JPH0813936B2 - Monoazo lake pigment and printing ink 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 in order to improve the coloring power, and the pigmentlet 57 described above is treated with 20 to 30% by weight of rosin with respect to the pigment content.

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 proposed a method for synthesizing a monoazo lake pigment. A monoazo lake pigment obtained by using a benzene-based amine having a group (however, R ₁ and R ₂ are the same as above) as a part of the diazo component solves the above-mentioned drawbacks and has excellent sharpness,
It has been found that the pigment composition has transparency and is very improved as a pigment for printing inks and paints.

[Structure of Invention]

(Means for Solving the Problems) The present invention will be described in detail. Aromatic amines used as diazo components in the present invention are known, and for example, 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.

The coupler component is also a known compound such as β-naphthol, β-oxynaphthoic acid and naphthol AS.

The method for producing an azo pigment using the above raw materials can be performed according to a conventional method for producing a monoazo pigment.
Ie Add a benzene-based amine having a group to the diazo component,
Diazotization is carried out according to a conventional method. Then, the above-mentioned coupler component is mixed and coupled according to a conventional method, and the dye is laked with a lake agent, or the diazo component,
A monoazo lake pigment having improved suitability according to the method of the present invention can be obtained by adding a laker in advance to the coupler component and coupling them.

Of course, 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.

In the present invention The benzene-based amine having a group is a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen atom and It may be substituted with a substituent selected from a nitro group. Also, As R ₁ and R ₂ of the group, a group selected from a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms and an optionally substituted aryl group is represented.

More specifically, for example, 4-amino-benzenesulfonamide, 3-amino-4-methoxybenzenesulfonamide, 3-amino-4-methylbenzenesulfonamide, 3
-Amino-4-ethylbenzenesulfonamide, 3-amino-4-methoxy-N-butylbenzenesulfonamide, 3-aminobenzenesulfonamide, 3-amino-4-
Methylbenzenesulfonamide, 3-amino-4-methyl-N, N-dimethylbenzenesulfonamide, 3-amino-
4-methoxy-N, N-diethylbenzenesulfonamide,
2-amino-N-ethyl-N-phenylbenzenesulfonamide, 3-amino-4-methoxy-N-eicosanebenzenesulfonamide, 4-amino-N-dodecylbenzenesulfonamide, 3-amino-N-octylbenzene Examples include sulfonamide, 3-amino-4-chlorobenzenesulfonamide, 3-amino-4-nitro-benzenesulfonamide and the like.

Of the present invention The benzene-based amine having a group 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.

As the vehicle for the printing ink of the present invention, for example, in the case of offset ink, rosin-modified phenolic resin, petroleum resin, alkyd resin, or 20 to 50 parts by weight of resin such as drying oil-modified resin, linseed oil, tung oil, soybean oil 0 to 30 parts by weight of vegetable oil such as n-paraffin, isoparaffin, aromatech, naphthene, solvent such as α-olefin 10 to 60
It consists of parts by weight. This offset ink vehicle is mixed with the monoazo lake pigment of the present invention, and other known additives such as an ink solvent, a drier, a leveling improver and a thickener are appropriately mixed to obtain a printing ink composition.

Further, as gravure ink, gum rosin, wood rosin, tall oil rosin, calcified rosin, lime rosin, rosin ester, maleic acid resin, gilsonite,
Resin mixture such as dammar, shellac, polyamide resin, vinyl resin, nitrocellulose, cyclized rubber, chlorinated rubber, ethyl cellulose, cellulose acetate, ethylene-vinyl acetate copolymer resin, urethane resin, polyester resin, alkyd resin 10 to 50 weight Parts, n-hexane, toluene,
Solvents such as ethanol, methanol, acetone, ethyl acetate, ethyl lactate, cellosolve, diacetone alcohol, chlorobenzene, ethyl ether, acetal ethyl ether, ethyl acetoacetate, butyl cellosolve acetate
30 to 80 parts by weight, monoazo lake pigment of the present invention 3 to 35 parts by weight, barium sulfate, barium carbonate, calcium carbonate, gypsum, white alumina, clay, silica, silica white, talc, calcium silicate, precipitated magnesium carbonate, etc. It is composed of 0 to 20 parts by weight of an extender pigment, and optionally contains, as an auxiliary agent, a plasticizer, a UV inhibitor, an antioxidant, an antistatic agent and the like.

