JP2001261998A - Method for producing copper phthalocyanine pigment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a brilliant copper phthalocyanine pigment having excellent dyeability and flowability in excellent productivity without using a grinding auxiliary. SOLUTION: This method for producing the copper phthalocyanine pigment, characterized by pigmenting crude copper phthalocyanine having an average primary particle diameter of 0.001 to 0.1 μm in the presence of an organic solvent in an amount corresponding to a weight ratio of 0.5 to 3.0 to the amount of the used crude copper phthalocyanine in the absence of a grinding auxiliary.

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 copper phthalocyanine pigment useful as a coloring agent for, for example, lithographic inks, gravure flexographic inks, and the like.

[0002]

2. Description of the Related Art Conventionally, as a method for pigmenting crude copper phthalocyanine, crude copper phthalocyanine is dissolved by mechanical grinding using equipment such as a kneader in the presence of an organic solvent together with a grinding aid such as salt and sodium sulfate. A salt milling method, or a solvent milling method in which fine crude copper phthalocyanine obtained by dry-grinding crude copper phthalocyanine with an attritor or the like is treated in an organic solvent may be used.

[0003]

However, there are many problems with the described method. For example, in the above-mentioned solvent salt milling method, a greenish and clear β-type copper phthalocyanine pigment can be obtained, but a great deal of time and cost are required to recover the grinding aid and the organic solvent.

In the solvent milling method, the ratio of the solvent to the crude copper phthalocyanine is high, and the throughput of the crude copper phthalocyanine in one production is low. Further, although the cost required for recovering the organic solvent is small, the hue is reddish and the fluidity by lithographic ink evaluation is inferior to that of the solvent salt milling method. That is, none of these methods was industrially satisfactory.

[0005]

In view of the above situation,
The present inventors have conducted intensive studies on a method for producing a β-type copper phthalocyanine pigment, and as a result, refined crude copper phthalocyanine is subjected to a pigmentation treatment without using a grinding aid and using a relatively small amount of an organic solvent. As a result, the inventors have found that the above-mentioned disadvantages are solved, and have reached the present invention.

[0006] Further, the fine copper phthalocyanine obtained by dry-milling the crude copper phthalocyanine is kneaded with an organic solvent in a state where a treating agent is added thereto in order to impart pigment suitability as required. Have found a method of obtaining a β-type copper phthalocyanine pigment which is greenish and has excellent fluidity by lithographic ink evaluation.

Further, it has been found that in the recovery step after pigmentation, the labor required for recovery is greatly reduced by not using a grinding aid as compared with the conventional solvent salt milling method.

That is, the present invention provides the following invention. 1. A crude copper phthalocyanine having an average primary particle size of 0.001 to 0.1 μm is prepared by adding a crude copper phthalocyanine in the absence of a grinding aid and in the presence of 50 to 300 parts by weight of an organic solvent per 100 parts by weight of the crude copper phthalocyanine. A method for producing a β-type copper phthalocyanine pigment, comprising subjecting the pigment to a hydrophilization treatment. 2. 2. The method according to the above 1, wherein water is further used in combination with the organic solvent. 3. 1 or 2 above, wherein the organic solvent is at least one kind of solvent comprising an alcohol solvent and an aromatic solvent.
The manufacturing method as described. 4. 4. The production method according to the above 1, 2, or 3, wherein the temperature of the pigmentation treatment is from 20C to 200C. 5. 5. The production method according to the above 1, 2, 3 or 4, wherein the pigmentation treatment is a kneading treatment in a closed system. 6. 6. The production method according to the above 1, 2, 3, 4 or 5, wherein the crude copper phthalocyanine is a crude copper phthalocyanine containing an α-type crystal and having an average primary particle diameter of 0.001 to 0.1 μm. 7. 7. The method according to the above 1, 2, 3, 4, 5 or 6, wherein the copper phthalocyanine pigment is a copper phthalocyanine pigment for lithographic ink. 8. Further, in the presence of at least one or more surface treatment agents selected from the group consisting of copper phthalocyanine derivatives, surfactants, and rosins, pigmentation treatment is performed.
7. The production method according to 4, 5 or 6.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present invention, by kneading a fine crude copper phthalocyanine with an organic solvent without a grinding aid and forming a pigment, it is possible to obtain a β-type copper phthalocyanine pigment having a greenish hue and excellent fluidity. Features.

