JPH051253A - Printing ink - Google Patents

Abstract

PURPOSE:To provide an oxidatively polymerizing printing ink which contains only a small amt. of a solvent, has no problem with a solvent vapor. and enables printing on an object made of a synthetic resin. CONSTITUTION:A printing ink comprising a colorant and an oxidatively polymerizing resin varnish which consists mainly of a drying or semidrying oil wherein 0.5-2. 0 unsatd. carboxylic acid components have been substd. by satd. or unsatd. carboxylic acids having less carbon atoms than said acid components or wherein 0.5-2.0 unsatd. carboxylic acid components have undergone transesterification with satd. or unsatd. alcohols.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing ink, and more specifically, it is an excellent printing ink free from the problem of volatilized solvent and free from problems such as waviness when printed on synthetic paper or synthetic film. For the purpose of providing.

[0002]

2. Description of the Related Art Conventionally, printing inks, particularly oxidative polymerization type printing inks, are mainly composed of a coloring agent which is a pigment, a resin varnish which is a vehicle, an ink solvent and an additive such as a drying aid, and has a liquid absorbing property. Used to print some paper.
As the varnish resin for these conventional oxidative polymerization type printing inks, natural or synthetic oxidative polymerization type resins are used, and various ink solvents are used in order to adjust the viscosity, tack, flow, etc. of the ink. Used in proportions that make up weight percent. In addition to adjusting the viscosity of the ink solvent, the solvent is absorbed by the paper after printing, contributing to the acceleration of drying of the printing ink by improving the concentration of the printing ink on the paper.

[0003]

[Problems to be solved by the invention] However,
When printing with the above conventional printing ink, the solvent in the ink is volatilized into the working atmosphere during drying, which eventually causes air pollution.Therefore, the printing factory is required to have equipment to prevent the solvent from being released into the atmosphere. It came to be like. This equipment burden is unbearable in small and medium-sized printing plants. In addition, there is a tendency that the oxidation polymerization type ink is used for a printing material having a low liquid absorbing property such as a synthetic paper made of a synthetic resin or a plastic film (sheet) as a printing material. However, there is a problem in that the material to be printed is corrugated during or after printing due to its low liquid absorbability, swelling of the synthetic resin due to liquid absorption, etc., which makes subsequent handling difficult. Therefore, an object of the present invention is to provide an oxidative polymerization type printing ink which has a low solvent content, does not have the problem of a volatile solvent, and can be printed on a synthetic resin printing material.

[0004]

The above object can be achieved by the present invention described below. That is, the present invention is a printing ink containing a colorant and an oxidative polymerization type resin varnish, wherein the main component of the varnish resin is 0.5 to 0.5% of the drying oil or the semi-drying oil.
Printing inks characterized in that 2.0 unsaturated carboxylic acid components are replaced by saturated or unsaturated carboxylic acids having a lower number of carbons, and among the drying or semi-drying oils described above. A printing ink characterized in that 0.5 to 2.0 unsaturated carboxylic acid components are transesterified with a saturated or unsaturated alcohol.

[0005]

When a low molecular weight alcoholysis compound or carboxylis compound of a drying oil or a semi-drying oil is used as the main component of the varnish resin of the printing ink, the resulting mixture itself has a low viscosity, so that it is required for adjusting the viscosity. It is possible to reduce or eliminate unnecessary ink solvent.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. The main component of the varnish resin, which characterizes the present invention mainly, is a low molecular weight alcoholic compound or carboxylis compound of a drying oil or a semi-drying oil. Examples of the drying oil and semi-drying oil used for these include, for example,
Flaxseed oil, soybean oil, safflower oil, cinnamon oil, Japanese kiri oil, sunflower oil, eno oil, hemp oil, tall oil, sesame oil, wheat germ oil, corn oil, rapeseed oil, rice bran oil conventionally used for printing inks. Examples thereof include oil, dehydrated castor oil, cottonseed oil, squid oil, fish oil, whale oil, and various modified products thereof. These drying oils and semi-drying oils are triglycerides of glycerin, and their acid components are often unsaturated fatty acids having 14 or more carbon atoms.

