JPH0826243B2 - Monoazo lake pigment and pigment dispersion composition - Google Patents

Description

Detailed Description of the Invention [Object of the Invention] (Field of Industrial Application) The present invention relates to various uses, particularly to a monoazo lake pigment useful for coloring a printing ink and a printing ink composition using the same.

(Prior Art) Conventionally, a monoazo lake pigment obtained from an aromatic amine having a soluble group and β-naphthol or β-oxynaphthoic acid has been widely used for coloring printing inks, paints, plastics, and particularly Pigment Red 57 (CI1585
0) is often used as a pigment for process red ink.
These monoazo lake pigments make the color tone clear,
In addition, the rosin treatment is performed at a rate of 1 to 30% by weight to improve the coloring power, and the above Pigment Red 57 is treated with 20 to 30% by weight of rosin with respect to the pigment component.

When these pigments are used in printing inks, for example, gravure inks only give high-viscosity inks and their stability over time becomes poor, and offset inks dissolve rosin components in dampening water, making offset inks water-soluble. There is a drawback that the fluidity changes when emulsified and the surface tension of the ink emulsified water decreases, and the printability decreases.

In order to improve such drawbacks, a method for synthesizing a rosin-less pigment or a pigment in which the amount of rosin used is reduced to 1 to 7% by weight has been studied, but the hue is unclear and the tinting strength is lowered.

(Problems to be Solved by the Invention) As a method for solving the above-mentioned drawbacks, the present inventors have solved the above-mentioned drawbacks by using an electron-withdrawing group as a part of a diazo component when synthesizing a monoazo lake pigment. However, they have found that the pigment composition has excellent sharpness and transparency and is very improved as a pigment for printing ink.

[Structure of Invention]

(Means for Solving the Problems) That is, the present invention provides a benzene-based amine containing an electron-withdrawing group selected from a nitro group, a trifluoromethyl group, and a cyano group and having no soluble group. Aromatic amine having a group 99.9 to 80 mol% as a mixed diazo component, and coupled as at least one coupler component selected from β-naphthols, β-oxynaphthoic acids, acetanilides, simultaneously with or after coupling. The present invention relates to a laked monoazo lake pigment.

The benzene-based amine containing an electron-withdrawing group and having no soluble group according to the present invention is represented by the following general formula.

(In the formula, X is an electron-withdrawing group selected from a nitro group, a trifluoromethyl group, and a cyano group, and Y represents hydrogen, chlorine, a methyl group, an ethyl group, a methoxy group, and an ethoxy group.) Specifically, 4-nitro-6-methylaniline, 4-
Nitro-6-methoxyaniline, 3-nitro-6-methylaniline, 3-nitro-6-methoxyaniline, 4-nitro-5-methylaniline, 4-nitro-5-methoxyaniline, 3-nitro-5-methyl Aniline, 3-nitro-5-methoxyaniline, o-aminobenzenetrifluoride, m
Examples thereof include cyanoaniline.

The aromatic amine having a soluble group of the present invention includes 1
-Amino-4-methylbenzene-2-sulfonic acid, 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid, 1-amino-4-methyl-5-chlorobenzene-2-
Sulfonic acid, 1-aminonaphthalene-2-sulfonic acid, 1-
Amino-4-chloro-5-methylbenzene-2-sulfonic acid and the like. Examples of the coupler component in the present invention include β-naphthol, β-oxynaphthoic acid, naphthol AS, and acetoacetanilides.

In the present invention, the method for producing a monoazo lake pigment can be performed according to a conventional method for producing a monoazo pigment. That is, a benzene-based amine having an electron-withdrawing group is added to an aromatic amine having a soluble group to form a diazo component, which is then diazotized by a conventional method. Then, the above-mentioned coupler component is mixed and coupled in a conventional manner to form a lake with a lake-forming agent, or a diazo component or a coupler component is added with a lake-forming agent in advance and coupled to form a monoazo lake pigment. Is obtained. Examples of coupling metals include calcium, barium, strontium, manganese, etc., with calcium being preferred.

The surface treatment of the pigment can be performed by adding a water-soluble resin, a surfactant, and other additives to the diazo component, the coupler component, the dye or the pigment slurry.

The benzene-based amine having an electron-withdrawing group of the present invention is preferably 0.1 to 20 mol% in the diazo component. If it is less than 0.1 mol%, the effect of high coloring power, large clarity, large transparency and good fluidity is not observed, and if it is used in excess of 20 mol%, the effect of the used amount cannot be obtained.

The pigment composition of the present invention includes paints and printing inks.

The paint comprises 0.1 to 15% by weight of the monoazo lake pigment of the present invention, 99.9 to 55% by weight of the vehicle for paint, and 0 to 30% by weight of other auxiliary agents and extender pigments. The vehicle for the paint includes acrylic resin, alkyd resin and epoxy. Resin, Chlorinated rubber, Vinyl chloride, Synthetic resin emulsion, Silicone resin, Water-soluble resin, Polyurethane, Polyester, Melamine resin, Urea resin or 80 to 20% by weight of a mixture thereof and hydrocarbon, alcohol, ketone, ether, ester water The solvent is composed of 60 to 10% by weight.

