JP2020172615A - Lithographic printing ink composition and printed matter - Google Patents

Abstract

To provide a lithographic printing ink composition which can suppress odor occurrence without causing printing troubles such as base contamination and gloss ghost, can obtain a printed matter excellent in scratch resistance, and contain vegetable oil and/or vegetable oil ester.SOLUTION: A lithographic printing ink composition contains a compound that reduces diffusion of an aldehyde compound by chemical adsorption, a binder resin, vegetable oil and/or vegetable oil ester (C), and a pigment (D), in which the compound that reduces diffusion of the aldehyde compound by chemical adsorption contains a compound (A) having an NH group as a partial structure, the binder resin contains a rosin-modified phenol resin (B), and a content of the vegetable oil and/or vegetable oil ester (C) is 40-55 mass% in the total amount of the lithographic printing ink composition.SELECTED DRAWING: None

Description

The present invention relates to a lithographic printing ink composition and a printed matter thereof. More specifically, the present invention relates to a lithographic printing ink composition capable of suppressing the generation of odor and further obtaining a printed matter having excellent scratch resistance.

In recent years, in the printing industry, awareness of environmental consideration for printed matter and printing workers has been increasing, and high environmentally friendly performance is also required for the ink used for the printing. In flat plate printing ink compositions used in offset printing, in response to these demands, replacement of highly volatile petroleum-based solvents with aroma-free solvents (solvents containing less than 1% by mass of aromatic components) and , Inks (Non-VOC inks) that do not substantially contain volatile organic compounds (VOCs) are being studied and developed (see Patent Documents 1 and 2). In particular, with the spread and expansion of the biomass mark (Japan Organic Resources Association), which is certified for environment-friendly products using biological resources, there is a need for non-VOC inks containing vegetable oil, which is a biomass material. Is getting stronger.

On the other hand, in the "oxidation polymerization type" drying method generally used in offset printing, the components in the lithographic printing ink composition applied to a printing substrate such as paper undergo oxidative polymerization by oxygen in the air and solidify.・ It dries. In the case of the above-mentioned Non-VOC ink containing a vegetable oil component, since the vegetable oil, which is the main component, is involved in the oxidative polymerization reaction, a printed matter having excellent film curability, scratch resistance, and paper surface gloss can be obtained. In the process of the oxidative polymerization reaction, the vegetable oil undergoes rancidification and deterioration, and a gaseous aldehyde compound is generated as a by-product. The emission of this aldehyde compound causes odor problems and printing troubles called gloss ghosts. In particular, formaldehyde, which is a kind of aldehyde compound, may be a causative substance that causes sick house syndrome, and the generation of aldehyde compound is an important problem to be solved from the viewpoint of environmental consideration for printing workers.

In order to solve the above problems, for example, Patent Document 3 discloses a method of using a catechin compound, a tannin compound, or the like having a specific structure as a deodorant. However, as a result of studies by the present inventors, it has been found that the deodorant may impair the emulsifying properties of the lithographic printing ink composition and cause phenomena such as ground stains.

Further, Patent Documents 4 to 5 disclose lithographic printing ink compositions containing a hydrazide compound and acetylacetone as compounds that reduce the emission of aldehyde compounds by chemical adsorption. However, the amount of vegetable oil contained in the lithographic printing ink composition specifically disclosed in Patent Document 4 is 25% by mass, and in Patent Document 5, it is only about 10% by mass. With these lithographic printing ink compositions, it is difficult to obtain printed matter with excellent film curability, scratch resistance, and paper gloss (see Examples for details), and it also goes against the market demand for environment-friendly products. Is.

As described above, the content of vegetable oil (and / or vegetable oil ester) is not excessively reduced, printing troubles such as background stains and gloss ghosts are not caused, odor generation can be suppressed, and scratch resistance is also excellent. It is hard to say that a lithographic printing ink composition capable of obtaining a printed matter has existed so far.

