JP4045606B2 - Method for producing β-type copper phthalocyanine pigment - Google Patents

Description

【００５７】
【発明の効果】
本発明の製造方法によれば、乾式摩砕と溶剤処理法を組み合わせることによって、ニーダー法に匹敵した色相の緑味調のプロセスインキに適したβ型銅フタロシアニン顔料を製造することができるので、ニーダー法の大きな問題である副原料のジエチレングリコールと食塩の回収が不要となり製造コストの大幅な削減が可能となる。また、本発明の製造方法によれば、高ＣＯＤ排水の激減により、環境負荷を著しく小さくすることができ、更に、顔料化工程を短縮できるので、本発明の製造方法は、工業的に優れた方法である。
【図面の簡単な説明】
【図１】製造例２で得た粗製銅フタロシアニンの乾式粉砕物のＸ線回折図である。
【図２】α型銅フタロシアニン顔料のＸ線回折図である。
【図３】β型銅フタロシアニン顔料のＸ線回折図である。[0001]
BACKGROUND 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 advantageously producing a β-type phthalocyanine pigment exhibiting a clear green tone suitable for the process color of printing ink.
[0002]
[Prior art]
Conventionally, greenish tone β-type phthalocyanine pigments are industrially produced by a method of grinding crude copper phthalocyanine using an apparatus such as a kneader together with an inorganic salt and a binder such as ethylene glycol. The pigment obtained by this method has a green hue and high coloring power, and is optimal as a process color for printing ink.
[0003]
However, this method uses grinding aids other than the pulverized product at the time of grinding, so that productivity is poor, high COD wastewater is generated, environmental measures are required, and these are collected and reused. There were problems such as high costs and high costs.
[0004]
[Problems to be solved by the invention]
In order to solve these problems, JP-A-50-157419, JP-A-52-69435, etc. disclose dry pulverization of crude copper phthalocyanine to obtain α-type copper phthalocyanine and β-type copper phthalocyanine. After obtaining a mixture, a method for obtaining a β-type copper phthalocyanine pigment for transferring α-type copper phthalocyanine to β-type copper phthalocyanine by immersing the mixture in a crystallization solvent such as xylene is disclosed.
[0005]
Japanese Patent Publication No. 6-51846 discloses an easily dispersible copper phthalocyanine pigment obtained by adding rosins to crude copper phthalocyanine and dry milling, and then heat-treating the obtained milled product in a butyl cellosolve aqueous solution. A method of obtaining is disclosed.
[0006]
However, the β-type copper phthalocyanine pigment obtained by the methods described in JP-A-50-157419, JP-A-52-69435, etc. is a conventional crude copper phthalocyanine that has a viscosity similar to that of an inorganic salt and ethylene glycol. Compared to the method of grinding with a kneader using a binder, the hue is reddish, the dispersibility of the pigment in the vehicle is poor, and the coloring power is also inferior. It was difficult.
[0007]
Moreover, the hue of the copper phthalocyanine pigment obtained by the method described in Japanese Patent Publication No. 6-51846 was reddish and was not suitable for printing ink processes. In addition, since the rosin used in this method has a low softening point of about 60 ° C., it is melted by the frictional heat during attritor grinding, causing an adhesion phenomenon on the inner wall of the attritor, and triggering ignition due to abnormal heating. There was a danger.
[0008]
The reason why the hue of the β-type copper phthalocyanine pigment obtained by the method described in JP-B-6-51846 is reddish is as follows: (1) When a mixture of α and β types is crystallized into β type in butyl cellosolve, It is thought that it grows into a needle-like large crystal.
[0009]
The problem to be solved by the present invention is to provide a method for producing a β-type copper phthalocyanine pigment having a green hue, excellent coloring power and dispersibility, industrially and economically, and high safety. There is to do.