In the present invention, fine crude copper phthalocyanine is used, which has an average primary particle diameter of 0.00.
1 to 0.1 μm (hereinafter, referred to as semi-crude).
In this semi-crude, fine particles smaller than crude copper phthalocyanine described later are strongly aggregated. This average primary particle diameter can be measured, for example, by an electron micrograph.

The crude copper phthalocyanine (hereinafter referred to as crude) used in the present invention is produced by a conventionally known method. This crude has a particle diameter of more than 0.1 μm and 50 μm. General methods for obtaining copper phthalocyanine are broadly classified into the Weyler method and the phthalodinitrile method. Specifically, the crude copper phthalocyanine used in the present invention can be prepared, for example, by adding phthalic anhydride or a derivative thereof, urea or a derivative thereof and a copper source, or a phthalodinitrile and a copper source to a catalyst, if necessary, and adding an organic solvent. 180 ° C in the presence or absence
And a production method obtained by a heating reaction at a temperature of 300 ° C.

In this case, phthalic acid derivatives include phthalic acid salts, phthalic anhydride, phthalimide, phthalamic acid and salts or esters thereof, phthalonitrile, etc .; urea derivatives include urea and ammonia; copper sources include metallic copper; Copper (II) or copper (II) halides, copper oxide, copper sulfate, copper sulfide, copper hydroxide, etc .; catalysts include molybdenum compounds such as ammonium molybdate and molybdenum oxide; titanium compounds such as titanium tetrachloride and titanate; , Zirconium chloride, zirconium carbonate and other zirconium compounds, antimony oxide, boric acid and the like, organic solvents such as alkylbenzenes, aromatic hydrocarbons such as alkylnaphthalene, alkylcyclohexane, alicyclic hydrocarbons such as decalin, decane, dodecane and the like Aliphatic hydrocarbons, nitrobenzene, nitrol Aromatic nitro compounds such as down, trichlorobenzene, aromatic halogenated hydrocarbons such as chloronaphthalene are known. The copper phthalocyanine compound to be obtained by the reaction is a copper phthalocyanine having no substituent on the phthalocyanine ring.

The copper phthalocyanine obtained by the reaction is
It is preferable to further reduce the content of an organic compound other than the copper phthalocyanine compound in that the coloring power and dispersibility of the finally obtained pigment can be further increased, and for this purpose, washing with an inorganic base solution is performed. Is preferred. After washing with an inorganic base solution, washing with an inorganic acid solution or washing with an inorganic base solution while introducing steam into the inorganic base solution is most preferred. After washing, usually
After filtering and drying, the crude is semi-crude.

The semi-crude can be obtained by grinding the crude by mechanical means. For example, dry grinding can be suitably employed. In carrying out this grinding, it is preferable not to use grinding aids such as sodium chloride and sodium sulfate. As means, for example, attritor, ball mill, vibration mill, sand grinder, kneader,
Banbury mixer and the like can be mentioned.

Thus, the crude copper phthalocyanine obtained by milling by mechanical means has an average primary particle size of 0.1 including α-form crystals.
001-0.1 μm of crude copper phthalocyanine. This is a typical example of semi-crude.

In the production process of the present invention, semi-crude is converted into a pigment by using a pigmentation treatment without using a grinding aid and with a smaller amount of an organic solvent than in the prior art.