Japanese Unexamined Patent Publication No. 2004-204203 Japanese Unexamined Patent Publication No. 2005-60693 JP-A-2002-212484 Japanese Unexamined Patent Publication No. 2015-151481 Japanese Unexamined Patent Publication No. 2005-239923

The present invention has been made to solve the above problems, and an object of the present invention is to provide a printed matter which can suppress the generation of odor and has excellent scratch resistance without causing printing troubles such as background stains and gloss ghosts. It is an object of the present invention to provide a lithographic printing ink composition containing a vegetable oil and / or a vegetable oil ester which can be obtained.

As a result of diligent research by the present inventors in order to solve the above problems, the following compounds (A), binder resins (B), vegetable oils and / or vegetable oil esters that reduce the emission of aldehyde compounds by chemical adsorption ( A flat plate printing ink composition containing C) and a pigment (D) was found, and the present invention was completed.

That is, the present invention is a lithographic printing ink composition containing a compound that reduces the emission of an aldehyde compound by chemical adsorption, a binder resin, a vegetable oil and / or a vegetable oil ester (C), and a pigment (D).
The compound that reduces the emission of the aldehyde compound by chemisorption contains the compound (A) having an NH group as a partial structure.
The binder resin contains a rosin-modified phenolic resin (B).
It relates to a lithographic printing ink composition in which the content of the vegetable oil and / or the vegetable oil ester (C) is 40 to 55% by mass in the total amount of the lithographic printing ink composition.

The present invention also relates to the lithographic printing ink composition in which the compound (A) contains hydrazines.

The present invention also relates to a printed matter obtained by printing the lithographic printing ink composition on a base material.

INDUSTRIAL APPLICABILITY According to the present invention, a lithographic printing ink composition containing a vegetable oil and / or a vegetable oil ester can be obtained, which can suppress the generation of odor and have excellent scratch resistance without causing printing troubles such as background stains and gloss ghosts. It has become possible to provide things.

The lithographic printing ink composition of the present invention will be described in detail below. It should be noted that the present invention is not limited to the following embodiments, and includes modified examples implemented without changing the gist of the present invention. Unless otherwise specified, "parts" and "%" represent "parts by mass" and "% by mass".

As described above, the lithographic printing ink composition of the present invention (hereinafter, also simply referred to as “lithographic ink” or “ink”) is a compound that reduces the emission of aldehyde compounds by chemical adsorption, a binder resin, and vegetable oil and / or vegetable oil. By using the ester in combination, it is possible to obtain a printed matter in which the odor is suppressed without causing deterioration of scratch resistance, ground stains, gloss ghosts and other printing troubles without excessively reducing the content of vegetable oil. The principle that the problem of the present invention can be solved by the lithographic ink having the above structure will be described below. The following is an inference and does not limit the present invention in any way.

As described in the prior art, in the case of a flat plate ink containing a vegetable oil, the vegetable oil and / or the vegetable oil ester undergoes an oxidative polymerization reaction, and drying proceeds. At that time, in the process of the oxidative polymerization reaction, a gaseous aldehyde compound is generated as a by-product, and this aldehyde compound causes an odor.

Therefore, the flat plate ink composition of the present invention uses the compound (A) having an NH group as a partial structure as a compound that reduces the emission of the aldehyde compound by chemical adsorption.
The NH group contained in the structure of compound (A) reacts with the aldehyde group to form a bond. As a result, the odor can be reduced without reducing the amount of the vegetable oil and / or the vegetable oil ester, and further, the diffusion of the gaseous aldehyde compound can be suppressed and the gloss ghost can be improved.

Further, the lithographic ink composition of the present invention contains vegetable oil and / or vegetable oil ester (C) in an amount of 40 to 55% by mass based on the total amount of the lithographic ink composition. By increasing the amount of the vegetable oil and / or the vegetable oil ester (C) present in the lithographic ink composition to the above range, the film formed by the oxidative polymerization reaction can be strengthened, and the printed matter can be scratch-resistant. Improves sex. As described above, since the aldehyde compound is generated in the process of the oxidative polymerization reaction, there is a high possibility that odor and gloss ghost will be generated in the lithographic ink composition containing the above amount of vegetable oil and / or vegetable oil ester (C). However, in the case of the present invention, the aldehyde compound is chemically adsorbed by the compound (A) to suppress the occurrence of the above phenomenon. Further, although the details are unknown, the NH groups present in the structure of the compound (A) promote the oxidative polymerization reaction, so that the cross-linking of the vegetable oil and / or the vegetable oil ester (C) is uniformly and promptly carried out in the printed layer. As it progresses, further improvement in scratch resistance can be realized.

