JP2000281924A - Production method of blue-blue pigment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pigment composition which has a clearer hue than mixing a separately prepared blue pigment and violet pigment, and does not require a color mixing step in preparing an ink or the like. SOLUTION: A mixture of crude copper phthalocyanine (A) which may be ground and crude dioxazine violet (B) which may be ground is subjected to a pigmentation treatment.

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 blue-black pigment useful as a coloring agent such as flexographic ink.

[0002]

2. Description of the Related Art Conventionally, in the field of gravure and flexographic inks,
In the field of paints and the like, blue-black inks and paints are mixed with inks and paints made from blue pigments and inks and paints made from purple pigments. It is carried out by a method of obtaining a dark blue color by converting the compounded pigment into an ink and a paint.

[0003]

However, there are many problems with the described method. For example, the above-mentioned method of obtaining a gravure / flexo ink having a blue-black color tone by mixing the pigments of the respective colors or mixing the inks of the respective colors has the following disadvantages.

(1) Even if a blue pigment and a violet pigment, which are separately prepared, are mixed, the color becomes unclear due to the mixture, and the sharpness of each pigment cannot be obtained. (2) In the ink-forming step, in addition to the disadvantage of (1), it is necessary to produce two kinds of inks, blue and purple, and the process is complicated.

[0005]

In view of the above situation,
The present inventors have conducted intensive studies on a method for producing a blue-black pigment, for example, by subjecting a mixture of crude copper phthalocyanine, which may be ground, and crude dioxazine violet, which may be ground, to a pigmentation treatment. The present inventors have found that a blue-blue pigment having high chroma, vividness, and high coloring power and good dispersibility can be obtained without the above-mentioned disadvantages, and the present invention has been achieved.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present invention, before becoming a pigment, may be milled crude copper phthalocyanine, which may be ground, before the pigment, may be milled crude dioxazine violet, and then pigmentation. The biggest feature.

[0007] By doing so, the copper phthalocyanine pigment obtained in advance by grinding the crude copper phthalocyanine as necessary and then forming a pigment, and the crude dioxazine violet is optionally ground and then converted into a pigment. It exhibits excellent technical effects that cannot be achieved with a pigment composition obtained by mixing a dioxazine violet pigment obtained in advance.

As the crude copper phthalocyanine which may be milled and the crude dioxazine violet which may be milled, any known and commonly used one may be used in the present invention. These can all be manufactured by a conventionally known method.

The crude copper phthalocyanine used in the present invention can be produced, for example, by the following method. (1) Reaction of phthalic anhydride or a derivative thereof, urea or a derivative thereof, and a copper source. (2) reacting phthalodinitrile and a copper source;

In this case, phthalic acid derivatives include, for example, phthalic acid salts, phthalic anhydride, phthalimide, phthalamic acid and salts or esters thereof, and phthalonitrile. Urea derivatives include, for example, urea, ammonia, and the like.
Examples of the copper source include metal copper, cuprous or cupric halides, copper oxide, copper sulfate, copper sulfide, copper hydroxide, and the like.As the catalyst, for example, ammonium molybdate, molybdenum compounds such as molybdenum oxide, Titanium tetrachloride, titanium compounds such as titanates, zirconium compounds such as zirconium chloride and zirconium carbonate, antimony oxide, boric acid and the like; organic solvents such as aromatic hydrocarbons such as alkylbenzene and alkylnaphthalene, alkylcyclohexane, decalin And the like; aliphatic hydrocarbons such as decane and dodecane; aromatic nitro compounds such as nitrobenzene and nitrotoluene; and aromatic halogenated hydrocarbons such as trichlorobenzene and chloronaphthalene.

In producing crude copper phthalocyanine by the reaction of the above-mentioned production method (1) or (2), a catalyst is added to each of the above-mentioned raw materials, if necessary, in the presence or absence of an organic solvent. For example, 180 ° C.-3
Heat at 00 ° C. for 1-5 hours.

On the other hand, as the crude dioxazine violet used in the present invention, any known and commonly used one can be used. Crude dioxazine violet is obtained, for example, by reacting 3-amino-N-alkyl (C1-C4) carbazole with chloranil in an inert solvent in the presence of a deoxidizing agent to obtain a condensate. Production methods obtained by cyclizing by heating in the presence of an organic acid in an inert solvent, and the like.