The organic solvent used in the present invention is, for example,
Alcohol solvents, that is, glycerin, ethylene glycol, diethylene glycol, or polyethylene glycol, and one or more selected from the group consisting of aromatic solvents, carbitol solvents, cellosolve solvents, and ketone solvents Can be selected from mixed systems. Above all, as the organic solvent, at least one or more solvents including an alcohol-based solvent and an aromatic-based solvent can be suitably used.

The amount of the organic solvent used in the present invention is preferably 0.5 to 3.0 weight ratio to semi-crude (crude copper phthalocyanine having an average primary particle diameter of 0.001 to 0.1 μm). A weight ratio of 0.5 to 2.0 is most preferable in terms of quality and cost. At a weight ratio of less than 0.2, it is not sufficient to wet the surface of the crude copper phthalocyanine ground by mechanical means. At a weight ratio of more than 3.0, not only the productivity is lowered but also the cost required for recovery is reduced. In any case, it is not preferable. The preferred weight ratio corresponds to 50 to 300 parts by weight per 100 parts by weight of semicrude, or 50 to 200 parts by weight per 100 parts by weight of semicrude, in arithmetic conversion.

In the pigmentation treatment, only the above-mentioned selected organic solvent can be used, and further, the above-mentioned selected organic solvent and water can be used in combination and mixed. As the water used here, it is preferable to use a component which has an adverse effect on the pigmentation treatment, for example, a water which does not contain inorganic salts as much as possible. In this case, the ratio of water to the organic solvent is, for example, 0.01 to the weight of the organic solvent relative to the amount used.
It is preferable to use an amount equivalent to 1.00 times.

In the pigmentation treatment in the present invention, the grinding aids such as salt and sodium sulfate which have been conventionally used in the pigmentation treatment by the solvent salt milling method are not used, and the grinding aid is not used. The pigmentation treatment is performed in the presence.

This pigmentation treatment can be performed by sufficiently exposing semi-crude to the above-mentioned organic solvent. The temperature of the pigmentation treatment is not particularly limited, but may be, for example, 2 in terms of productivity of the pigment and control of the crystal type / crystal particle diameter.
It is preferably performed at 0 to 200 ° C.

The temperature of the pigmentation treatment according to the present invention depends on the organic solvent used. For example, 90 ° C. to 150 ° C. is preferable for diethylene glycol, and 20 ° C. to 60 ° C. is preferable for xylene.

This pigmentation step is not particularly limited as long as the semi-crude is sufficiently exposed to the organic solvent, but may be a kneading treatment of kneading the semi-crude and the organic solvent in a closed system. preferable. In the present invention, kneading means mixing without grinding. That is, by this kneading, the aggregation of the semi-crude is released, the crystal conversion of the released particles into β-type crystals and the growth of the crystal particles to a size suitable as a pigment are performed. Here, if the system is a closed system, when kneading semi-crude in a state where α-type crystals and β-type crystals are mixed, the organic solvent is not diffused out of the system, and the intended desired characteristics are substantially obtained. It becomes easier to stably obtain a pigment consisting of only β-form crystals.

According to the knowledge of the present inventors, in the pigmentation step, the viscosity in the system is changed at a critical point where the state where α-type crystals and β-type crystals coexist is changed to only β-type crystals. The viscosity may rise sharply, but by pre-existing a certain amount of the organic solvent in the system, this viscosity change can be mitigated. Danger due to operation in the state can be prevented, and generation of heterogeneous pigments and reaggregation of the obtained pigments can be suppressed.

The total amount of the organic solvent used may be mixed with semi-crude in advance to form a pigment, but the total amount of the organic solvent used is 0.5 to 3.0 of the crude copper phthalocyanine.
Within the range of the weight ratio (that is, 50 to 300 parts by weight per 100 parts by weight of semi-crude), the total amount is divided and used, and an additional organic solvent is added at any stage during the pigmentation treatment. Alternatively, pigmentation may be performed.