[0010]
[Means for Solving the Problems]
As a result of diligent research, the present inventors have determined that a mixture of α-type copper phthalocyanine and β-type copper phthalocyanine obtained by dry milling a mixture containing crude copper phthalocyanine and a compound having a rosin basic skeleton, alcohol, ketone and ester By using a method of heat-treating an organic solvent such as a single or two or more mixed solutions or a mixed solvent thereof with water, the hue is green and the coloring power and dispersibility are excellent, comparable to the conventional kneader method. The inventors have found that a β-type copper phthalocyanine pigment can be produced economically and safely, and have completed the present invention.
[0011]
That is, in order to solve the above-mentioned problems, the present invention provides a mixture of α-type copper phthalocyanine and β-type copper phthalocyanine obtained by dry-grinding a mixture containing a crude copper phthalocyanine and a compound having a basic skeleton of rosin. Characterized by being heat-treated in a single organic solvent selected from the group consisting of ketones, esters, in a mixed solvent consisting of two or more organic solvents, or in a mixed solvent thereof with water Provided is a method for producing a β-type copper phthalocyanine pigment exhibiting a tone.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the compound having a basic rosin skeleton used in the production method of the present invention include gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin and the like, or metal salts or esters thereof; Examples include acid resins, rosin-modified phenol resins, rosin-modified fumaric acid resins, rosin-modified polyester resins, rosin-modified polyamide resins, rosin-modified acrylic acid resins, rosin-modified alkyd resins, and various rosin-modified resins such as metal salts or esters thereof. It is done.
[0013]
The basic skeleton of rosin is roughly divided into four types: abietane, pimaran, isopimaran, and labdane type, but the compounds having the rosin basic skeleton used in the production method of the present invention include all of them and exclude the carboxyl group. It includes everything that has a skeleton part.
[0014]
In the dry grinding, it is more convenient to treat the rosin in an unmelted state because the crystal growth prevention effect is high and the production process does not cause adhesion to the interior of an attritor or the like. If the rosin is used as it is, it will be necessary to sufficiently cool it. However, by using rosin as a metal salt, its softening point becomes 300 ° C or higher, resulting in flame retardancy and a phenomenon of melt adhesion. In addition, the treatment effect is enhanced and it is industrially advantageous. The same effect can be obtained by increasing the softening point by reacting rosin with a resin.
[0015]
The metal species of the metal salt of rosin is not particularly limited, and examples thereof include Na, K, Ca, Ba, Sr, Al, Ti and the like.
[0016]
The amount of the compound having the basic skeleton of rosin is preferably in the range of 0.5 to 50% by weight, particularly preferably in the range of 3 to 20% by weight, based on the amount of the crude copper phthalocyanine charged.
[0017]
A method of mixing a metal salt of a compound having a crude copper phthalocyanine and basic skeleton of rosin may be a method of adding a metal salt of a compound having a basic skeleton of rosin crude copper phthalocyanine in grinding time, pre crude copper A method of treating a metal salt of a compound having a basic rosin skeleton with phthalocyanine may also be used.
[0018]
In the production method of the present invention, examples of the apparatus used for dry grinding include an attritor, a ball mill, a bead mill, a vibration mill, and a hammer mill.
[0019]
In dry grinding, when the peak heights of the X-ray diffraction diagrams representing the α-type and β-type crystal forms of the copper phthalocyanine pigment are Lα and Lβ, the α-type content is ≧ from the calibration curve of Lα / Lβ and the content rate. It is preferable to carry out until it becomes 30%. The most industrially advantageous is that the α-type content is about 60% to 75%. In the X-ray diffraction diagram, Lα has a peak height of 6.8 °, and Lβ has a peak height of 9.2 °.
[0020]
Examples of the organic solvent used in the production method of the present invention include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, 2-butanol, 4-butanol, amyl alcohol, isoamyl alcohol, 2-amyl alcohol, tert- Alcohol solvents such as amyl alcohol, hexyl alcohol, cyclohexanol, methylcyclohexanol, heptyl alcohol; ketone solvents such as acetone, methyl acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone; ethyl acetate, butyl acetate And ester solvents such as cyclohexyl acetate, methoxybutyl acetate, and cellosolve acetate. These organic solvents can be used as a mixture of two or more kinds, or a mixed system of these organic solvents or a mixture thereof and water can be used. Of these, fats having 4 carbon atoms, such as isobutanol and 2-butanol, are excellent in terms of crystal conversion ability from α-type to β-type, ease of solvent recovery, and excellent pigment quality, particularly hue and dispersibility. It is preferable to use a group alcohol.