In the present invention, 0.5 to 2.0, preferably 0.8 to 1.5, of the three acid components of the above-mentioned conventional drying oil or semi-drying oil is added to carbon. Substitution with a few saturated or unsaturated carboxylic acids or transesterification with saturated or unsaturated alcohols. If the acid substitution or transesterification is less than 0.5, the effect of reducing the solvent is insufficient, while if the acid substitution or transesterification exceeds 2.0, problems occur in the drying property and film strength. , And the number is an average value). Examples of the saturated or unsaturated fatty acids include, as alkanoic acids, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid. Acids, tridecylic acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid, nonadecyl acid, arachidic acid, behenic acid and the like can be mentioned.

Examples of the branched monoalkanoic acid include isobutyric acid, α-methylbutyric acid, isovaleric acid, trimethylpropanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 4-isocaproic acid and 2-ethylhexanoic acid. , 4-
Propylpentanoic acid, 4-ethylpentanoic acid, 2-methyldecanoic acid, 3-methyldecanoic acid, 4-methyldecanoic acid, 5-methyldecanoic acid, 6-methyldecanoic acid, 7-methyldecanoic acid, 9-methyldecanoic acid, 6-ethylnonanoic acid, 5-propyloctanoic acid, 3-methylhendecanoic acid, 6-propylnonanoic acid, 2-methyldodecanoic acid, 3
-Methyldodecanoic acid, 4-methyldodecanoic acid, 5-methyldodecanoic acid, 11-methyldodecanoic acid, 7-propyldecanoic acid, 2-methyltridecanoic acid, 12-methyltridecanoic acid, 2-methyltetradecanoic acid, 4 -Methyltetradecanoic acid, 13-methyltetradecanoic acid, 14-methylpentadecanoic acid, 2-ethyltetradecanoic acid, 15-
Methylhexadecanoic acid, 2-propyldecanoic acid, 2-ethylhexadecanoic acid, 14-ethylhexadecanoic acid, 1
4-methylheptadecanoic acid, 15-methylheptadecanoic acid, 16-methylheptadecanoic acid, 2-butyltetradecanoic acid, 2-methyloctadecanoic acid, 3-methyloctadecanoic acid, 4-methyloctadecanoic acid, 5-methyloctadecanoic acid , 6-methyloctadecanoic acid, 7-methyloctadecanoic acid, 8-methyloctadecanoic acid, 9-methyloctadecanoic acid, 10-methyloctadecanoic acid, 11-
Methyl octadecanoic acid, 14-methyl octadecanoic acid,
15-methyloctadecanoic acid, 16-methyloctadecanoic acid, 17-methyloctadecanoic acid, 15-ethylpentadecanoic acid, 3-methylnonadecanoic acid, 2-ethyloctadecanoic acid, 2-methylicosanoic acid, 2-propyloctadecanoic acid, 2-butyloctadecane Acid, 2-methyldocosanoic acid, 10-methyldocosanoic acid, 2-pentyloctadecanoic acid, 2-methyltricosanoic acid, 3-methyltricosanoic acid, 22-methyltricosanoic acid, 20-ethyldocosanoic acid, 18-propylhexaicosane Acid, 2-hexyl octadecanoic acid, 12-hexyl octadecanoic acid,
2-methyltetracosanoic acid, 3-methyltetracosanoic acid, 6-methyltetracosanoic acid, 10-methyltetracosanoic acid, 12-methyltetracosanoic acid, 14-methyltetracosanoic acid, 18-methyltetracosanoic acid, 23 -Methyl tetracosanoic acid, 2-heptyl octadecanoic acid, 9
-Octylheptadecanoic acid, 24-methylheptacosanoic acid, 2-ethyltetracosanoic acid, 2-butyldocosanoic acid, 2-hexylcosanoic acid, 2-octyloctadecanoic acid, 2-decylhexadecanoic acid, 2-methylhexacosanoic acid, 10 -Methylhexacosanoic acid, 2-nonyloctadecanoic acid, 2-decyloctadecanoic acid, 2-hendecyloctadecanoic acid, 2-dodecyloctadecanoic acid, 33-
Methyl tetratricontanoic acid etc. are mentioned.