In this case, as the deoxidizing agent, for example, sodium carbonate, ammonia, soda ash, sodium bicarbonate, caustic, potassium carbonate, etc., and as the inert solvent, for example, monochlorobenzene, ortho-dichlorobenzene, trichlorobenzene, nitrobenzene, etc. Examples of organic acids such as toluene and xylene include acetic acid, monocarboxylic acids such as propionic acid and benzoic acid, oxalic acid, dicarboxylic acids such as phthalic acid and terephthalic acid, benzenesulfonic acid,
And sulfonic acids such as toluenesulfonic acid.

To obtain this condensate, for example,
Heating is performed at 80 to 260 ° C. for 4 to 8 hours, and for cyclization, for example, heating is performed at 160 to 180 ° C. for 4 to 8 hours.

Both the crude phthalocyanine and the crude dioxazine violet may be in the form of a slurry immediately after production or in the form of a wet cake.
It is preferably in a dry state. As these crude products, those having an average primary particle diameter of 10 to 100 μm can be used.

The mixing ratio of the crude copper phthalocyanine and the crude dioxazine violet can be freely selected,
In order to obtain a commonly used dark blue ink, it is preferable to use 0.1 to 10.0% by weight of crude dioxazine violet based on crude copper phthalocyanine.

The mixture of the crude copper phthalocyanine and the crude dioxazine violet can be used as it is, and the mixture of the crude copper phthalocyanine and the crude dioxazine violet, or the mixture of those individually ground, Alternatively, a mixture obtained by grinding a mixture of crude copper phthalocyanine and crude dioxazine violet can be used. Above all, it is better to perform pigmentation described later using the latter two, when used for gravure ink or flexographic ink, the gloss and coloring power of the finally obtained colored coating film will be more excellent It is preferred.

By grinding the crude product, a smaller average primary particle size, such as from 0.001 to
It can be 0.1 μm. In order for the obtained milled material to show its effect effectively, the average primary particle size of the milled material is 0.0
It is preferably from 0.01 to 0.005 μm.

Regarding the grinding of the crude product, whether copper phthalocyanine or dioxazine violet, known and commonly used grinding means can be employed. As grinding means, dry grinding is less likely to cause excessive aggregation than wet grinding,
It is more preferable because crystal conversion can be performed more easily and workability is excellent.

Dry milling is performed, for example, in the presence or absence of grinding aids such as sodium chloride and sodium sulfate, which have no reactivity with copper phthalocyanine or dioxazine violet, and do not dissolve them. It can be easily implemented using a vibration mill or the like. Dry grinding is more preferably performed in the presence of a grinding aid and in the presence of a dispersion medium such as glass beads and metal beads.

The crude product is pigmented as it is in an unmilled state or after being milled.

The pigmentation treatment can be carried out in the same manner as the conventionally known pigmentation method for crude copper phthalocyanine which may be ground. For example, conventional pigmentation methods include (1) a solvent salt milling method of mechanically grinding crude copper phthalocyanine or ground copper phthalocyanine together with an inorganic salt and an organic solvent, and (2) a crude copper phthalocyanine ground. There are a method of heating and stirring with an organic solvent alone or with an organic solvent and water, (3) an acid paste method and an acid slurry method of dissolving or suspending in concentrated sulfuric acid, followed by pouring into water and reprecipitating.

According to the invention, these pigmentation treatments are carried out, for example, in the presence of a mixture of crude copper phthalocyanine and crude dioxazine violet or of a milled mixture of crude copper phthalocyanine and crude dioxazine violet. Among them, the solvent salt milling method is the most effective pigmentation treatment method as a means for obtaining the effects of the present invention.

The details of the solvent salt milling method, which is the most effective pigmentation method for the present invention, will be described. A mixture of unmilled crude copper phthalocyanine and unmilled crude dioxazine violet, or a mixture of crude copper phthalocyanine and crude dioxazine violet, and crude copper phthalocyanine and crude dioxazine violet each alone For the mixture of those milled in, adjust the water-soluble inorganic salt and organic solvent that are insoluble in organic solvent, so that the milled material can obtain the most effective grinding viscosity, for example, mechanically with a mill After milling, the milled material is taken out into water and filtered to remove inorganic salts and organic solvents.By performing pigmentation, unmilled and milled crude products are obtained before pigmentation. Can obtain a pigment having a small particle diameter, for example, 0.02 to 0.2 μm.