[0021]
The amount of the organic solvent used is preferably 5 parts by weight or more with respect to 100 parts by weight of the ground product, and particularly preferably in the range of 100 to 300 parts by weight.
[0022]
The treatment temperature with the organic solvent can be appropriately selected from room temperature to the boiling point of the solvent system or the azeotropic point of the mixed solvent depending on the crystal growth ability of the treatment solvent system. For example, isobutanol and water In the case of a mixed solvent, the azeotropic point of 89 ° C. is preferable.
[0023]
The treatment time with the organic solvent also varies depending on the crystal growth ability of the treatment solvent system, but a range of 4 to 8 hours is preferable.
[0024]
After the solvent treatment, it is recovered by distillation, preferably by azeotropy with water. The recovered solvent can be used again.
[0025]
[Action]
The basic skeleton of rosin has a strong affinity for the b-axis surface, which is the crystal growth surface of copper phthalocyanine, due to the mechanochemical action by dry grinding. As a result, it has a great effect on preventing crystal growth caused by the solvent treatment for converting the crystal form from α type to β type at the time of pigmentation, and also has the effect of relaxing the aggregation of pigments and facilitating the deagglomeration. This is considered to make it possible to obtain a pigment having a green hue and high coloring power.
[0026]
【Example】
Hereinafter, the present invention will be described in more detail using production examples, examples, and comparative examples. In the following description, “part” and “%” represent “part by weight” and “% by weight”, respectively.
[0027]
<Production Example 1> (Production of crude copper phthalocyanine)
A reactor is charged with 4000 parts of a mixture of 1218 parts of phthalic anhydride, 1540 parts of urea, 200 parts of anhydrous cuprous chloride, 5 parts of ammonium molybdate and an alkylbenzene having an alkyl group of 5 to 8 carbon atoms as a solvent. The mixture was heated up 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, followed by suction filtration. The cake thus obtained was thoroughly washed with warm water at 80 ° C. and then dried to obtain crude copper phthalocyanine.
[0028]
<Production Example 2> (Method for producing rosin metal salt)
100 parts of hydrogenated rosin (stevelite rosin), 20 parts of sodium hydroxide and 1000 parts of water were charged into a beaker and then dissolved by heating to 70 ° C. or higher to obtain an aqueous rosin solution. To the rosin aqueous solution thus obtained, a calcium hydroxide aqueous solution consisting of 27 parts of calcium chloride and 200 parts of water was added with stirring to precipitate a rosin calcium salt. The pH of the rosin calcium salt precipitation solution was adjusted to 8, then filtered, and the resulting residue was washed with hot water and dried to obtain a rosin calcium salt.
[0029]
<Production Example 3> (Production of dry pulverized product of crude copper phthalocyanine)
Using 500 parts of crude copper phthalocyanine obtained in Production Example 1 and 25 parts of stevelite rosin calcium salt obtained in Production Example 2 using an attritor with a capacity of 5 liters (including 13 kg of steel balls having a diameter of 3/8 inch) The mixture was pulverized at a temperature of 90 to 110 ° C. for 60 minutes to obtain a mixture composed of 71% α-type copper phthalocyanine and 29% β-type copper phthalocyanine.
[0030]
The weight ratio (α / β) of α-type copper phthalocyanine and β-type copper phthalocyanine is the peak height Sα at the diffraction angle (2θ) = 6.8 ° representing the α-type crystal form of the X-ray diffraction diagram shown in FIG. And the peak height Sβ at the diffraction angle (2θ) = 9.2 representing the β-type crystal form.
[0031]
The measurement conditions of X-ray diffraction at this time are: target: Cu, filter: Ni, voltage: 40 KV, current: 30 mA.