On the other hand, when the compound (A) is used, the viscosity of the lithographic printing ink composition at the time of printing decreases, and / or the compound (A) is adsorbed on the non-image portion of the printing plate, and the non-image portion There is a risk of soil pollution troubles occurring by making the ink lipophilic. Therefore, in the present invention, a rosin-modified phenolic resin (B) is further used as the binder resin. The carboxyl groups and hydroxyl groups present in the rosin-modified phenolic resin (B) and the nitrogen atoms present in the compound (A) are bonded to each other by hydrogen bonds, thereby increasing the viscosity of the ink and the non-image area. It is considered that the adsorption to the soil is suppressed and the soil stain resistance is improved. Further, the rosin-modified phenolic resin (B) is suitable from the viewpoint of particularly improving the scratch resistance of the printed matter.

As described above, in order to obtain a printed matter which can suppress the generation of odor and has excellent scratch resistance without causing printing troubles such as background stains and gloss ghosts, the composition of the lithographic printing ink composition of the present invention is used. Indispensable.

Subsequently, the main materials constituting the lithographic ink of the present invention will be described in detail below.

As described above, the compound used in the present invention for reducing the emission of the aldehyde compound by chemical adsorption includes the compound (A) having an NH group as a partial structure.
Examples of the compound (A) include amines, ureas, amides, imides, azoles, azolidins, hydrazines, semicarbazides, and derivatives thereof.
The content of the compound (A) is preferably 0.1 to 3.0% by mass, more preferably 1.0 to 2.0% by mass, based on the total amount of the lithographic ink. By keeping the content of the compound (A) within the above range, the aldehyde compound generated during the oxidative polymerization reaction is chemically adsorbed without being missed, and the effect of continuously reducing the odor can be obtained. Further, when the content is 0.1% by mass or more, the diffusion of the aldehyde compound is suitably suppressed and the gloss ghost is also eliminated. Further, by setting the content to 3.0% by mass or less, in the case of a solid deodorant, the pilling resistance on the printing machine is improved and the smoothness of the printed surface is maintained, so that the scratch resistance is also improved. It will improve again. Further, by binding to the rosin-modified phenolic resin (B), the viscosity of the ink becomes suitable, the adsorption of the printing plate to the non-image area can be suppressed, and the stain resistance can be improved.

Among the above, specific examples of amines include dodecylamine, tridecylamine, tetradecylamine, diamilamine, cyclohexylamine, naphthylamine, diethylene glycolamine, melamine, ammonium sulfamate, polyvinylamine, polyallylamine, melamine resin and the like. ..
Specific examples of ureas and amides include urea, ethylene urea, dicyandiamide, hexanediamide, and N-acetylacetamide.
Specific examples of imides include phthalimide, succinimide, maleimide, and glutarimide.
In addition, examples of the nitrogen-containing complex 5-membered ring compound (azoles, azolidines) include imidazole compounds, pyrazole compounds, triazole compounds, pyrrolidine compounds, and the like, specifically, 2-butylimidazole, 2-undecylimidazole, and the like. 3,5-Dimethylpyrazole, 2,4-dimethylimidazole, 3,5-dimethyl-1,2,4-triazole, 3,5-di-n-butyl-1,2,4-triazole, 2,5- Examples include dimethylpyrrolidine.
Examples of hydrazines include monohydrazide compounds and dihydrazide compounds. Specific examples thereof include propionic acid hydrazide, octanoic acid hydrazide, lauric acid hydrazide, palmitate hydrazide, stearate hydrazide, salicylate hydrazide, hydroxybenzoate hydrazide, and the like. Examples thereof include hydroxynaphthoic acid hydrazide, adipic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, succinic acid dihydrazide, dodecane dihydric acid dihydrazide, and isophthalic acid dihydrazide.
Examples of semicarbazides include 1,1-dimethylsemcarbazide, 1,4-diphenylsemcarbazide, and 4,4'-hexamethylenebis (1,1-dimethylsemcarbazide).
In addition, only one kind of the said compound may be used, or two or more kinds may be used in combination.