As the branched polyalkanoic acid, for example, 2
-Butyl-5-methylpentanoic acid, 2-isobutyl-5
-Methylpentanoic acid, 2,3-dimethylnonanoic acid, 4,
8-dimethylnonanoic acid, 2-butyl-5-methylhexanoic acid, 4,4-dimethyldecanoic acid, 2-ethyl-3-methylnonanoic acid, 2,2-dimethyl-4-ethyloctanoic acid, 2-propyl-3 -Methylnonanoic acid, 2,2-dimethyldodecanoic acid, 2,3-dimethyldodecanoic acid, 4,1
0-dimethyldodecanoic acid, 2-butyl-3-methylnonanoic acid, 2-butyl-2-ethylnonanoic acid, 3-ethyl-
3-Butylnonanoic acid, 4-butyl-4-ethylnonanoic acid, 3,7,11-trimethyldodecanoic acid, 2,2-dimethyltetradecanoic acid, 3,3-dimethyltetradecanoic acid, 4,4-dimethyltetradecanoic acid, 2- Butyl-2
-Pentylheptanoic acid, 2,3-dimethyltetradecanoic acid, 4,8,12-trimethyltridecanoic acid, 14,1
4-dimethylpentadecanoic acid, 3-methyl-2-peptylnonanoic acid, 2,2-dipentylheptanoic acid, 2,2-
Dimethylhexadecanoic acid, 2-octyl-3-methylnonanoic acid, 2,3-dimethylheptadecanoic acid, 2,2-dimethyloctadecanoic acid, 2,3-dimethyloctadecanoic acid, 2,4-dimethyloctadecanoic acid, 3,3- Dimethyl octadecanoic acid, 2-butyl-2-heptylnonanoic acid and the like can be mentioned.

Examples of the straight chain alkenoic acid include acrylic acid, crotonic acid, isocrotonic acid, acetovinyl acid,
β-ethylacrylic acid, β-pentenoic acid, acetoallylic acid, β-propylacrylic acid, 3-hexenoic acid, 4-hexenoic acid, 5-hexenoic acid, 2-heptenoic acid, 3-heptenoic acid, 5-heptenoic acid, 6-heptenoic acid, 2-octenoic acid (cis), 2-octenoic acid (trans), 3-octenoic acid, 2-nonenoic acid (cis), 2-nonenoic acid (trans), 3-
Nonenoic acid, 2-decenoic acid, 4-decenoic acid, caproleic acid, 9-undecylenic acid, 10-undecylenic acid, 2-
Lauroleic acid, Lindelic acid, 5-lauroleic acid, 1
1-lauroleic acid, 2-tridecenoic acid, 12-tridecenoic acid, tsuzuic acid, 5-myristoleic acid, myristoleic acid, 2-pentadecenoic acid, 14-pentadecenoic acid, 2
-Palmitoleic acid, 7-palmitoleic acid, zomarinic acid, trans-9-palmitoleic acid, 2-heptadecenoic acid, petroselinic acid, petroceredic acid, oleic acid, elaidic acid, bassenic acid, codonic acid, gondonic acid, trans-gondoin Acid, 11-docosenoic acid (c
is), erucic acid, brassic acid and the like.

Examples of branched monoenoic acids include α
-Methylacrylic acid, 2-methyl-2-butenoic acid (cis)
, 2-methyl-2-butenoic acid (trans), 3-methyl-
2-butenoic acid, 2-methyl-2-pentenoic acid (trans),
4-methyl-3-pentenoic acid, 2-methyl-2-hexenoic acid (cis), 2-methyl-2-hexenoic acid (trans), 2
-Methyl-2-heptenoic acid (trans), 3-methyl-2-
Nonenoic acid, 5-methyl-2-nonenoic acid, 5-methyl-2
-Hendecenoic acid, 2-methyl-2-dodecenoic acid, 5-methyl-2-tridecenoic acid, 2-methyl-9-octadecenoic acid, 2-ethyl-9-octadecenoic acid, 2-propyl-9-octadecenoic acid, 2 -Methyl-2-icosenoic acid,
2-methyl-2-hexacosenoic acid, 3,4-dimethyl-
3-pentaenoic acid, 5,9-dimethyl-2-decaenoic acid, 2,5-dimethyl-2-heptadecaenoic acid, 2,2
-Dimethyl-11-icosaenoic acid, 2,4-dimethyl-
13-n-amyl-2-icosaenoic acid, 2,4,6-trimethyl 2-tetracosaenoic acid and the like can be mentioned.