[0032]
<Production Example 4> (Rosin treatment of crude copper phthalocyanine)
500 parts of the crude copper phthalocyanine obtained in Production Example 1 was dispersed in 5000 parts of water and heated to 70 ° C. to obtain an aqueous dispersion of crude copper phthalocyanine. To the aqueous dispersion of crude copper phthalocyanine thus obtained, an aqueous rosin solution in which 50 parts of tall oil rosin was dissolved by heating in an aqueous sodium hydroxide solution consisting of 10 parts of sodium hydroxide and 500 parts of water was added. To this mixture, an aqueous solution in which 13.5 parts of calcium chloride was dissolved in 100 parts of water was added. After adjusting the pH of the mixed solution to 8, the resulting precipitate was collected by filtration, washed with hot water, and dried to obtain a rosin calcium salt-containing crude copper phthalocyanine rosin.
[0033]
<Production Example 5> (Production of dry pulverized product of crude copper phthalocyanine)
500 parts of rosin calcium salt-containing crude copper phthalocyanine obtained in Production Example 4 was pulverized for 60 minutes at an internal temperature of 90 to 110 ° C. using an attritor having a capacity of 5 liters (including 13 kg of 3/8 inch diameter steel balls). Thus, a mixture comprising 72% α-type copper phthalocyanine and 28% β-type copper phthalocyanine was obtained. The ratio of α type and β type was determined by the same method as in Production Example 3.
[0034]
<Production Example 6> (Production of metal salt of rosin-modified resin)
100 parts of rosin-modified maleic acid resin ("Harimak T-80" manufactured by Harima Kasei), 13 parts of sodium hydroxide and 850 parts of water are charged into a beaker and dissolved by heating to 80 ° C to obtain an aqueous solution of rosin-modified maleic resin. Got. To the aqueous solution of the rosin-modified maleic resin thus obtained, an aqueous calcium chloride solution comprising 48 parts of calcium chloride and 400 parts of water was added with stirring to precipitate the calcium salt of the rosin-modified maleic resin. The pH of the calcium salt precipitation solution of rosin-modified maleic acid resin was adjusted to 8, then filtered, and the resulting residue was washed with hot water and dried to obtain a calcium salt of rosin-modified maleic resin.
[0035]
<Production Example 7>
Using 500 parts of the crude copper phthalocyanine obtained in Production Example 1 and 25 parts of the calcium salt of the rosin-modified maleic resin obtained in Production Example 6 using an attritor having a capacity of 5 liters (including 13 kg of steel balls having a diameter of 3/8 inch). Then, the mixture was pulverized for 60 minutes at an internal temperature of 90 to 110 ° C. to obtain a mixture composed of 69% α-type copper phthalocyanine and 31% β-type copper phthalocyanine. The ratio of α type and β type was determined by the same method as in Production Example 3.
[0036]
<Production Example 8>
500 parts of the crude copper phthalocyanine obtained in Production Example 1 and 50 parts of rosin-modified maleic acid resin ("Harimak T-80" manufactured by Harima Kasei Co., Ltd.) containing an attritor (13Kg of 3/8 inch diameter steel balls) having a capacity of 5 liters. ) To obtain a mixture composed of 67% α-type copper phthalocyanine and 33% β-type copper phthalocyanine.
[0037]
<Comparative Example 1> (kneader method)
500 parts of the crude copper phthalocyanine obtained in Production Example 1, 2500 parts of crushed salt, 500 parts of diethylene glycol and 30 parts of xylene were kneaded at 80 ° C. for 6 hours using a kneader having a capacity of 8 liters. 100 parts of the obtained kneaded material was dispersed together with 2000 parts of a 1% aqueous hydrochloric acid solution at 80 ° C. for 2 hours, followed by filtration. The resulting residue was washed with water and dried to obtain a copper phthalocyanine pigment. The crystal form of copper phthalocyanine thus obtained was analyzed by X-ray diffractometry. As a result, it was β type.
[0038]
<Comparative Example 2> (Production of dry pulverized product of crude copper phthalocyanine)
500 parts of the crude copper phthalocyanine obtained in Production Example 1 was ground for 60 minutes at an internal temperature of 90 to 110 ° C. using an attritor having a capacity of 5 liters (including 13 kg of steel balls having a diameter of 3/8 inch) to obtain α-type A ground product comprising 62% copper phthalocyanine and 38% β-type copper phthalocyanine was obtained. The ratio of α type and β type was determined by the same method as in Production Example 3.