The conditions under which the ground material is most effectively obtained by the grinding viscosity are appropriately adjusted depending on the type of the grinding machine and the like. What is necessary is just to select the condition which becomes the highest crushing efficiency.

As the inorganic salt, the above-mentioned grinding aid can be used, and as the organic solvent, there is no reactivity with the above-mentioned copper phthalocyanine or dioxazine violet and the grinding aid which does not dissolve them. Agents can be used.

More specifically, 100 to 1000 parts by weight of an inorganic salt and 100 to 150 parts by weight of an organic solvent are added to 100 parts by weight of a mechanically ground mixture, and the mixture is polished by a kneader or a Banbury mixer. This is a method of mechanically grinding for 2 to 10 hours with a crusher, taking out the crushed product into water, and removing the inorganic salt and the organic solvent by filtration to obtain a pigment.

After removing the inorganic salt and the organic solvent, if necessary, washing with water or hot water is repeated, followed by filtration, so that inorganic salts and impurities can be further reduced. For example, when washing, the washing water has a specific conductivity of 10%.
The process is performed until the value becomes 0 S / m × 10 ⁻⁴ or less.

The wet material thus obtained can be dried, for example, at 50 to 200 ° C. with a dryer or the like to obtain a dried blue-black pigment. Of course, it is also possible to dry with a spray dryer or the like in the state of a dispersion liquid to which water has been added after the filtration, or in the state of a dispersion liquid containing washing water.

The thus-dried azure blue pigment is easily loosened to such an extent that it can be used as it is.
If necessary, pulverization may be further performed, or classification may be performed to sharpen the particle size distribution.

The blue-black pigment of the present invention can be used in the known and used fields,
For example, general-purpose inks such as gravure inks and flexo inks, general-purpose paints such as baking coatings, UV coatings, and ever-drying coatings, coloring of thermoplastic molded articles, toners for electrophotography, jet printer inks, and known and common recording materials such as color filters. It can be used for various applications.

The blue-black pigment of the present invention is particularly suitable for preparing a gravure ink or a flexographic ink.

Gravure inks or flexo inks are
For example, it can be prepared by dispersing the pigment composition obtained in the present invention in a vehicle. The vehicle is usually prepared by uniformly mixing a resin, water and / or an organic solvent as a main component and other additives. When preparing an oil-based ink, a hydrophobic organic solvent as a solvent,
When a water-soluble ink is prepared by using a resin that is soluble in the solvent, water or water and a hydrophilic organic solvent are used as the solvent, and a resin that is stably dissolved or dispersed in the solvent is used.

The blue-black pigment obtained by the present invention most effectively shows its characteristics in an aqueous flexographic ink, and the vehicle used here is usually a resin, a solvent,
It is prepared using plasticizers, waxes, lubricants, defoamers and the like.

Examples of the resin include natural resin-based shellac, synthetic resin-based rosin-modified maleic resin,
In addition to styrene-acrylic acid resin, acrylic acid-acrylic acid ester resin, polyester resin, water-soluble polyamide resin, aqueous polyurethane resin, and the like. The solvent may be water alone, but a hydrophilic organic solvent is generally used in combination. As the hydrophilic organic solvent, for example, alcohol solvents such as methanol, ethanol, propanol, and butanol are suitably used.

In preparing the ink, the pigment composition of the present invention is used in an amount of 200 to 60 parts by weight per 100 parts by weight of the resin nonvolatile component.
It is prepared so as to be 0 parts by weight.

When the blue-black pigment of the present invention is used for an oil-based ink, the ink which has been previously pigmented can be mixed with a varnish for an oil-based ink to prepare an ink. For example, it is also possible to simultaneously perform the pigmentation treatment and the inking treatment on the ground crude product in the presence of a varnish for oil-based ink.

The ink thus obtained can be printed by coating and drying on a known and commonly used printing medium. Examples of the print medium include paper, resin-coated paper,
Examples include synthetic resin films and sheets.

[0039]

EXAMPLES Examples, reference examples and comparative examples will be described below. In Examples and Reference Examples, “parts” means “parts by weight” and “%” means “% by weight”.

