JPH0826242B2 - Method for producing β-type copper phthalocyanine pigment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION “Object of the Invention” (Field of Industrial Application) The present invention relates to a method for producing a novel β-type copper phthalocyanine pigment. More specifically, a method for producing a β-type copper phthalocyanine pigment, which comprises dry-milling a crude copper phthalocyanine to an α-type crystal form content of 40% or more, and then wet-milling in the presence of an inorganic salt and an organic liquid. Is.

(Prior Art) Finely-divided copper phthalocyanine pigment has a beautiful color tone, a large coloring power, and various performances such as weather resistance and heat resistance.
Moreover, it is widely used.

Crude copper phthalocyanine is usually a phthalic anhydride, urea and a copper source, or phthalodinitrile and a copper source in the presence or absence of a catalyst such as ammonium molybdate or titanium tetrachloride, such as alkylbenzene, trichlorobenzene or nitrobenzene. It is produced by reacting in an organic solvent under normal pressure or increased pressure. However, the synthesized phthalocyanine molecules undergo crystal growth one after another in the synthesis solvent, and their major axis is 10
It can be obtained only with coarse needle-like particles of about 200 μm, and its value is very low or not at all as a coloring pigment for inks, paints, plastics and the like.

Therefore, the crude copper phthalocyanine is required to be finely colored particles, that is, to be finely divided to about 0.01 to 0.5 μm (hereinafter, the operation is referred to as pigmentation).

Although various methods have been conventionally proposed as the pigmenting means, as a method for producing a micronized β-type copper phthalocyanine pigment, USP2686010 contains crude copper phthalocyanine, anhydrous sodium ferrocyanide or anhydrous barium chloride. Such a grinding aid and a so-called dry salt milling method in which dry grinding is performed at a high temperature of 100 to 150 ° C. for a long time are described, but it is necessary to grind for a long time, productivity is very poor, and an apparatus A method that is very unfavorable from an industrial point of view because it has the drawback that it easily adheres to a wall or dispersion media such as steel balls, and that it cannot be obtained from the desired high-quality pigment such as sharpness and coloring power. Met.

JP-A-50-157419 and JP-A-52-69435 describe a so-called dry milling method in which crude copper phthalocyanine is dry-milled in the absence of a grinding aid and an organic liquid. As a result, the crystalline form shifts from β type to α type and strongly aggregates. Generally, it cannot be used as a pigment as it is.
There is described a method of obtaining a copper phthalocyanine pigment having suitability as a pigment by immersing a copper phthalocyanine pigment having mixed types in a crystallization solvent such as xylene, transferring α type to β type and dispersing. However, this method requires the use of a large amount of organic solvent, which is problematic in terms of hygiene and pollution, and when immersed in a solvent, large needle-like crystals are formed along with crystal growth, resulting in a decrease in coloring power and a decrease in hue. It has a drawback that only β-type copper phthalocyanine pigments which are reddish and generate a large amount of bronze can be obtained.

As an industrial method, as shown in JP-A-51-28119, a crude copper phthalocyanine is combined with a grinding aid, which is a water-soluble inorganic salt such as sodium chloride, and an organic liquid such as alcohol, polyol and amine. A so-called solvent salt milling method is described in which it is charged in a mold kneader and wet-milled. However, a large amount of milling aid and its contents and the like are kept in good wearing condition with respect to crude copper phthalocyanine. Therefore, since a large amount of organic liquid proportional to the grinding aid is used, the production cost increases, and at the same time, the wastewater treatment requires a lot of labor and time. Further, it has a drawback that it has to be ground for a long time and requires excessive energy. As a method for improving the above-mentioned wet milling method, a crude copper phthalocyanine was added to α
The crystal salt type content is 40% or less, and the solvent salt milling method using crude copper phthalocyanine whose bulk is dry crushed to 60% or less of crude copper phthalocyanine is described, but the gloss and sharpness are insufficient. However, it has drawbacks such as low production efficiency.

