JPS62172078A - Printing ink composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent water-resistance and printability, by adding cured granule of an aminosulfonic acid-modified condensate compound having low molecular weight or its precondensate. CONSTITUTION:The objective ink composition contains granules produced by acidifying and curing an aqueous solution of a low-molecular-weight condensable triazine compound modified with an aminosulfonic acid (e.g. sulfamic acid, aminobenzenesulfonic acid, etc.) [preferably condensable melamine (2,4,6- triamino-1,3,5-s-triazine) modified with aminosulfonic acid, etc.] and/or its precondensate and, if necessary, crushing or grinding the cured product.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a printing ink composition, and more particularly to a printing ink composition having excellent water resistance.

(Prior art) Conventionally, lithographic printing inks have been widely used as printing inks, but such lithographic printing inks are used in printing methods that take advantage of the ink's water repellency, and are Sufficient water resistance is required.

(Problem to be Solved by the Invention) Most lithographic printing inks are manufactured by the so-called flushing method, in which an aqueous slurry of pigment is flushed with an ink vehicle, the pigment is transferred from hydrated to an oil phase, and water is removed. ing.

At this time, surfactant substances that have a certain degree of wood affinity may be used to improve flushing efficiency, and as a result, the resulting printing ink often suffers from water loss during printing, resulting in printing defects. .

Therefore, there is a demand for a lithographic printing ink that does not cause water loss during printing and has sufficient water resistance even when used by the flushing method.

The inventor of the present invention has solved the above-mentioned drawbacks of the prior art and has conducted extensive research to obtain a printing ink with sufficient water resistance. The present invention was completed based on the finding that the water resistance of the material can be significantly improved.

(Means for Solving the Problems) That is, the present invention provides a printing ink composition containing granules obtained by curing an aminosulfonic acid-modified condensable triazine-based low-molecular compound and/or an initial condensate thereof. It is a thing.

To explain the present invention in detail, the granules used in the present invention and which mainly characterize the present invention are amide/sulfonic acid-modified condensable triazine-based low-molecular compounds and/or their initial condensates prepared by a conventional method. It is obtained by curing and forming into one granule.

The condensable triazine-based low molecular weight compounds or their initial condensates used in the production of such granules before modification include methylolated products, alkoxylated products, halogenomethylated products, etc. of conventionally known triazine-based amino compounds. , methylol group-containing compounds, and various methylol group-modified 'A derivatives and triazine-based amine compounds.

As the triazine-based amino compound, a 1.3°5-triazine-based amino compound is preferred, such as melamine (2,4,6-triamino-1,3,5-s-1
riazine), ammeline (2,4-diamino-6-hydroxy-1,3゜5-s-triazine), ammelide (2-monoamine/-4,6-hydroxy-1,3.5
-s-triazine), benzoguanamine (2,4-diamino-6-phenyl-1,3,5-3-triazine),
Acetoguanamine (2,4-diamino-6-methyl-1
, 3,5-5-triazine), -oxidation+N-+N-

In the above, melamine and benzoguanamine are the most preferred triazine-based amino compounds. Therefore, the most preferred compounds as condensable triazine-based low-molecular compounds and their initial condensates are methylolmelamine having 2 to 6 methylol groups and its alkoxymethyl derivatives, methylolbenzoguanamine having 2 to 4 methylol groups and its Alkoxymethyl derivatives and their initial condensates.

The ami/sulfonic acid preferably used in the present invention refers to a compound having both an amino group and a sulfonic acid group in the molecule, such as sulfamic acid, aminobenzenesulfonic acid, metanilic acid, naphthylaminosulfonic acid, ami/sulfonic acid, etc.
Examples include phenolsulfonic acid, aminonaphtholsulfonic acid, and any other aminosulfonic acid.

Particularly preferred are aminosulfonic acid-modified methylolaminotriazine compounds, realkoxymethylaminotriazine compounds, and their initial condensates.For example, aminosulfonic acid-modified methylolmelamine obtained using melamine is particularly preferred. It is obtained by adding, for example, about 0.05 to 3 mol of amino acid carboxylic acid per 1 mol/m of methylol melamine during or after the production of methylol melamine.

The granules used in the present invention are obtained by curing the above-mentioned aminosulfonic acid-modified triazine-based low-molecular compounds and/or their initial condensates. Creating an aqueous solution of a modified condensable triazine-based low-molecular compound and/or an initial condensate thereof, acidifying the pH of the aqueous solution,
Preferably by acidifying to about pH 4-6.

The ami/sulfo/acid-modified condensable triazine low molecular weight compounds or their initial condensates are polycondensed with each other to produce water-insoluble particulates.

A particularly preferred method is to produce an aminosulfonic acid-modified condensable triazine-based low-molecular compound and/or an initial condensate thereof in an aqueous solution to form an aqueous solution with a concentration of about 5 to 40% by weight. The aqueous solution is added dropwise to an acidic aqueous solution and stirred vigorously.
Fine particles with a particle size of 5-100 microns are produced.

By adjusting the dropping rate, stirring rate, p)I and temperature of the dropping liquid and resistant aqueous solution, the particle size can be freely adjusted within the range of 0.005 to 100 microns.

Further, an acid is added to the aqueous solution of the above aminosulfonic acid-modified condensable triazine-based low-molecular compound and/or their initial condensate, and the pH of the mixture is finally made acidic, preferably at a pH of 4 to 6. In this case, the bulk resin is milled by a ball mill, a sand mill, or other known milling means to obtain a powder having a particle diameter of preferably 0.05 to 100 microns. Granules can be obtained. Also l-
After drying the bulk resin described above, the granules used in the present invention having a particle size of 0.005 to 100 microns can be obtained by dry pulverizing using various types of pulverizers.