Among the above compounds, hydrazines are preferably used, dihydrazide compounds are more preferably used, and adipic acid dihydrazide and sebacic acid dihydrazide are particularly preferable.

The above compound may be used as it is, or may be supported on the surface of inorganic fine particles such as silica, alumina, titania, activated carbon, and zeolite.

The flat plate ink of the present invention contains a rosin-modified phenolic resin (B) as a binder resin. In order to preferably exhibit the effects of the present invention, the content of the rosin-modified phenolic resin (B) is preferably 15 to 50% by mass, more preferably 20 to 35% by mass, based on the total amount of the lithographic ink. ..

Further, from the viewpoint that by binding to the compound (A) to each other, the soil stain resistance can be suitably improved, and further, the generation of odor and gloss ghost can be suitably suppressed, the rosin with respect to the content of the compound (A) can be preferably suppressed. The ratio of the contents of the modified phenol resin (B) ((B) / (A)) is preferably 9 to 25, and particularly preferably 15 to 20.

As described above, the rosin-modified phenolic resin (B) is a resole-type phenol from the viewpoint of forming a hydrogen bond with the NH group existing in the structure of the compound (A) and improving the soil stain resistance. It is preferably manufactured using a resin.

Further, the flat plate ink of the present invention contains petroleum resin, alkyd resin, petroleum resin alkyd, ester gum, rosin alkyd resin, rosin ester resin, styrene maleic acid resin, and maleic acid as binder resins other than the rosin-modified phenol resin (B). The resin or a modified product of these resins may be used in combination with the rosin-modified phenolic resin (B). Further, only one kind of these binder resins may be used, or two or more kinds thereof may be used in combination.

As described above, the lithographic ink of the present invention contains vegetable oil and / or vegetable oil ester (C). In the present invention, the "vegetable oil" refers to triglyceride, which is an esterification reaction product of glycerin and a fatty acid, and monoglyceride and diglyceride obtained by a partial transesterification reaction thereof. The fatty acid may contain a saturated fatty acid.

The vegetable oil ester that can be used as the vegetable oil and / or the vegetable oil ester (C) is a fatty acid ester obtained by a partial transesterification reaction of the vegetable oil. Specifically, as fatty acids that bind to glycerin, saturated fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid, monovalent saturated fatty acids such as palmitooleic acid, oleic acid, and ellaic acid, linoleic acid, and γ-linoleic acid. , Alpha linoleic acid and the like, but are not limited to the above.

The content of the vegetable oil and / or the vegetable oil ester (C) is 40 to 55% by mass, more preferably 43 to 52% by mass, based on the total amount of the lithographic ink. By keeping the content of the vegetable oil and / or the vegetable oil ester (C) within the above range, the film strength after the coating film is dried becomes suitable, and the scratch resistance is improved. Further, when the content is 40% by mass or more, the permeability and leveling of the ink are improved, and the gloss of the printed matter is improved. Further, when it is 55% by mass or less, excessive generation of the aldehyde compound can be suppressed, and odor and gloss ghost can be reduced.

Further, from the viewpoint of obtaining an ink having all of odor, gloss ghost, stain resistance, and scratch resistance, the ratio of the content of the vegetable oil and / or the vegetable oil ester (C) to the content of the compound (A) ((( C) / (A)) is preferably 30 to 500.

The iodine value of the vegetable oil used in the present invention is not limited, but it is preferable to use one in the range of 50 to 120 mg / 100 mg. By keeping the iodine value within the above range, in addition to suppressing odor and gloss ghost, the amount of the drying accelerator added can be made suitable, and the drying property of the ink is improved. Furthermore, the stability of the ink on the printing machine can be ensured.

Further, it is particularly preferable to use a vegetable oil having an iodine value in the range of 50 to 120 mg / 100 mg and a vegetable oil having an iodine value of 150 mg / 100 mg or more in combination. By using a vegetable oil of 150 mg / 100 mg or more in combination, the film can be strengthened and the scratch resistance of the printed matter becomes suitable.