[Structure of the Invention] (Means for Solving the Problems) The inventors of the present invention have conducted extensive studies to solve the above-mentioned drawbacks, and as a result, by dry-milling purified copper phthalocyanine, which is wet-milled, it is possible to obtain a high temperature in a short time. The inventors have found that a high quality β-type copper phthalocyanine pigment can be obtained, and completed the present invention.

That is, the present invention is a dispersion machine equipped with a dispersion medium such as a ball mill, a vibration mill, an attritor, etc. in the absence of a grinding aid or an organic liquid, and a purified copper phthalocyanine α in an X-ray diffraction diagram. Type 2θ = 15.6 °, 1
Let Sα and Sβ be the peak areas at 2θ = 18.1 ° and 18.4 °, which represent 6.6 ° and β type, respectively.
(Sα + Sβ) × 100 After dry pulverizing until the α-type crystal content is 40% or more, in the coexistence of an organic liquid consisting of at least one inorganic salt and at least one alcohol or polyol as a grinding aid. A method for producing a β-type copper phthalocyanine pigment by wet grinding, which can shorten the pigmentation time, reduce the amount of grinding aid and organic liquid used, and further reduce the grinding energy. It is possible to obtain a β-type copper phthalocyanine pigment excellent in quality such as gloss and vividness of a colored product.

As described above, the crude copper phthalocyanine is generally coarse particles, and a large amount of air is strongly adsorbed on the crystal surface and the pores. Pre-mixing is required. Therefore, it consumes a lot of time and requires a large amount of energy. However, with the dry-milled crude copper phthalocyanine according to the invention, its wetting is very good and therefore premixing is almost unnecessary, so that the pigmenting time can be greatly reduced and the amount of organic liquid can be reduced.

In the wet grinding step, when the crude copper phthalocyanine whose particles have been refined by the dry grinding according to the present invention is used, the transition from α type to β type by organic solvent and crystal growth,
And, due to the grain size regulating effect by the interaction of the growth prevention to the needle-like crystal shape by the weak grinding energy, the rice grain-like particle shape,
Since pigments having a uniform particle size can be obtained, the pigmentation mechanism is completely different from the atomization of particles by strong grinding energy, which is necessary in the wet grinding process using crude copper phthalocyanine without dry grinding. Therefore, the pigmentation time can be significantly shortened, and the wet grinding energy can also be significantly reduced. That is, in the present invention, it is possible to obtain a pigment having a quality equal to or higher than the quality of the pigment using the crude copper phthalocyanine as a starting material in a wet grinding time of 2/3 or less, and when the wet grinding time is constant, it is possible to obtain 3 minutes. With an inorganic salt and an organic liquid of 2 or less, it is possible to obtain a pigment having a quality equal to or higher than that of the pigment using crude copper phthalocyanine as a starting material. Further, if the pigmentation is carried out with the conventional amounts of the inorganic salt and organic liquid and the pigmentation time, it is possible to obtain a β-type copper phthalocyanine pigment having extremely excellent quality such as gloss and vividness of a colored product.

When using a crude copper phthalocyanine having an α-type crystal form content of less than 40% by dry pulverization, the wettability with the organic liquid of the crude copper phthalocyanine in the dry pulverization step shows the same effect as that of the present invention. Pigmentation by crushing is centered on miniaturization as in the case of using crude copper phthalocyanine that is not dry-milled, particle growth and sizing hardly occur, and the pigmentation mechanism is essentially different from the present invention. Is taking.

Inorganic salts and organic liquids are collected and reused in accordance with wastewater regulations, but the present invention is also effective in greatly reducing the heat energy at the time of collection by reducing the large amount of inorganic salts and organic liquids.