Printing inks include offset inks and gravure inks. For offset inks, the monoazo lake pigment of the present invention is used in an amount of 3 to 35% by weight and a vehicle for offset ink.
It consists of 97 to 45% by weight and 0 to 20% by weight of other auxiliaries and extender pigments. Vehicles for offset inks include rosin-modified phenolic resin, petroleum resin, aluminum resin, or resins such as dry oil-modified resin 20- 50 parts by weight, vegetable oil such as alni oil, tung oil, soybean oil 0 to 30 parts by weight, n-paraffin, isoparaffin, aromatech, naphthene, α-
It is composed of 10 to 60 parts by weight of a solvent such as olefin.

Further, as the gravure ink, the monoazo lake pigment of the present invention 3 to 20% by weight, the vehicle for gravure ink 97 to
60% by weight, 0 to 20% by weight of other auxiliaries and extenders. As a vehicle for gravure ink, gum rosin,
Wood rosin, tall oil rosin, calcified rosin, lime rosin, rosin ester, maleic acid resin, gilsonite, dammar, shellac, polyamide resin, vinyl resin, nitrocellulose, cyclized rubber, chlorinated rubber, ethyl cellulose, cellulose acetate, ethylene-acetic acid Resin mixture such as vinyl copolymer resin, urethane resin, polyester resin, aluminum resin 10 to 50 parts by weight, n-hexane, toluene, ethanol, methanol, acetone, ethyl acetate, ethyl lactate, cellosolve, diacetone alcohol,
It is composed of 30 to 80 parts by weight of a solvent such as chlorobenzene, ethyl ether, acetal ethyl ether, ethyl acetoacetate, butyrocellosolve acetate.

(Examples) Hereinafter, the present invention will be described with reference to Examples. In the examples, "parts" means "parts by weight" and "%" means "% by weight".

Example 1 1-Amino-4-methylbenzene-2-sulfonic acid 1
6.7 parts was stirred with 400 parts of water and 4 parts of sodium hydroxide at room temperature for 30 minutes to be completely dissolved. After adding 25 parts of 35% hydrochloric acid and acidifying, 2 parts of 3-nitro-6-methylaniline was added and dissolved. 20 parts of ice was added and cooled to 0 ° C to 3 ° C, 7 parts of sodium nitrite dissolved in 25 parts of water was added, and stirring was continued at 5 ° C or less for 30 minutes to obtain a diazo component.

On the other hand, 19 parts of β-oxynaphthoic acid was added to 1 part of natural rosin,
Dissolve it at 15 ° C with 1000 parts of water and 10 parts of sodium hydroxide, and use this as the coupler component. The diazo component was added dropwise to this coupler component over 30 minutes, and the mixture was further stirred for 1 hour to complete the coupling reaction. The pH of the coupling liquid was 9.5-10.0. Then, 58 parts of 35% calcium chloride aqueous solution was added and stirred for 2 hours to complete the lake formation reaction. After heating to 80 ℃, filtration, washing with water, drying and crushing 43
Some parts of monoazo lake pigment were obtained. For comparison, a pigment was obtained in the same manner as in this example except that 3-nitro-6-methylaniline was not used in the diazo component.

The pigments of this example and the comparative pigment were made into ink and tested. The varnish used is Tamanol 361 (Arakawa Chemicals:
20 parts of linseed oil to 50 parts of rosin-modified phenolic resin)
Part, No. 5 Solvent (Nippon Oil Co., Ltd .: Ink solvent) 30
Parts were added, and the mixture was heated and melted at 200 ° C and used. Then, 2 parts of aluminum octylate was added to 98 parts of this varnish to form a gel varnish.

70 parts of the obtained gel varnish, 20 parts of pigment, and 10 parts of No. 1 solvent (Nippon Oil Co., Ltd .: ink solvent) were mixed and mixed and kneaded with a three-roll to obtain an offset ink having a tack value of 9.0. The offset ink obtained in this example was remarkably transparent, clear (visual judgment) and excellent in coloring power as compared with the ink obtained from the comparative pigment. The tinting strength was judged by developing a mixture of white ink and dark color ink (drawdown). The ink using the pigment of this example had coloring power, and about 10% of white ink could be added to make it equivalent to the ink of the comparative pigment.

Example 2 1-Amino-4-methylbenzene-2-sulfonic acid 1
6.7 parts and 2 parts of 3-nitro-6-methylaniline were added to diazotize according to a conventional method, and 58 parts of 35% calcium chloride aqueous solution was added to obtain a diazo solution.

Separately, 19 parts of β-oxynaphthoic acid and 1 part of natural rosin are dissolved according to a conventional method to obtain a coupler solution. The diazo solution was rapidly mixed with the coupler solution to complete the coupling reaction and the lake reaction, heated to 80 ° C., filtered and washed with water to obtain 43 parts of a monoazo lake pigment. For comparison, a pigment was obtained in the same manner as in this example except that 3-nitro-6-methoxyaniline was not used in the diazo component.

The offset ink prepared from the pigment obtained in this example was remarkably transparent, clear and excellent in coloring power as compared with the comparative pigment.