Other acids include, for example, 2,4-pentadienoic acid, sorbic acid, trans-8 and trans-10.
-Octadecadienoic acid, cis-9, cis-12-octadecadienoic acid, trans-9, trans-12-octadecadienoic acid, cis-9, trans-11-octadecadienoic acid, trans-10, cis -12-octadecadienoic acid, cis-9, cis-11-octadecadienoic acid,
Cis-10, cis-12-octadecadienoic acid, trans-10, trans-12-octadecadienoic acid, * trans-9, trans-11-octadecadienoic acid, trans-8, trans-10-octadeca Dienoic acid, *
Trans-9, trans-11-octadecadienoic acid,
Cis-9, trans-11, trans-13-octadecatrienoic acid, trans-9, trans-11, trans-13-octadecatrienoic acid, cis-9, cis-1
1, trans-13-octadecatrienoic acid, cis-
9, cis-12, cis-15-octadecatrienoic acid,
Trans-9, trans-12, trans-15-octadecatrienoic acid, trans-10, trans-12,
Trans-14-octadecatrienoic acid, 9,11,1
3,15-octadecatraenoic acid, 2,2-dimethylcis-9, cis-12-octadecadienoic acid and the like can be mentioned. Examples of the method of substituting the desired number of acid components of triglyceride with the above lower acid include a method of heating triglyceride and a lower acid under normal pressure or under pressure in the absence of a catalyst or in the presence of an acid catalyst. It may be a method.
Although a new acid is liberated by the above substitution, at least a part of the free acid, for example, 10 to 100 mol% is esterified by adding a suitable alcohol to the liberated acid. Can be done.

Further, when the drying oil or the semi-drying oil is subjected to alcoholysis, an example of the saturated or unsaturated alcohol is 1
-As the alkanol, for example, 1-hexanol (caproyl), 1-heptanol, 1-octanol (caprylyl), 1-nonanol (nonyl), 1-decanol (capryl), 1-undecanol, 1-dodecanol (lauryl), 1 -Tridecanol, 1-tetradecanol (myristyl), 1-pentadecanol, 1-hexadecanol (cetyl), 1-heptadecanol, 1
-Octadecanol (stearyl), 1-nonadecanol, 1-icosanol (araquinyl), 1-henicosanol, 1-docosanol and the like can be mentioned.

Examples of 2-alkanol include 2-
Hexanol, 2-heptanol, 2-octanol,
2-nonanol, 2-decanol, 2-undecanol, 2-dodecanol, 2-tridecanol, 2-tetradecanol, 2-pentadecanol, 2-hexadecanol, 2-heptadecanol, 2-octadecanol, 2-nonadecanol, 2-icosanol, etc. are mentioned. Examples of β, γ unsaturated primary alcohols include 2-hexen-1-ol (cis) and 2-hexene-
1-ol (trans), 2-heptene-1-ol *, 2
-Octen-1-ol *, 2-dodecen-1-ol *, 2-undecen-1-ol (trans), 2-tetradecen-1-ol (cis), 2-pentadecen-1-ol (cis), 2-hexadecen-1-ol (cis), 2
-Heptadecen-1-ol (cis), 2-octadecen-1-ol (cis), 2-octadecen-1-ol (t)
rans) and the like.