In the present invention, the crude copper phthalocyanine is synthesized by a known method, and the production method is not particularly limited, but phthalic anhydride or a derivative thereof, urea and a copper source, or phthalodinitrile and copper are used. , In the presence or absence of a catalyst such as ammonium molybdate or titanium tetrachloride in an organic solvent such as alkylbenzene, trichlorobenzene or nitrobenzene at 120 to 250 ° C., preferably 170 to 230 ° C. for 2 to 15 hours, preferably It is produced by reacting for 3 to 7 hours under normal pressure or pressure. The crude copper phthalocyanine is preferably unsubstituted copper phthalocyanine, but one or less per one molecule of copper phthalocyanine, for example, copper phthalocyanine substituted with chlorine or a nitro group may be subjected to the treatment of the present invention.

Dry pulverization is performed with a disperser equipped with a dispersion medium such as a ball mill, a vibration mill, or an attritor, and the pulverization temperature is usually 100 ° C. or less, preferably 80 ° C., in the absence of a pulverizing auxiliary agent or organic liquid. Do the following: The α-type crystal form content of the pulverized product is 40% or more, preferably 50 to 80%. If the α-type crystal type content is less than 40%, the growth of particles by wet grinding and the particle size regulating effect become insufficient, and a pigment that gives a highly glossy and highly vivid colored product cannot be obtained. Usually, the crude copper phthalocyanine is β type, but when the crude copper phthalocyanine made α type by sulfuric acid treatment is dry pulverized, the α type crystal form content is 100.
%, But a β type pigment is obtained by wet grinding. However, the time required for crystal transition becomes slightly longer.

The grinding aid is at least one selected from water-soluble inorganic salts such as sodium chloride, sodium sulfate and calcium chloride. Further, it is preferable to use a grinding aid that has been previously crushed by a crusher. The amount used is 2 to 10 times by weight, preferably 3 to 8 times by weight that of the crude copper phthalocyanine.

The organic liquid is preferably at least slightly water-soluble, and is, for example, at least one selected from alcohols and polyols. Examples of alcohols include n-propyl alcohol, n-butyl alcohol, isopropyl alcohol and isobutyl alcohol, and examples of polyols include polyols, ethers of polyols, esters of polyols and chlorinated derivatives thereof, and examples thereof include ethylene. Glycol, diethylene glycol, triethylene glycol,
Examples thereof include tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and tetrapyrene glycol. The amount of the organic liquid used is 0.1 to 0.2 times by weight, preferably 0.3 to 1.5 times by weight, of the crude copper phthalocyanine.

As the wet milling device, a kneading machine which has been used in the conventional wet milling method, such as various mixers and kneaders, can be used as it is.

The wet milling time varies depending on the amount of equipment, milling aid and organic liquid, but is 1 to 15 hours, preferably 2 to 10 hours. If it is shorter than 1 hour, the α-type crystal form of the dry pulverized product is not completely converted to the β-type crystal form, which is inappropriate. Although it may be longer than 15 hours, it is not preferable because the quality of the pigment is hardly changed and the energy efficiency is deteriorated.

The wet milling temperature is 70 to 150 ° C., preferably 80 to 130 ° C., although it depends on the equipment, the amounts of the milling aid and the organic liquid, and the milling time. At a temperature lower than 70 ° C., it takes a long time for the α-type crystal form of the dry pulverized product to transform into the β-type crystal form, which is not preferable. If the temperature is higher than 150 ° C., the crystal growth is large and the wet milling needs to be performed for a short time, but the sizing time is shortened, which is not preferable in terms of quality. After the start of wet milling, the temperature gradually rises and reaches equilibrium at 90 to 120 ° C, so heating or cooling is performed as necessary.

The copper phthalocyanine pigment after wet milling is carried out by a conventional method. That is, the milled mixture is treated with water or a dilute acid, and the milling aid and organic liquid are removed by filtration and washing with water to isolate the pigment. The pigment can be used as it is in a wet state or can be used in a powder state by drying.

If necessary, a resin, a surfactant, a copper phthalocyanine derivative, and other additives may be added after wet milling.