Example 3 1-amino-4-methylbenzene-2-sulfonic acid 1
6.4 parts and 0.3 of 2-aminonaphthalene-1-sulfonic acid
Parts and 4-nitro-6-methylaniline were diazotized by a conventional method, and 58 parts of 35% calcium chloride aqueous solution was added to obtain a diazo solution. A coupler solution is obtained by dissolving 19 parts of β-oxynaphthoic acid and 1 part of natural rosin. Mix both components,
The coupling reaction and lake reaction were completed, heated to 80 ° C, filtered and washed with water to obtain 44.5 parts of monoazo lake pigment. For comparison, a pigment was obtained in the same manner as in this example except that 4-nitro-6-methylaniline was not used in the diazo component.

The offset ink prepared from the pigment obtained in this example was remarkably transparent, clear and excellent in coloring power as compared with the comparative pigment.

Example 4 42 parts of monoazo lake pigment was obtained in the same manner as in Example 2 except that 2 parts of 4-nitro-6-methoxyaniline was used instead of 3-nitro-6-methoxyaniline in Example 2. For comparison, 4-nitro-6-in the diazo component
A pigment was obtained in the same manner as in this example except that methoxyaniline was not used.

The published gravure ink prepared from the pigments obtained in this example was remarkably transparent, clear and excellent in tinting strength as compared with the comparative pigments.

In addition, this test method charged 200cc mayonnaise bottle with the following composition, pigment 10 parts lime rosin varnish (solid content 20%, toluene 75%, plasticizer 5%) 90 parts diameter 3mm glass beads 100 parts paint conditioner for 2 hours Shake and use this as the dark ink. Also, a light-colored ink was prepared by kneading 10 parts of white ink with 1 part of dark-colored ink, and the tinting strength was evaluated. The tinting strength was about 10% greater than the ink prepared from the comparative pigment.

Example 5 42 parts of monoazo lake pigment was obtained in the same manner as in Example 2 except that 2 parts of o-aminobenzenetrifluoride was used instead of 3-nitro-6methoxyaniline in Example 2. For comparison, a pigment was obtained in the same manner as in this example except that o-aminobenzenetrifluoride was not used in the diazo component.

The published gravure ink prepared from the pigments obtained in this example had a tinting strength of about 10% greater than the comparative pigments.

Example 6 22.5 parts of 1-amino-2-nitrobenzene-4-sulfonic acid sodium salt was stirred in 400 parts of water at room temperature for 30 minutes to completely dissolve it. 35 parts of 35% hydrochloric acid was added and dissolved, 2 parts of m-cyanoaniline was added and dissolved, and the diazo component was prepared by the same operation as in Example 1 below.

On the other hand, 22 parts of acetoacetoorthochloranilide was added to water.
After dissolving it with 700 parts and 12 parts of sodium hydroxide at 20 ° C, 90% acetic acid for 21.5 minutes was gradually added dropwise, and acid precipitation was performed as a coupler component.

As the coupler component, the above-mentioned diazo component was added dropwise over 20 minutes, stirring was continued for 1 hour to complete the coupling reaction, and 10 parts of sodium hydroxide dissolved in 100 parts of water was added dropwise to adjust the pH to 8.5. After that, heat to 90 ℃,
% Of calcium chloride aqueous solution was added to complete the lake formation reaction. After filtering, washing with water, drying and crushing, 44 parts of monoazo lake pigment was obtained. For comparison, a pigment was obtained in the same manner as in this example except that m-cyanoaniline was not used in the diazo component.

The pigment obtained in this example was shaken for 90 minutes in a bain conditioner with the following composition, and the resulting paint had excellent tinctorial strength of 5% and gloss of 5% as compared with the comparative pigment.

Pigment 8 parts Alumide resin varnish 50 parts Melamine resin varnish 30 parts Thinner 12 parts 2mm steel beads 300 parts [Effect of the invention] The monoazo lake pigment of the present invention has higher tinting strength, greater clarity, and transparency than conventional azo pigments. It is a big one. In addition, the fluidity is good while satisfying these effects.

Further, the conventional azo pigment treated with a large amount of rosin reduces printability when used in a printing ink, whereas the azo pigment of the present invention has good printability. Further, the azo pigment of the present invention is also excellent in thermal stability during the flushing operation. That is, in the conventional azo pigment, crystal growth and agglomeration of the pigment particles occurred during the heating operation at the time of flushing, and the opacity of the ink and the remarkable decrease in the coloring power occurred. It is a thermally stable pigment that does not occur.

Claims (2)

[Claims] 1. A benzene-based amine having an electron-withdrawing group selected from a nitro group, a trifluoromethyl group, and a cyano group and having no soluble group, 0.1 to 20 mol%, and an aromatic amine having a soluble group, 99.9 to 80 mol. % As a mixed diazo component,
A monoazo lake pigment obtained by coupling at least one selected from β-naphthols, β-oxynaphthoic acids and acetanilides as a coupler component, and forming a lake at the same time as or after coupling. 2. A pigment dispersion composition comprising the monoazo lake pigment according to claim 1 and a dispersing resin.