[0039]
<Comparative Example 3> (Solvent method)
After 100 parts of the milled product obtained in Comparative Example 2, 300 parts of isobutanol and 600 parts of water were heated at an azeotropic temperature for 4 hours in a flask having a capacity of 1 liter, the solvent was completely removed and recovered by azeotropy. The solid content was filtered and dried to obtain a pigment. As a result of analyzing the crystal form of the copper phthalocyanine pigment thus obtained by X-ray diffraction, it was β type.
[0040]
<Example 1>
100 parts of the dry milled product of crude copper phthalocyanine obtained in Production Example 3 was heated together with 300 parts of isobutanol and 600 parts of water in a 1 liter flask at an azeotropic temperature for 8 hours, and then the solvent was completely removed by azeotropy. Removed and recovered. The solid content was filtered and dried to obtain a pigment. As a result of analyzing the crystal form of the copper phthalocyanine pigment thus obtained by X-ray diffraction, it was β type.
[0041]
When the hue of the obtained copper phthalocyanine pigment was compared with the pigment obtained by the kneader method of Comparative Example 1, the hue was a substantially greenish-tone β-type copper phthalocyanine pigment. Moreover, the coloring power was also equivalent.
Table 1 shows the evaluation results.
[0042]
<Example 2>
In the same manner as in Production Example 3, 50 parts of disproportionated rosin (Harima Kasei “Bandis T-25K”) Ca salt was added instead of 25 parts of stevelite rosin Ca salt, and dry milled product 100 Parts were heated together with 300 parts of isobutanol, 30 parts of isopropyl alcohol and 600 parts of water in a 1 liter flask at an azeotropic temperature for 8 hours, and then the solvent was completely recovered by azeotropic distillation, and the solid content was filtered and dried. To obtain a pigment. As a result of analyzing the crystal form of the copper phthalocyanine pigment thus obtained by X-ray diffraction, it was β type.
[0043]
When the hue of the obtained copper phthalocyanine pigment was compared with that of the pigment of Comparative Example 1, the hue was almost the same and the dispersibility and fluidity were excellent.
Table 1 shows the evaluation results.
[0044]
<Example 3>
100 parts of the crude copper phthalocyanine dry milled product obtained in Production Example 4, 300 parts of isobutanol, 30 parts of isopropyl alcohol and 600 parts of water were heated at an azeotropic temperature for 8 hours in a flask having a capacity of 1 liter. Completely removed and recovered by boiling. The solid content was filtered and dried to obtain a pigment. As a result of analyzing the crystal form of the copper phthalocyanine pigment thus obtained by X-ray diffraction, it was β type.
[0045]
When the hue of the obtained copper phthalocyanine pigment was compared with that of the pigment of Comparative Example 1, the hue was almost the same and the dispersibility and fluidity were excellent.
Table 1 shows the evaluation results.
[0046]
<Example 4>
100 parts of the crude copper phthalocyanine dry milled product obtained in Production Example 7, 300 parts of isobutanol, 30 parts of isopropyl alcohol and 600 parts of water were heated at an azeotropic temperature for 8 hours in a flask having a capacity of 1 liter. Completely removed and recovered by boiling. The solid content was filtered and dried to obtain a pigment. As a result of analyzing the crystal form of the copper phthalocyanine pigment thus obtained by X-ray diffraction, it was β type.
[0047]
When the hue of the obtained copper phthalocyanine pigment was compared with the pigment of Comparative Example 1, the hue and tinting strength were also equivalent. Moreover, both dispersibility and fluidity were good.
Table 1 shows the evaluation results.
[0048]
<Example 5>
After heating 100 parts of the crude copper phthalocyanine dry product obtained in Production Example 8, 300 parts of 2-butanol and 600 parts of water at an azeotropic temperature in a 1 liter flask for 8 hours, the solvent was completely removed by azeotropy. Removed and recovered. The solid content was filtered and dried to obtain a pigment. As a result of analyzing the crystal form of the copper phthalocyanine pigment thus obtained by X-ray diffraction, it was β type.