Examples of the terminal unsaturated alcohol include, for example,
5-hexene-1-ol, 6-hepten-1-ol, 8-nonen-1-ol, 10-undecen-1-
All, 11-dodecen-1-ol, 12-tridecen-1-ol, 15-hexadecen-1-ol and the like can be mentioned. Other unsaturated long-chain alcohols include:
For example, oleyl alcohol, elaidyl alcohol,
Linoleyl alcohol, linolenyl alcohol, eleostearyl alcohol (α), eleostearyl alcohol (β), ricinoyl alcohol, and substituents (R)
Benzyl alcohol R-Ph-, which may be substituted with
Examples include aromatic alcohols represented by CH ₂ OH (R = H, CH ₃ , C ₂ H ₅ , alkyl groups such as C ₃ H _{7 and the} like). Examples of the method for alcoholysis with the alcohol include, for example, a method of heating triglyceride and alcohol with no catalyst, preferably in the coexistence of an acid catalyst or an alkali catalyst, and heating under normal pressure or pressure, but other methods may be used. Good. Further, due to the above-mentioned alcoholysis, free hydroxyl groups are generated in glycerin, but it is possible to esterify at least a part of the hydroxyl groups, for example, 10 to 100 mol% by adding an appropriate carboxylic acid to the hydroxyl groups. I can.

In the present invention, such a modified oil may be used as the entire oxidative polymerization type resin of the varnish of the printing ink, or may be used in combination with a conventionally known oxidization polymerization type resin. When used in combination with a conventionally known oxidation polymerization type resin,
Above 10% by weight of the modified oil in the total oxidation polymerization type resin,
It is preferable to occupy 30% by weight or more, and 1
If the amount used is less than 0% by weight, the effect of reducing the solvent, which is the intended purpose of the present invention, is insufficient. As the conventionally known oxidation-polymerizable resin that can be used in combination, in addition to the drying oil and / or the semi-drying oil as described above, any known oxidation-polymerizable resin that has been conventionally used as a varnish resin may be used. I can. The colorant is a pigment used in conventional printing inks, and any conventionally known pigment can be used as it is as a colorant for the printing ink of the present invention. Also, the amount thereof may be the same as that of the conventionally known printing ink, for example,
A proportion of about 10 to 40 parts by weight in 100 parts by weight of printing ink is common.

As the dryer, cobalt, manganese,
Naphthenic acid of polyvalent metal such as cerium, zirconium, lead, iron, zinc, copper, vanadium, barium, calcium,
Octyl acid, resin acids, oil-soluble carboxylic acids such as tall oil fatty acids, salts of resin acids, and the like, and these dryers can be used in an amount of about 0.005 to 0.
It is generally used in a proportion of 5% by weight. The printing ink of the present invention may contain an ink solvent, a leveling improver, a thickener, an anti-skinning agent, and other conventionally known additives in addition to the above-mentioned colorant, oxidative polymerization type resin and dryer. For example, the ink solvent is added to modify the viscosity, consistency, flow, etc. of the ink,
Any of various organic solvents conventionally used for printing inks, such as light oil, spindle oil, various ink solvents, machine oil and the like can be used. The usage is
The amount is generally less than about 10 parts by weight in 100 parts by weight of the printing ink, preferably 0 to 5 parts by weight.
The manufacturing method itself of the printing ink of the present invention as described above may be a conventionally known method.

[0018]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the text, parts and% are based on weight unless otherwise specified. Example 1 23 parts of 880 parts of soybean oil and 268 parts of oleyl alcohol.
By heating at 0 ° C. for 8 hours, a modified oil having an average degree of substitution of 1.0 was obtained. Example 2 876 parts of linseed oil and 108 parts of benzine alcohol were azeotropically dehydrated in xylene, and then 5 parts of sodium methoxide were added. The mixture was heated at 180 ° C. for 6 hours and washed with water to obtain a modified oil having an average degree of substitution of 1.0. Example 3 23 parts of 876 parts of linseed oil and 402 parts of oleyl alcohol
By heating at 0 ° C. for 8 hours, a modified oil having an average substitution degree of 1.5 was obtained.

Example 4 880 parts of soybean oil and 200 parts of lauric acid were mixed at 230 ° C. for 6 hours.
After heating for an hour, a modified oil having an average degree of substitution of 1.0 was obtained. Example 5 876 parts of linseed oil and 172 parts of decanoic acid
After heating for an hour, a modified oil having an average degree of substitution of 1.0 was obtained. Example 6 876 parts of linseed oil and 258 parts of decanoic acid
After heating for an hour, a modified oil having an average degree of substitution of 1.5 was obtained.

