarized in.

A larger value of Δa ^* indicates a reddish color, and a larger value of relative coloring strength indicates a higher coloring strength.

(Pigment dispersibility) In order to compare the pigment dispersibility, a coating material dispersed for 60 minutes was prepared, an object to be coated was prepared in the same manner as above, and the color measurement results are summarized in Tables 2 and 3. Showed.

The smaller the difference in relative tinting strength between the coating film dispersed for 60 minutes and the coating film dispersed for 15 minutes, the better the pigment dispersibility.

(Measurement of Specific Surface Area) In order to compare the size of the pigment particles, the specific surface area was measured by the BET method. Generally, the larger the value, the finer the pigment particles.
The results are summarized in Tables 2 and 3.

(Crystal Stability) As a measure of the crystal stability of the pigment, the pigments obtained in Examples and Comparative Examples were boiled in xylene (130 ° C., 1 hour), the solvent was filtered off, and the pigment was dried. did. The pigment thus obtained was used to prepare a primary color paint and an object to be coated according to the paint preparation method, and the relative tinting strength of the pigment after boiling was compared with the pigment before boiling as a reference. The smaller the difference is, the more stable the pigment particles are. The results are qualitatively shown in Tables 2 and 3 as ◯, Δ, and x.

In the ground product obtained by the dry grinding method, since the particles are extremely fine but extremely aggregated, the value is usually small.

If any unpigmented ground material remains, boiling produces coarse particles which leads to a reduction in tinting strength. When such a pigment is used for plastics, a problem occurs in heat resistance.

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

The α-type copper phthalocyanine pigment obtained by the production method of the present invention has excellent dispersibility, exhibits a clear reddish blue hue, and has high coloring power, and has weather resistance, heat resistance and solvent resistance. It has excellent properties such as properties and is particularly useful as a coloring agent for paints and plastics.

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[Procedure amendment]

[Submission date] November 15, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0003

[Correction method] Change

[Correction contents]

Generally, α-type copper phthalocyanine pigments include chloro-free copper phthalocyanine in which one molecule of copper phthalocyanine has an average number of chlorine atoms of 0, semecrole copper phthalocyanine having 0 or more and less than 1 and monochloro copper phthalocyanine having one. In some cases, it is classified and called. Among these, the cemicrole copper phthalocyanine pigment is known to have improved solvent resistance and heat resistance as compared with the chlor-free copper phthalocyanine pigment because a part of the copper phthalocyanine molecule is replaced with a chlorine atom. . Also,
Since the number of chlorine atoms substituted is small, it is possible to maintain the original reddish blue color of the chloro-free copper phthalocyanine pigment. Therefore, as a pigment for coloring paints, plastics and the like, the semi-microl copper phthalocyanine pigment is useful.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction contents]

[0056]

The α-type copper phthalocyanine pigment obtained by the production method of the present invention has excellent dispersibility, exhibits a clear reddish blue hue, and has high coloring power, and has weather resistance, heat resistance and solvent resistance. It has excellent suitability in terms of properties and is particularly useful as a coloring agent for paints and plastics.

Claims (2)

[Claims] 1. A dry milling of (1) a mixture of monochloro copper phthalocyanine and a crude mixture of copper phthalocyanine, or (2) a crude crude of monochlorophthalic acid or a cemicrole copper phthalocyanine synthesized from an alkali metal thereof and phthalic acid. The process and dry-milled crude is 65% to 75% of the total amount of crude
A method for producing an α-type copper phthalocyanine pigment composition, which comprises a second step of treating the mixture in sulfuric acid at a temperature of 20 to 80 ° C., and then diluting it in water to separate the pigment. 2. The average number of chlorine atoms in one molecule is 0.3 to.
2. The value α according to claim 1, which is in the range of 0.6.
Method for producing type copper phthalocyanine pigment composition.