[0049]
When the hue of the obtained copper phthalocyanine pigment was compared with that of the pigment of Comparative Example 1, the hue was almost the same and the dispersibility and fluidity were excellent.
Table 1 shows the evaluation results.
[0050]
≪Evaluation method≫
The color difference, coloring power and fluidity of the pigments in the above examples were measured by the following methods, and the results are summarized in Table 1 below.
[0051]
<Manufacture of lithographic ink>
(Dark ink)
After premixing 84 parts of rosin-modified phenolic resin varnish and 16 parts of β-type copper phthalocyanine pigment, ink was prepared by three passes using a three-roller made by Buehler.
[0052]
The vehicle for lithographic ink is not limited to the above-mentioned rosin-modified phenolic resins, and other resins such as petroleum resins, alkyd resins, or these drying oil-modified resins, and if necessary, alkani oil, tung oil, soybean oil, etc. And those comprising a solvent such as n-paraffin, isoparaffin, aromatech, naphthene, α-olefin and the like. Moreover, well-known additives, such as an ink solvent, a drier, a leveling improver, a thickener, can be suitably mix | blended as needed.
[0053]
(Light color ink)
0.020 parts of the dark ink and 4.000 parts of white ink (Dainippon Ink & Chemicals New Champion AT White 179) are mixed with a Hoover Mahler. Mixing conditions: Weight 50 lb, 50 rotations x 3 times.
[0054]
<Evaluation method of coloring power and hue>
The light-colored ink produced above was spread on a fine paper with a spatula, and the upper color (meat color) was measured using a spectrophotometer “SPM50” manufactured by Gretag. The hue is shown by the difference from the pigment obtained in Comparative Example 1 (color difference: Δa). The smaller the Δa value, the greener. The coloring power was expressed as a cyan density ratio using the pigment of Comparative Example 1 as a standard.
[0055]
<Fluidity>
The dark ink prepared above was placed on a glass plate tilted at 70 degrees, and the evaluation was made based on the distance passed after 1 hour. In Table 1, the value of the ink produced using the pigment obtained in Comparative Example 1 was set to 100, and the ratio was shown.
[0056]
[Table 1]

[0057]
【The invention's effect】
According to the production method of the present invention, it is possible to produce a β-type copper phthalocyanine pigment suitable for a greenish process ink having a hue comparable to the kneader method by combining dry grinding and a solvent treatment method. Recovery of diethylene glycol and salt as secondary materials, which is a major problem of the kneader method, is not required, and the manufacturing cost can be greatly reduced. Further, according to the production method of the present invention, the environmental load can be remarkably reduced by drastically reducing high COD wastewater, and further, the pigmentation step can be shortened. Therefore, the production method of the present invention is industrially excellent. Is the method.
[Brief description of the drawings]
1 is an X-ray diffraction pattern of a dry pulverized product of crude copper phthalocyanine obtained in Production Example 2. FIG.
FIG. 2 is an X-ray diffraction pattern of an α-type copper phthalocyanine pigment.
FIG. 3 is an X-ray diffraction pattern of a β-type copper phthalocyanine pigment.

Claims (3)

A mixture of α-type copper phthalocyanine and β-type copper phthalocyanine obtained by dry-grinding a mixture containing a metal salt of a compound having a basic skeleton of crude copper phthalocyanine and rosin is selected from the group consisting of alcohol, ketone and ester A β-type copper phthalocyanine pigment exhibiting a greenish tone, characterized by being heat-treated in a single organic solvent, in a mixed solvent selected from two or more organic solvents, or in a mixed solvent thereof with water Production method. The process according to claim 1, wherein the compound having a rosin basic skeleton is a metal salt of a resin modified with rosin or a metal salt of an ester modified with rosin . The production method according to claim 1 or 2 , wherein the organic solvent is an aliphatic alcohol having 1 to 7 carbon atoms.

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