Example 7 500 parts of the modified oil of Example 1 and 500 parts of phenol-modified rosin having a softening point of 163 ° C. and an acid value of 22.6 were heated to 200 ° C.
It was heated and melted for 1 hour to obtain a varnish. 700 parts of this varnish and 200 parts of Disazo Yellow were mixed and kneaded with a three-roll mill, 5 parts of manganese octylate having a manganese content of 8%, 80 parts of the modified oil of Example 1, 10 parts of Nisseki # 0 solvent and ethyl acetate. 10 parts of cellosolve were mixed to obtain an offset printing ink of the present invention having an incometer tack value (400 rpm.) Of 9.8. Example 8 400 parts of the modified oil of Example 2 and 500 parts of phenol-modified rosin having a softening point of 163 ° C. and an acid value of 22.6 are heated to 200 ° C.
It was heated and melted for 1 hour to obtain a varnish. 700 parts of this varnish and 200 parts of phthalocyanine blue were mixed and kneaded with a three-roll mill to give 5 parts of manganese octylate having a manganese content of 8%.
Parts, 100 parts of modified oil of Example 2 and ethyl cellosolve 1
0 parts were mixed, and the tack value of the incometer (400 rp
m. ) 9.8 inventive offset printing inks were obtained.

Example 9 400 parts of the modified oil of Example 3, 500 parts of phenol-modified rosin having a softening point of 163 ° C. and an acid value of 22.6 and Nisseki # 0.
50 parts of solvent was heated and dissolved at 200 ° C. for 1 hour to obtain a varnish. 700 parts of this varnish and 20 carbon blacks
Mix 0 parts with 3 rolls and knead meat, manganese content 8%
5 parts of manganese octylate, 70 parts of the modified oil of Example 3,
Nisseki # 5 solvent 10 parts and cellosolve acetate 1
0 parts were mixed, and the tack value of the incometer (400 rp
m. ) A 9.6 offset printing ink of the invention was obtained. Example 10 500 parts of the modified oil of Example 4, 400 parts of phenol-modified rosin having a softening point of 163 ° C. and an acid value of 22.6, and Nisseki # 5.
50 parts of solvent was heated and dissolved at 230 ° C. for 1 hour, and 50 parts of butyl carbitol was added to obtain a varnish. 700 parts of this varnish and 200 parts of Disazo Yellow were mixed and kneaded with a three-roll mill, 5 parts of manganese octylate having a manganese content of 8% and 90 parts of the modified oil of Example 4 were mixed, and the tack value of the incometer ( An offset printing ink of the invention of 400 rpm) 9.8 was obtained.

Example 11 400 parts of the modified oil of Example 5, 500 parts of phenol-modified rosin having a softening point of 168 ° C. and an acid value of 23.2 and Nisseki # 0.
100 parts of solvent was heated and dissolved at 220 ° C. for 1 hour to obtain a varnish. 700 parts of this varnish and 200 parts of Brilliant Carmine 6B were mixed and kneaded with a triple roll, and 5 parts of manganese octylate having a manganese content of 8%, 20 parts of Nisseki # 0 solvent and 10 parts of castor oil fatty acid were mixed to form a parakeet. An offset printing ink of the present invention having a tack value (400 rpm.) On a meter of 9.6 was obtained. Example 12 300 parts of modified oil of Example 6, 500 parts of phenol-modified rosin having a softening point of 165 ° C. and an acid value of 23.6, and Nisseki # 5.
100 parts of solvent was heated and melted at 260 ° C. for 1 hour to obtain a varnish. 700 parts of this varnish and 200 parts of phthalocyanine blue were mixed and kneaded with a triple roll, and mixed with 5 parts of manganese octylate having a manganese content of 8%, 10 parts of Nisseki # 0 solvent, and 5 parts of ethylene oxide adduct of nonylphenol. The incometer tack value (400 rp
m) An offset printing ink of the invention of 9.8 was obtained.