For kneading for the pigmentation used in the present invention, a conventional kneading apparatus capable of forming a closed system, for example, a kneader, a Banbury mixer, a Nauta mixer, an extruder, etc., is used so as to form a closed system. Useful.

This pigmentation step may be carried out from a state in which α-type crystals and β-type crystals coexist to a state in which it is substantially changed to β-type crystals only, for example, in a range of 30 minutes to 4.5 hours. Is preferred from the viewpoint of the productivity of the pigment. The end point of the pigmentation step can be determined by the change in the viscosity of the kneaded material described above.However, a specific kneading device is kneaded by shaking the kneading temperature and the kneading time under various device operating conditions in advance, and the appropriate kneading is performed. It is convenient and preferable to select an end point under the conditions, to fix the operation conditions of the apparatus and the kneading temperature, for example, and to control the kneading time.

In the production method of the present invention, the fields of printing inks such as lithographic inks, gravure inks and flexo inks, coatings such as lacquers and baking paints, coloring of molded articles such as polyolefins and thermoplastic polyesters, jet inks,
It is possible to obtain a copper phthalocyanine blue pigment that can be used for various uses such as a high-tech use such as a color filter and an electrophotographic powder toner.

In the present invention, in order to impart properties suitable for end use as exemplified above to the copper phthalocyanine pigment,
Furthermore, pigmentation treatment can be carried out by including various surface treating agents that do not inhibit pigmentation. In the present invention, examples of the surface treatment agent used as necessary include a surfactant, a rosin, a copper phthalocyanine derivative, a resin varnish, and a metal salt.

The copper phthalocyanine pigment used in the lithographic printing ink is subjected to a pigmentation treatment in the presence of at least one or more surface treatment agents selected from the group consisting of copper phthalocyanine derivatives, surfactants, and rosins. By carrying out, it can obtain suitably.

As the surfactant, for example, any of cationic, nonionic and anionic surfactants is effective, and cationic and nonionic surfactants are particularly advantageous. The rosins include rosin, modified rosin, rosin salts, and specifically, gum rosin, wood rosin, tall oil rosin, disproportionated rosin, hydrogenated rosin, polymerized rosin,
There are rosin alcohol, phenol-modified rosin, maleic acid-modified rosin, and rosin metal salt. The copper phthalocyanine derivative has a substituent on at least one of the four benzene nuclei of the copper phthalocyanine, and the substituent includes a halogen atom, a sulfonic acid group, a carboxylic acid group or a metal salt thereof, an ammonium salt, and a cationic activity. Salts with the agent,
Further, various derivatives via a methylene group, a carbonyl group, a sulfonyl group, an imino group and the like are also advantageously used.

In the present invention, when a pigment is formed by using a surfactant in combination with an organic solvent, for example, the dispersibility of the pigment in the printing ink can be improved.
When a pigment is formed by using a hydrophobic organic solvent and water in combination,
The pigmentation can be performed in a more uniform state in the liquid medium used for the pigmentation, which is convenient. In the present invention, when a pigment is formed by using a copper phthalocyanine derivative in combination with an organic solvent, for example, the hue of the pigment can be made more greenish, and the particle size of the pigment can be made smaller.

The addition amount of these surface treatment agents is preferably 0.005 to 0.2 weight ratio to semi-crude, and most preferably 0.01 to 0.1 weight ratio in terms of quality and cost. Incidentally, the addition amount is, by arithmetic conversion,
0.5 to 20 parts by weight per 100 parts by weight of semi-crude,
Advantageously, it corresponds to 1 to 10 parts by weight per 100 parts by weight of semicrude.

After the pigmentation treatment in the present invention, the organic solvent and optionally used water are usually removed from the kneaded material outside the system by any appropriate means. In this way, it is possible to take out a copper phthalocyanine pigment consisting essentially of a β-type crystal while preventing a change in properties such as a crystal type and a particle diameter (a surface treatment may be performed if necessary).