In the present invention, when curing such an aminosulfonic acid-modified condensable triazine-based low-molecular compound and/or initial condensate into a granular material, the conventional method of curing condensable triazine-based low-molecular-compounds into fine particles is essential. Another positive feature is that it does not require the use of various surfactants.

In other words, even if no surfactant is used as in the prior art, uniform fine particles are produced without the particles sticking to the gel and becoming coarse or gelling when the resin is cured. This is thought to be because the condensable triazine-based low-molecular compound is moderately modified with 7-minosulfonic acid, and as a result, the balance between wood-philicity and hydrophobicity is maintained at an appropriate level.

The printing ink to which the above-mentioned particulate matter is added may be any conventionally known printing ink, and the effect of the present invention is most clearly achieved with a lithographic printing ink. Lithographic printing ink is a process in which pigments are separated into an ink vehicle that mainly contains oxidative polymerization type resins and drying oils, and also contains organic solvents, dryers, and other additives as necessary.
Therefore, all conventionally known lithographic printing inks may be subject to uninvention.

In the present invention, it has been discovered that the water resistance of these lithographic printing inks can be significantly improved by adding the above-mentioned specific particulate matter to these lithographic printing inks. The amount of the granules added to the feather printing ink is in the range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the lithographic printing ink. When Addition 41 is less than 0.1 parts by weight, the intended effect of the present invention is not sufficiently achieved, and when it is added in an amount exceeding 20 parts by weight, the printability of the lithographic printing ink deteriorates.

In addition, when adding such particulates to the 4i printing ink, it may be added to the lithographic printing ink as a product, it may be added at the time of manufacturing the lithographic printing ink, or it may be added to the top plate. The same effect can be achieved either by pre-mixing part of the ink vehicle of the printing ink with the granules and adding this mixture to the lithographic printing ink or its raw material.

(Operation Φ Effect) According to the present invention as described above, a printing ink Ml composition whose water resistance is significantly improved is provided, and by using such a printing ink composition, the printing ink wood is removed during printing. Since problems such as printing ink and emulsification of printing ink in damp ice do not occur, it is possible to provide excellent printed matter with excellent printability.

Next, the present invention will be explained in more detail with reference to Reference Examples and Examples. It should be noted that parts or percentages in the text are based on weight criteria unless otherwise specified.

Reference Example 1 40 parts of melamine, 100 parts of 35% formalin, 20 parts of methanol and 28 parts of water were mixed and stirred.

When the temperature was raised to 80°C, the mixture became colorless and transparent. Next, this solution was cooled to 45°C, 2.8 parts of sulfamic acid was added to react, one drop of the reaction was dropped into water, and the reaction was continued until the initial condensate was precipitated. The reaction was terminated by adding 5.8 parts of an aqueous sodium hydroxide solution and 20 parts of methanol. 20 parts of this resin solution is dissolved in 100 parts of water and used as a dropping liquid.

Add the above dropwise solution to 150 ml of water at 90°C with a pH of 5,6 to 6,0.
Add dropwise to 0 parts with vigorous stirring. Further, it was cured at 90°C for 1 hour, filtered, washed with water, and smoked at 100°C to give a 0.
1 to 0.2 gm of granules for use in the invention were obtained.

Reference example 2 80% aqueous solution of methylated methylolmelamine resin 100%
1 part was diluted and dissolved with 860 parts of wood, 8.5 parts of metanilic acid was added to the solution with stirring, and the reaction was carried out at 40°C for 60 minutes to precipitate the resin. This solution was neutralized by adding 16 parts of a 20% aqueous sodium hydroxide solution. After cooling, the solid content was filtered to obtain fine particles having a particle size of 2 to 58 Lm for use in the present invention.

Example 1 Flashed color of copper phthalocyanine blue pigment (pigment content 56%) 34.8i-It (
Mixed varnish for offset lithographic ink 62.0 parts 5% cobalt dryer 0.2 parts 8% manganese dryer 1.0 parts Reference example 10 Granules
1.0 part ink solvent vent
1.0゜Total
An offset lithographic ink was obtained from 100 g of the above components according to a conventional method.

In the above, the blended varnish for offset lithographic ink has the following composition.

Rosin modified phenol mlW 3 parts g Drying oil 250 Drying oil modified isophthalic acid alkyd 100 parts Ink Solvent
29.5 parts aluminum clear) o
, s.

When we printed on high-quality paper using an offset printing machine using the ink obtained from a total of 100 copies, there was no water loss of the printing ink at all.
A clear blue print was obtained.

Example 2 Varnish dispersion of carbon black pigment 94 parts 5% cobalt dryer 0.2 parts 8% manganese dryer 1.0 parts Granules of Reference Example 2
1.0 part upper Z earth ヱ earth Δヱ upper - 11111 - Uni 1 comparison total 1
00 parts''--The components listed above were thoroughly and uniformly mixed and kneaded according to a conventional method to obtain 1 carbon black ink. When I printed this on an offset printing machine, there was no water loss at all, and the blackness was high! Prints in 11 colors were obtained.

Applicant: Dai) I Karika Kogyo Co., Ltd. −′−

Claims (3)

[Claims] (1) A printing ink composition containing granules obtained by curing an aminosulfonic acid-modified condensable triazine-based low-molecular compound and/or an initial condensate thereof. (2) A granular material obtained by acidifying and hardening an aqueous solution of an aminosulfonic acid-modified condensable triazine-based low-molecular compound and/or an initial condensate thereof, and further crushing or grinding as necessary. The printing ink composition according to claim (1). (3) Claim No. 1, wherein the aminosulfonic acid-modified condensable triazine-based low-molecular compound is aminosulfonic acid-modified methylolmelamine or an initial condensate thereof.
The printing ink composition described in .