Comparative Example 1 400 parts of linseed oil and 100 parts of Nisseki # 5 solvent, phenol-modified rosin 5 having a softening point of 163 ° C. and an acid value of 22.6
00 parts were melted by heating at 230 ° C. for 1 hour to obtain a varnish.
700 parts of this varnish and 200 parts of Disazo Yellow were kneaded and kneaded with a triple roll, and 5 parts of manganese octylate having a manganese content of 8%, 90 parts of Nisseki # 5 solvent and 10 parts of ethyl cellosolve were mixed, An offset printing ink having a tack value of a meter (400 rpm) of 10.1 was obtained. Comparative Example 2 400 parts of polymerized linseed oil (Gardner viscosity X / Y) and 200 parts of Nisseki # 0 solvent, softening point of 163 ° C. and acid value of 2
400 parts of phenol-modified rosin of 2.6 was heated and dissolved at 200 ° C. for 1 hour to obtain a varnish. 700 parts of this varnish and 200 parts of phthalocyanine blue were kneaded and kneaded with a triple roll to form 5 parts of manganese octylate having a manganese content of 8%.
50 parts of linseed oil, 40 parts of Nisseki # 0 solvent and 10 parts of ethyl cellosolve were mixed to obtain an offset printing ink having a tack value (400 rpm) of an incometer of 9.9.

Comparative Example 3 400 parts of polymerized linseed oil (Gardner viscosity G / H), 200 parts of linseed oil, and 400 parts of phenol-modified rosin having a softening point of 163 ° C. and an acid value of 23.2 were heated and dissolved at 220 ° C. for 1 hour. I got a varnish. 700 parts of this varnish and 200 parts of Brilliant Carmine 6B were kneaded and kneaded with three rolls, and 5 parts of manganese octylate having a manganese content of 8% and Nisseki # 0.
Solvent 150 parts and castor oil fatty acid 10 parts were mixed to obtain an offset printing ink having an incometer tack value (400 rpm) of 9.8.

Comparison of Volatile Solvent The amount of volatilized solvent was measured according to ASTM D2369-87. Synthetic paper 6,000 with Roland Practica
Printing was performed at 0 sheets / hour, and the sheets were left standing for about 1 day in a state where 1,000 sheets were stacked, and the degree of waviness of the printed matter was examined. Example Volatile solvent amount Rippling Example 7 1% ○ No waviness. Example 8 0.5% ○ No waviness. Example 9 3% ○ No waviness. Example 10 0.3% ○ No waviness. Example 11 7% Δ Wavy is slightly observed. Example 12 6% Δ Rippling is slightly observed. Comparative Example 1 13% x waviness is observed. Comparative Example 2 15% × There may be a problem during printing on the upside. Comparative Example 3 12% × There may be a problem during printing on the upside.

[0026]

According to the present invention as described above, when a low molecular weight alcoholysis compound or carboxylis compound of a drying oil or a semi-drying oil is used as a main component of a varnish resin of a printing ink, the compound itself has a low viscosity. It is possible to reduce or eliminate the ink solvent required for adjusting the viscosity.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masafumi Nakano             3950-3 Kashiwayama, Moriya Town, Mizukaido City, Ibaraki Prefecture             Taniguchi Ink Manufacturing Co., Ltd.

Claims (5)

[Claims] 1. A printing ink containing a colorant and an oxidative polymerization resin varnish, wherein the main component of the varnish resin is 0.5 to 2.0 unsaturated carboxylic acid components of a drying oil or a semi-drying oil. Is substituted with a saturated or unsaturated carboxylic acid having a smaller number of carbon atoms. 2. A printing ink containing a colorant and an oxidative polymerization type resin varnish, wherein the main component of the varnish resin is 0.5 to 2.0 unsaturated carboxylic acid components of a drying oil or a semi-drying oil. Is a trans-esterified with saturated or unsaturated alcohol. 3. The content of the ink solvent is 1 in the total amount of the ink.
The printing ink according to claim 1 or 2, which accounts for less than 0% by weight. 4. The printing ink according to claim 1, wherein at least a part of the carboxylic acid generated by substitution in claim 1 is esterified with alcohol. 5. The printing ink according to claim 2, wherein at least a part of hydroxyl groups of glycerin generated in claim 2 is esterified with a carboxylic acid.