(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
7.0 parts are stirred with 400 parts of water and 4 parts of sodium hydroxide at room temperature for 30 minutes to completely dissolve them. Add 25 parts of 35% hydrochloric acid and acidify, then add 2.5 parts of the following compound (1) and dissolve. Further, 58 parts of 35% calcium chloride aqueous solution and 20 parts of ice are added and cooled to 0 ° C to 3 ° C. Add 7 parts of sodium nitrite dissolved in 25 parts of water and continue stirring at 5 ° C or lower for 30 minutes to obtain the 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 coupler solution is promptly mixed with the diazo solution to complete the coupling reaction and the lake reaction. The pH of the coupling solution from ^10.0 to 1
0. was ^5. After heating to 80 ° C, filter, wash with water, dry and crush 4
5 parts of monoazo lake pigment are obtained.

The obtained pigment was made into an ink and tested as a pigment composition.

The pigment obtained above was made into an ink and tested.
The varnish used was 200 parts of Tamanaru 361 (Arakawa Chemical Co., Ltd .: rosin modified phenolic resin) 50 parts, linseed oil 20 parts, No. 5 solvent (Nippon Oil Co., Ltd .: ink solvent), 200 parts.
It was heated and melted at ℃ to manufacture. 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 and 20 parts of the red pigment of the present invention obtained by using the compound (1) and 10 parts of No. 1 solvent (Nippon Petroleum Co., Ltd .: ink solvent) were blended and mixed and kneaded with a three-roll mill. An offset ink with a tack value of 9.0 was obtained. The obtained offset ink was remarkably transparent, clear (visual judgment) and excellent in coloring power as compared with the ink obtained from the pigment to which the compound (1) was not added. The tinting strength was determined by developing (drawing down) a mixture of white ink and dark ink. The ink using the pigment of the present invention 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
7.0 parts and 2.5 parts of the following compound (2) are added to diazotize according to a conventional method.

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 above-mentioned diazo component is added dropwise to this coupler component over 30 minutes, and then stirring is continued for another hour to complete the coupling reaction. Next, 58 parts of 35% calcium chloride aqueous solution is added and stirred for 2 hours to complete the lake reaction. After heating to 80 ° C, filtration, washing with water and drying were carried out to obtain 45 parts of solid content.

The offset ink prepared from the obtained pigment is
It was remarkably transparent, vivid and excellent in coloring power as compared with the conventional pigment not using the compound (2).

Example 3 1-amino-4-methylbenzene-2-sulfonic acid 1
6.5 parts and 2-aminonaphthalene-1-sulfonic acid 0.5
Part and the following compound (3) after diazotization according to the usual method, 35%
58 parts of an aqueous calcium chloride solution is added to obtain a diazo component. 19 parts of β-oxynaphthoic acid and 1 part of natural rosin are dissolved to obtain a coupler component. Both components were mixed to complete the coupling reaction and the lake reaction, heated to 80 ° C, filtered and washed with water to obtain 45.5 parts of monoazo lake pigment.

The offset ink prepared from the obtained pigment is
Compared to the conventional pigments that do not use the chemical substance (3), they were remarkably transparent, vivid and excellent in coloring power.

Example 4 44 parts of a monoazo lake pigment was obtained in the same manner as in Example 1 except that 2.5 parts of the following compound (4) was used instead of the compound (1) in Example 1.

The published gravure ink prepared from the obtained pigment was remarkably transparent, vivid and excellent in coloring power as compared with the conventional pigment not using the compound (4).

In addition, this test method was prepared by charging 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% higher than that of the ink prepared from the pigment containing no compound (4).

Example 5 1-Amino-4-methylbenzene-2-sulfonic acid 1
7.0 parts and 2 parts of the following compound (5) are added, diazotized in a conventional manner, and 58 parts of 35% calcium chloride aqueous solution is added to obtain a diazo solution.

On the other hand, according to a conventional method, 19 parts of β-oxynaphthoic acid and 1 part of natural rosin are dissolved to obtain a coupler solution. The coupler solution was rapidly mixed with the above diazo solution to complete the coupling reaction and the lake reaction, heated to 70 ° C., filtered and washed with water to obtain 44 parts of a solid content.

The offset ink prepared from the obtained pigment was remarkably transparent, washes the surface and was excellent in tinting strength as compared with the conventional pigment not using the following compound (5).

〔The invention's effect〕

The monoazo lake pigment of the present invention has higher tinting strength, greater clarity and greater transparency than conventional azo pigments. 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 a soluble group as a diazo component, and A benzene-based amine having a group (wherein R ₁ and R ₂ represent a group selected from a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms and an optionally substituted aryl group) ,the above The benzene-based amine having a group couples the diazo component, which is 0.1 to 20 mol% of the diazo component, with the coupler component selected from β-naphthol and β-oxynaphthoic acids, and simultaneously with or after the coupling Monoazo lake pigment that is made into a polymer. 2. A printing ink composition comprising the monoazo lake pigment according to claim 1 and a printing ink vehicle.