Example 1 300 parts of a mixture of 95% of unmilled crude copper phthalocyanine and 5% of unmilled crude dioxazine violet and 2100 parts of sodium chloride were charged into an 8 L double-arm kneader, and diethylene glycol was milled. Was added while being adjusted so as to be most effectively ground, and ground at 90 ° C. for 7 hours to perform a pigmentation treatment. Next, the ground material was taken out into water, stirred sufficiently, filtered, washed with a large amount of water, and dried to obtain a blue-black pigment. The average primary particle size of this pigment is 0.1.
It was 05 μm. The copper phthalocyanine contained here was of the β type.

Reference Example 1 500 parts of a mixture of 95% of unmilled crude copper phthalocyanine and 5% of unmilled crude dioxazine violet were put into a 5 L attritor loaded with steel beads and charged at 90 ° C. for 1 hour. Mechanical milling was performed to obtain a dry milled mixture of crude copper phthalocyanine and crude dioxazine violet. The average primary particle size of this was 0.1.
005 μm.

Example 2 A pigmentation treatment was carried out in the same manner as in Example 1, except that a mixture of the dry-ground crude copper phthalocyanine and the crude dioxazine violet obtained in Reference Example 1 was used. I got The average primary particle size of this pigment is 0.0
It was 3 μm. The copper phthalocyanine contained here is β
It was a mold.

Comparative Example 1 A pigmentation treatment was carried out in the same manner as in Example 1 except that only crude copper phthalocyanine which had not been ground was used to obtain a blue pigment. In addition, a crude dioxazine violet that had not been ground was used alone to perform a pigmentation treatment in the same manner, thereby obtaining a purple pigment. A blue-black pigment was obtained by blending 95 parts of a blue pigment and 5 parts of a purple pigment from the obtained pigment.

The indigo blue pigments obtained in Example 1, Example 2, and Comparative Example 1 were evaluated with an aqueous flexographic ink.
Table 1 shows the results. Although the evaluation was shown using an aqueous flexographic ink, the present invention is not limited to this.

[0045]

[Table 1] Table 1

* 1 Sharpness 40 parts of the blue-black pigment obtained in each of the above Examples and Comparative Examples, a vehicle (Johncryl 61J manufactured by Johnson Wax Co., Ltd.)
An aqueous dispersion of a styrene- (meth) acrylic acid- (meth) acrylate copolymer. Nonvolatile content 31%) 34.5
Parts, 34.5 parts of IPA (isopropanol) and 0.2 parts of an antifoaming agent together with 250 parts of 1/8 steel beads 25
Put in a 0cc container and use a paint mill (Toyo Seiki Co., Ltd.)
After running for 1 minute, each aqueous flexographic ink was obtained. The obtained water-based flexographic ink was spread on high-quality paper using a 0.15 mm bar coater, and the sharpness was visually determined.

* 2 Gloss: The haze-gloss meter (BY
The gloss was measured by K. Gardner). Comparative Example 1
Example 1 and Example 2 are compared as 00 (standard).

* 3 Coloring power 1.5 parts of aqueous flexo ink and 35 parts of white ink (Daiflex ACT709 white, manufactured by Dainippon Ink and Chemicals, Inc.) obtained in the evaluation of sharpness were mixed in a 100 cc container and mixed well to obtain a light color. An ink was obtained. 0.15 of the obtained light color ink
Using a bar coater to spread the color on high quality paper, SPECTRAFLA
The coloring power was measured using SH500 (manufactured by Data Color). Comparative Example 1 and Example 2 are compared with Comparative Example 1 as 100 (standard).

[0049]

The blue-black pigment of the present invention thus obtained has a sharper hue and higher tinting strength than the ink product of the compounded pigment. In addition, since the pigmentation step is one-step, the production process is simplified, and the production cost can be greatly reduced.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J037 AA30 DD05 EE28 EE29 EE43 EE44 FF08 4J039 BC53 BC60 BE01 CA06 DA02 DA05 EA16 EA42 GA03 GA09

Claims (3)

[Claims] 1. A blue-black pigment characterized by subjecting a mixture of a crude copper phthalocyanine (A) which may be ground and a crude dioxazine violet (B) which may be ground to a pigmentation treatment. Manufacturing method. 2. A gravure flexographic ink characterized in that a mixture of a crude copper phthalocyanine (A), which may be ground, and a crude dioxazine violet (B), which may be ground, is subjected to a pigmentation treatment. Method for producing blue-black pigments. 3. The method for producing a pigment according to claim 2, wherein the gravure flexographic ink is an aqueous flexographic ink.