The method of recovering the organic solvent at this time includes a method in which the kneaded material after pigmentation is taken out into a large amount of water and then steam distillation, and a method in which the kneaded material after pigmentation is taken out in a large amount of water.
A method of washing with filtered water and distilling the recovered filtrate can be used. In addition, filtration, washing, and drying can also be performed so that a pigment form suitable for a use form is obtained. These operations are
It is preferable to perform the treatment so that the crystal form (β form) does not change as much as possible.

[0036]

EXAMPLES Examples, reference examples and comparative examples will be described below.
In the embodiment, all of the above preferable technical items are combined. Unless otherwise specified, parts are parts by weight and percentages are percentages by weight.

Reference Example 1 500 parts of crude copper phthalocyanine having no substituent on the phthalocyanine ring (corresponding to crude) was charged into a 5 L attritor loaded with steel beads, and heated at 90 ° C. for 1 hour.
Mechanical grinding was carried out for hours to obtain crude copper phthalocyanine ground by mechanical means (corresponding to semi-crude).
The average primary particle size was 0.085 μm.

Example 1 1200 parts of crude copper phthalocyanine milled by mechanical means obtained in Reference Example 1 and diethylene glycol 1400
The mixture was charged into an 8 L double-arm kneader, kneaded at 95 ° C. for 50 minutes, and subjected to a pigmentation treatment (corresponding to a kneading treatment in a closed system). Thereafter, the kneaded material was taken out into water, sufficiently stirred, filtered and washed with water, and the cake after filtration was dried to obtain a β-type copper phthalocyanine pigment. Further, diethylene glycol was recovered by distilling the filtrate after filtration.

Example 2 1200 parts of crude copper phthalocyanine milled by mechanical means obtained in Reference Example 1, 36 parts of a copper phthalocyanine derivative (imidomethylated copper phthalocyanine), and a mixed solvent 1300 containing 9: 1 diethylene glycol and water The portion was charged into an 8 L double-arm kneader and kneaded at 115 ° C. for 90 minutes to perform a pigmentation treatment (corresponding to a kneading treatment in a closed system). Thereafter, the same operation as in Example 1 was performed.

Example 3 1000 parts of crude copper phthalocyanine milled by mechanical means obtained in Reference Example 1, 10 parts of a cationic surfactant (Coatamine 24P manufactured by Kao), and a mixture of xylene and water at a ratio of 5: 5 Charge 1000 parts of the solvent into a 5 L Nauter mixer, 30
The mixture was kneaded at 3 ° C. for 3 hours to perform a pigmentation treatment (corresponding to a kneading treatment in a closed system). Thereafter, the same operation as in Example 1 was performed.

Comparative Example 1 430 parts of crude copper phthalocyanine, 2150 parts of sodium chloride, and 480 parts of diethylene glycol were charged into an 8-L double-arm kneader and kneaded at 95 ° C. for 7 hours to perform a pigmentation treatment. afterwards,
The kneaded product was taken out into water, sufficiently stirred, filtered and washed with water, and the cake after filtration was dried to obtain a β-type copper phthalocyanine pigment. Here, time is required for the production of the pigment, and much time is required for recovering the salt and diethylene glycol after the pigmentation.

Comparative Example 2 60 parts of crude copper phthalocyanine, 200 parts of isobutanol
Parts and 400 parts of water in a 1 L separable flask 89
After stirring at 4 ° C. for 4 hours, isobutanol is steam distilled. Then, after filtration and washing with water, the cake after filtration was dried to obtain a β-type copper phthalocyanine pigment. here,
As a result of requiring more liquid medium per unit volume of the container used for pigmentation, the pigment yield per unit volume of the container was small.

Using the pigments obtained in Examples 1, 2 and 3, and Comparative Examples 1 and 2, lithographic inks were prepared, and each was evaluated for comparison. Table 1 shows the results.