The iodine value is a value measured by the standard fat analysis test method (Japan Oil Chemists' Society), 2.3.4.1-1996 (Wiiss-cyclohexane method). Specifically, 0.15 g of the target vegetable oil is dissolved in 10 ml of cyclohexane, 25 ml of Wyeth solution is added, and the flask is left at room temperature in a dark place for about 1 hour. Then, titration is performed with a 0.1 mol / l sodium thiosulfate standard solution, and the iodine value is calculated from the amount of the sodium thiosulfate standard solution added dropwise until the end point is reached.

As the vegetable oils, palm oil, neem oil, sunflower oil, camellia oil, castor oil, rice bran oil (rice oil), soybean oil, capoc oil, poppy oil, sesame oil, large fuko oil, corn oil, niger oil, gentou oil, cotton seed oil. , Pepper oil, yuzu oil, etc., but are not limited to the above. Among the above, those having an iodine value of 50 to 120 mg / 100 mg are preferably selected, and among them, one or more selected from rice oil, rice bran oil, neem oil, and sesame oil are further selected from the viewpoint of scratch resistance. It is preferably selected, and rice bran oil is particularly preferably selected.

As the vegetable oil, a vegetable oil that has been used for producing foods and drinks and has been regenerated (hereinafter, also referred to as "regenerated vegetable oil") can be used. In the present invention, it is preferable that the vegetable oil contains a regenerated vegetable oil. The reason is that by adjusting the conditions of the regeneration treatment, the iodine value can be artificially and easily kept in the above-mentioned suitable range, and by reducing the water content of the recycled vegetable oil, it is contained together with water. It is possible to remove impurities that adversely affect the stability and printability of the ink on the printing machine. The water content of the regenerated vegetable oil is preferably 0.3% by mass or less.

In the present invention, 50% by mass or more of the vegetable oil and / or the vegetable oil ester (C) is vegetable oil from the viewpoint of obtaining a printed matter having high film strength and excellent scratch resistance and suppressing the occurrence of ground stains. Is preferable, and it is particularly preferable that 80% by mass or more is a vegetable oil.

The lithographic ink of the present invention contains a pigment (D). As the pigment, conventionally known organic pigments and / or inorganic pigments can be arbitrarily used. Further, the extender pigment may be contained as the pigment. The blending amount of the pigment (D) in the present invention (however, the blending amount of the pigment (D) does not include the blending amount of the extender pigment) does not impair the effect of the present invention, and the color development and sharpness of the printed matter are not impaired. It is preferable that the amount is such that Specifically, it is preferably 10 to 40% by mass, and particularly preferably 15 to 35% by mass, based on the total amount of lithographic ink.

Further, the lithographic ink of the present invention may contain a petroleum-based solvent. As the petroleum-based solvent, the content of aromatic hydrocarbon is 1% or less, the aniline point is 60 to 130 ° C., preferably 80 to 100 ° C., and the boiling point is 240 to 400 ° C., preferably 270 to 350 ° C. Petroleum-based solvents in the range of can be preferably used. The blending amount of the petroleum-based solvent in the present invention is preferably an amount that can ensure the gloss, dryness, and scratch resistance of the printed matter without impairing the effect of the present invention. Specifically, it is preferably 20% by mass or less, more preferably 10% by mass or less, based on the total amount of lithographic ink.

Further, the lithographic ink of the present invention may contain a gelling agent. Specific examples of the gelling agent include an aluminum chelate compound, a metal soap, an alkanolamine, and the like, and the blending amount thereof is preferably 1% by mass or less based on the total amount of the flat plate ink.

Further, in the lithographic ink of the present invention, in addition to the above components, various additives such as existing emulsifiers, emulsion inhibitors, scratch resistant agents, set-off inhibitors, drying accelerators, antioxidants, etc. are appropriately used. be able to. The total amount of the compounding amount is preferably 10% by mass or less with respect to the total amount of lithographic ink.