(Effects of the Invention) The advantages of the method for producing a β-type copper phthalocyanine pigment of the present invention are listed below. (1) A pigment having excellent gloss and vividness can be obtained for colored products such as inks, paints, and plastics. 2) Pigmentation time can be shortened, the pigmentation energy accompanying it can be greatly reduced, and it is advantageous in energy saving. (3) The amount of grinding aid and organic liquid can be reduced, which is advantageous in resource saving. Also, the wastewater treatment of the treatment agent can be reduced, and (4) it is extremely easy to increase the production amount. Therefore, it is extremely useful as an industrial pigment production method. In the present invention, various resins, surfactants and other additives may be added before, during or after the dry pulverization step.

Β-type copper phthalocyanine pigment obtained by the present invention,
It can be widely used as a coloring material for printing inks, plastics, paints, etc.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples.

 In the examples, “part” means “part by weight”.

Example 1 A crude copper phthalocyanine (purity 95%) was mixed with an attritor.
Dry pulverization was performed for 60 minutes to obtain a dry pulverized product having an α-type crystal form content of 42%. Charge 100 parts of this dry pulverized product, 500 parts of pulverized sodium chloride, and 25 parts of diethylene glycol into a 1000-part volume dual-arm kneader and add the diethylene glycol necessary to maintain a dense lump (dough) at 100 to 110 ° C. While kneading for 3 hours. The total amount of diethylene glycol used was 80 parts. After wet milling, the product was taken out in 1300 parts of a 1% sulfuric acid aqueous solution at 70 ° C., stirred for 1 hour while being kept warm, filtered, washed with water and dried to obtain 93 parts of β-type copper phthalocyanine pigment.

Examples 2, 3, 4 and Comparative Examples 1, 2, 3, 4 As shown in Table-1, the dry milling time and wet milling conditions were changed, and the same treatment as in Example 1 was carried out.
Β-type copper phthalocyanine pigments of 3, 4 and Comparative Examples 1, 2, 3, 4 were obtained.

Example 5 100 parts of crude copper phthalocyanine (purity 95%) was treated with 500 parts of 98% sulfuric acid aqueous solution at room temperature for 2 hours, filtered, washed with water and dried to obtain α-type crude copper phthalocyanine.
A β-type copper phthalocyanine pigment was obtained by performing the same treatment as described above.

Examples 6 and 7 As shown in Table 1, the dry milling time and wet milling conditions were changed, and the same treatment as in Example 1 was carried out.
To obtain a β-type copper phthalocyanine pigment.

(Evaluation method) An offset ink having a pigment content of 15% was prepared using a rosin-modified phenol resin varnish using three rolls, and proof printing was performed to measure the density, sharpness and gloss of the printed matter.

The density was measured with a reflection densitometer. The higher the value, the higher the concentration. Sharpness measures L, a, b with a color machine,
C value The higher the value, the higher the clarity.) Was used.
The gloss was measured with a gloss meter at 60 degrees. The higher the value, the higher the gloss.

Table 2 shows the measurement results of Examples 1 to 7 and Comparative Examples 1 to 4.

From the results of Tables 1 and 2, Examples 1 to 5 and Comparative Examples 1 and 3
As shown in, when wet milling under the same conditions, there is little difference in concentration, but high gloss and high clarity are obtained. Further, as shown in Comparative Examples 2 and 4, even if the wet milling time is extended by the conventional method, the gloss and the sharpness do not reach those of the short-time wet milled products shown in Examples 1 to 5. . Further, as shown in Example 6, when the wet milling time is extended, a pigment having excellent gloss and sharpness can be obtained. Furthermore, as shown in Example 7, even if the amounts of the grinding aid and the organic liquid were 60% and 50% of those of Example 1, respectively, wet grinding was performed by the conventional method shown in Comparative Examples 2 and 4. A pigment almost equivalent to that obtained by extending the time is obtained.

Claims (1)

[Claims] 1. A crude copper phthalocyanine is dry pulverized by a disperser equipped with a dispersion medium to an α-type crystal content of 40% or more, and then an organic salt selected from alcohols or polyols with an inorganic salt as a pulverization aid. Β prepared by wet-grinding in the presence of liquid and then removing the inorganic salt and the organic liquid
Method for producing type copper phthalocyanine pigment.