<Preparation Method of Lithographic Ink> Using the pigment obtained in Comparative Example 1, a lithographic ink was prepared by the following method. 0.3 g of pigment and 1.2 g of resin varnish for ink MG-63 (manufactured by Dainippon Ink and Chemicals, Inc.) were dispersed with a Hoover Maller to prepare a dark ink. A light-colored ink was prepared by mixing 0.1 g of the dark-colored ink obtained above and 2 g of a white ink containing 30% of white pigment. The dark ink described above (referred to as a standard) and the dark ink increased by + 5% (referred to as a comparative standard) with the amount of pigment used in 1% increments were prepared. From the standard and comparative dark inks, corresponding light-colored inks were prepared according to the above-described light-colored ink preparation method, and used as standard light-colored inks and comparative standard light-colored inks, respectively. Using the pigments obtained in Examples 1, 2, 3 and Comparative Example 2, dark and light inks were prepared in the same manner as described above.

<Evaluation Method of Hue> The standard dark ink obtained by using the copper phthalocyanine pigment of Comparative Example 1 and the dark ink obtained by using the pigments obtained in Examples 1, 2, and 3 and Comparative Example 2 were used. After the color was spread on the developed color paper with a spatula, the hue was visually determined. In the table, "clear" means that it is sharper than the standard,
“Green” means greener than the standard, and “reddish” indicates reddish than the standard.

<Evaluation Method of Coloring Power> Each of the inks obtained above was used as a test ink, and the coloring power was evaluated. That is, the tinting strength of the light-colored ink using the pigments obtained in Examples 1, 2, 3, and Comparative Example 2 and the comparative standard light-colored ink was compared by applying a spatula to a color-developed paper and using a spatula. Was determined as the coloring power of the pigment.

<Method of Evaluating Fluidity> A test ink lightly mixed with a spatula is placed on the upper part of a glass plate having an inclination angle of 70 °, and is allowed to flow on the glass plate. Leave it for one hour,
The leading edge of the ink flowing portion is measured, and the flow is regarded as glass plate fluidity. A glass sheet having a large measured fluidity is judged to have a high fluidity. Thus, the relative evaluation of each Example and Comparative Example with respect to the measured value of the fluidity of the dark color ink of Comparative Example 1 as a reference (1.0) was expressed by a numeral.

<Evaluation Method for Dispersibility> The pigment particle size distribution of the dark ink of Comparative Example 1 was measured by image analysis.
Using the measured value of the particle size distribution as a criterion (5), the relative evaluation of each of Examples and Comparative Examples with respect to the value was represented by a numeral.

[0049]

[Table 1]

[0050]

The β-type copper phthalocyanine pigment of the present invention thus obtained has a good coloring property and good fluidity by lithographic ink evaluation, which is equal to or higher than that of the conventional solvent salt milling method, and In the recovery of organic solvents,
Due to the features such as not using a grinding aid, the time and labor required for recovery can be greatly reduced, which can contribute to the productivity of the pigment.

Claims (5)

[Claims] An average primary particle diameter of 0.001 to 0.1 μm
Of crude copper phthalocyanine in the absence of a grinding aid and 50 to 100 parts by weight of the crude copper phthalocyanine.
A method for producing a β-type copper phthalocyanine pigment, which is subjected to a pigmentation treatment in the presence of 300 parts by weight of an organic solvent. 2. The method according to claim 1, wherein the organic solvent is at least one solvent composed of an alcohol solvent and an aromatic solvent. 3. The method according to claim 1, wherein the crude copper phthalocyanine is a crude copper phthalocyanine containing an α-type crystal and having an average primary particle size of 0.001 to 0.1 μm. 4. The method according to claim 1, wherein the copper phthalocyanine pigment is a copper phthalocyanine pigment for lithographic ink. 5. The production method according to claim 1, wherein the pigmentation treatment is further performed in the presence of at least one or more surface treatment agents selected from the group consisting of copper phthalocyanine derivatives, surfactants, and rosins.