The lithographic ink of the present invention can be suitably used for any of the heat set type, oxidative polymerization type, and permeation drying type drying methods. Above all, since the lithographic ink of the present invention contains a certain amount of vegetable oil and / or vegetable oil ester (C), it can be suitably used particularly in offset printing having an oxidative polymerization type drying method. Further, the printing base material used is not particularly limited, and by using a general printing paper such as coated paper, a printed matter in which the effects of the present invention are suitably exhibited can be obtained. ..

Hereinafter, the present invention will be described in more detail with reference to Examples, but the embodiments of the present invention are not limited to these examples.

(Production example of gel varnish 1-9)
45 parts of rosin-modified phenolic resin (Hariphenol 512 manufactured by Harima Kasei Group Co., Ltd.) and rice bran oil 54 in a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, a gas introduction pipe, and a thermometer. After charging the part and one part of the gelling agent (ALCH manufactured by Kawaken Fine Chemicals Co., Ltd.), heat to 190 ° C while introducing nitrogen gas, and heat and stir for 1 hour while maintaining the temperature. As a result, gel varnish 1 was produced.
Further, gel varnishes 2 to 9 were produced in the same manner as in the case of gel varnish 1 except that the materials and amounts charged in the four-necked flask were changed as shown in Table 1 below.

The details of the materials used in Table 1 above are as follows.
Rosin ester resin: Harima Chemicals Group Co., Ltd. Hariester KT-3
AF-5: AF Solvent No. 5 manufactured by JXTG Energy Co., Ltd.

(Manufacturing of lithographic inks 1 to 30)
The gel varnish produced above, a compound that reduces the emission of aldehyde compounds by chemical (or physical) adsorption, vegetable oil and / or vegetable oil ester, petroleum solvent, drying accelerator (cobalt metal dryer), and carbon pigment. (Mitsubishi Carbon MA7 manufactured by Mitsubishi Chemical Co., Ltd.) is mixed with the compositions shown in Table 2 below, and then the flat plate inks 1 to 30 are dispersed by using three rolls according to a conventional method. Obtained.

Of the materials used in Table 2 above, details of materials not listed in Table 1 and above are as follows.
Kesmon NS-231: Dihydrazide adipic acid supported on alumina, manufactured by Toa Synthetic Co., Ltd. Kesmon NS-103: Dihydrazide adipate supported on zeolite manufactured by Toa Synthetic Co., Ltd. Chemcatch H-6000: Otsuka Chemical Co., Ltd. Dihydrazide Kiracle AL-07, manufactured by Nikka Kagaku Co., Ltd., silica compound A having an amino group on the surface: Diethylene glycol amine supported on silica (Japanese Patent Laid-Open No. 2013-75067) Deodorant composition described in Example 1)

The lithographic inks 1 to 30 produced above were evaluated as shown below. The standard of evaluation was lithographic ink 24, and a comparison was made with this. The evaluation results are as shown in Table 2.

<Printing conditions>
Printing machine: LITHRONE26 (manufactured by Komori Corporation)
Paper: Pearl Coat N Paper (manufactured by Mitsubishi Paper Mills Limited)
Damping water: Aqua Unity C 2.0% tap water diluent (manufactured by Toyo Ink Co., Ltd.)
Water volume value: 20 points (However, in the ground pollution resistance test, it was as described below)
Printing speed: 6000 sheets / hour version: SUPERIA XP-F (manufactured by FUJIFILM Global Graphic Systems Co., Ltd.)
Number of prints: 2000 (However, in the background stain resistance test, it was as described below)

(Odor test)
In the above printing machine, a solid paper surface (2000th sheet) printed so that the paper surface density is 1.8 is cut into 1 cm x 5 cm on Pearl Coated N paper (coated paper manufactured by Mitsubishi Paper Mills Limited). , Enclosed in a 200 cc glass bottle. After storing at 40 ° C. for 24 hours, the lid of the glass bottle was opened and the odor was evaluated by a sensory test. Based on the evaluation criteria shown in Table 3 below, the evaluation was made on a four-point scale, with 2 or more being considered practically preferable. The paper surface density is a value measured using X-Rite eXact (manufactured by X-Rite Co., Ltd.) under the conditions of CIESstatusE and a viewing angle of 2 °.

(Gloss ghost test)
In the above printing machine, a solid paper surface (2000th sheet) printed so that the paper surface density is 1.8 on pearl coated N paper (coated paper manufactured by Mitsubishi Paper Mills Limited) is dried at room temperature for 12 hours. Then, a solid pattern was printed on the back side of the paper surface in the same manner as the front surface. Then, after storing at room temperature for 24 hours, the presence or absence of a gloss difference on the printed surface printed later was visually confirmed. Based on the evaluation criteria shown in Table 4 below, the evaluation was made on a 4-point scale, and 2 or more was considered to be practically preferable. The paper surface concentration is a value measured under the same conditions as the odor test.

(Ground stain resistance test)
First, the water amount value was set to 20 points in the printing machine, and 200 copies of each of the lithographic inks were printed. After printing, when the printed matter was visually observed and no stain was found, the water amount value was lowered by 1 point, and 200 copies were printed again. By repeating the above, the water amount value when the printed matter was found to be dirty was confirmed. Based on the evaluation criteria shown in Table 5 below, the evaluation was made on a 4-point scale, and 2 or more was considered to be practically preferable. The paper surface concentration is a value measured under the same conditions as the odor test.

(Abrasion resistance test)
Using the above printing machine, the color was developed on Pearl Coated N Paper (coated paper manufactured by Mitsubishi Paper Mills Limited) so that the paper surface density was 1.8. After color development, it is dried for 24 hours, and a blank paper (Pearl Coat N Paper manufactured by Mitsubishi Paper Mills Limited) is applied to the printing surface using a Gakushin type abrasion resistance tester, and a load of 0.2 kg is applied to 20. I rubbed back and forth. After the test, the degree of adhesion of the ink to the blank paper applied to the printed surface was visually observed. The evaluation results were based on the evaluation criteria shown in Table 6 below, and were evaluated as a four-stage relative evaluation of the lithographic inks 1 to 30, and 2 or more were considered to be practically preferable. The paper surface concentration is a value measured under the same conditions as the odor test.

As is clear from Table 2, when the lithographic printing ink composition having the constitution of the present invention is used, gloss ghost, deterioration of scratch resistance and ground are observed even under the condition containing a certain amount of vegetable oil and / or vegetable oil ester. It was possible to obtain a printed matter in which the generation of odor was suppressed without causing printing troubles such as stains.

On the other hand, in lithographic inks 22 to 25, which do not contain compound (A) as a compound that reduces the emission of the aldehyde compound by chemisorption, deterioration of odor, gloss ghost, and stain resistance was confirmed. Further, in the lithographic inks 26, 29 to 30, the content of the vegetable oil and / or the vegetable oil ester (C) is less than 40% by mass in the total amount of the lithographic printing ink composition even if the compound (A) is contained. Although the odor and gloss ghost could be reduced, the printed matter was inferior in scratch resistance. The lithographic ink 29 is a reproduction of Example 8 of Patent Document 4, and the lithographic ink 30 is a reproduction of Example 1 of Patent Document 5.

Furthermore, the lithographic ink 27, which contains more than 55% by mass of the vegetable oil and / or the vegetable oil ester (C) in the total amount of the lithographic printing ink composition, cannot completely improve the odor and gloss ghost, and the binder resin. It was confirmed that the lithographic ink 28, which does not contain the rosin-modified phenolic resin (B), deteriorates the scratch resistance.

Claims (3)

A lithographic printing ink composition containing a compound that reduces the emission of an aldehyde compound by chemical adsorption, a binder resin, a vegetable oil and / or a vegetable oil ester (C), and a pigment (D).
The compound that reduces the emission of the aldehyde compound by chemisorption contains the compound (A) having an NH group as a partial structure.
The binder resin contains a rosin-modified phenolic resin (B).
A lithographic printing ink composition in which the content of the vegetable oil and / or the vegetable oil ester (C) is 40 to 55% by mass in the total amount of the lithographic printing ink composition. The lithographic printing ink composition according to claim 1, wherein the compound (A) contains hydrazines. A printed matter obtained by printing the lithographic printing ink composition according to claim 1 or 2 on a base material.