JP2005225903A - Active energy ray curable printing ink composition, method for printing and print thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an active energy ray curable printing ink composition printable with a printing machine for an oily ink and to provide a print having highly glossy and beautiful high class feeling by combination with an active energy ray curable overprinting varnish. <P>SOLUTION: The active energy ray curable printing ink composition is characterized as comprising 0.1-20 wt.% of a vegetable oil, its fatty acid ester or a modified material thereof (A), 1-40 wt.% of an alkyd resin (B), 10-70 wt.% of an acrylate or a methacrylate monomer (C) of an alcohol having a 1-18C alkyl group and 1-40 wt.% of a colorant or an extender pigment (D). The alkyd resin (B) is obtained by carrying out an esterifying reaction of a monobasic acid (B1) with a polyol (B2) and a polybasic acid (B3) and has a cyclic structure and 50-180°C softening point. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an alkyd resin having a cyclic structure obtained by an esterification reaction of vegetable oil, a fatty acid ester thereof or a modified product thereof, a monobasic acid, a polyol or a polybasic acid, and an alkyl group of C1 to C18. An active energy ray-curable printing ink composition characterized by containing a (meth) acrylate monomer of alcohol having the active energy ray-curable ink composition printed on a substrate, and the printing ink is uncured or A printing method comprising applying an active energy ray-curable overcoat varnish or an overprint varnish in a cured state and irradiating with an active energy ray, and printing the active energy ray-curable printing ink composition Or a printed matter obtained by the printing method.

Ink is used for the purpose of imparting aesthetic luxury and various resistances (friction resistance, water resistance, oil resistance, solvent resistance) in the printing of various paper containers, books, posters, calendars, labels, wrapping paper, cards, etc. After printing, it has been generally practiced to apply an overcoat varnish, particularly an active energy ray overcoat varnish. For example, a method of printing oil-based ink (oxidative polymerization), sticking it until several days after the ink is dried, and then applying an active energy ray-curable overcoat varnish (oil-based ink / active energy ray-curable varnish Off-line system), a method of applying active energy ray curable overcoat varnish immediately after printing active energy ray curable ink (inline system of active energy ray curable ink / active energy ray curable varnish), etc. It was taken. However, in the case of the former off-line system, work efficiency is low, and in the case of the latter in-line system, there are problems such as high cost of the active energy ray-curable ink.

  Furthermore, the oil-based ink often uses a volatile hydrocarbon-based ink solvent that is a mineral oil fraction. In recent years, however, there has been an increasing need for VOCS (volatile organic compound) free inks in which volatile hydrocarbon-based ink solvents are completely excluded from the oil-based inks in consideration of the environment. For example, according to Fukuda and Ishii et al. (Japan Printing Society Journal, Vol. 37, No. 5, p. 51), if it becomes possible to make VOCS-free offset printing ink, more than 40,000 tons of petroleum for printing ink It is said that the solvent can be reduced.

  In order to solve the above problems, a coater machine and an active energy ray irradiation device are installed after the multi-color printing machine for oil-based ink, and the active energy ray-curable overcoat varnish is applied and cured immediately after printing the oil-based ink. Attempts have been made to produce glossy prints, but with this method the gloss gradually decreases, especially when the ink is overprinted with multiple colors over a single color and becomes thicker. The deterioration continued for several days (gross back), and there was a problem that the aesthetic luxury was lost and the commercial value was lost.

  On the other hand, in a printing maker having only a multi-color printing machine for oil-based inks, when trying to obtain a printed matter with the above-mentioned inline system of active energy ray curable ink / active energy ray curable varnish, the active energy ray When the curable ink infiltrates and swells in the rubber roll or blanket of the printing press, ink transfer failure occurs, or when the next printing is performed by changing the pattern, the printed pattern trace in the swollen area is thinly ghosted in the next printed matter. Appear, and the merchandise value as printed matter is lost. In addition, there are various problems such as the fact that the cleaning fluid for printing presses cannot be used for oil-based inks, and it can be changed to rubber rolls and blankets for printing that are durable for active energy ray-curable inks, or dedicated to active energy ray-curable inks. There were problems such as the need to introduce a new multicolor printing machine.

In order to solve the above problems, attempts to mix components of oil-based inks and components of active energy ray-curable inks are also known (see, for example, Patent Document 1 and Patent Document 2). Energy beam curable inks have poor compatibility, and fluidity deteriorates, resulting in poor transfer during printing. In general, rosin-modified phenolic resins and vegetable oils or their fatty acid esters, which are oily materials, and (meth) acrylic monomers or (meth) acrylic oligomers having ethylenically unsaturated double bonds with active energy ray curability may be difficult to dissolve. Many.

  Therefore, for the reasons described above, there is a demand for development of an ink / varnish system that can suppress gloss back after varnish application and that can be printed without problems on a multicolor printing machine for oil-based inks.

JP-A-7-138516 JP-A-8-283529

  The present invention relates to an alkyd resin having a cyclic structure obtained by an esterification reaction of vegetable oil, a fatty acid ester thereof or a modified product thereof, a monobasic acid, a polyol or a polybasic acid, and an alkyl group of C1 to C18. The solubility of the (meth) acrylic monomer or (meth) acrylic oligomer having an oily material and an active energy ray-curable ethylenically unsaturated double bond can be maintained by containing the (meth) acrylate monomer of the alcohol having Is possible.

  By using a curable ink such as a curable coating composition that has both oxidative polymerization and acrylic polymerization properties, general oil-based printing inks have good anti-swelling properties, detergency, emulsification printability, good properties such as misting, low Even if an in-line printing method is used, in which an active energy ray-curable overcoat varnish is applied by bar stacking or wet immediately after multi-color printing, and the active energy ray is irradiated while maintaining cost, the gloss back It has become possible to provide a curable ink that does not cause ink.

  A further feature of the present invention is to provide a curable ink that does not use any volatile organic compounds (VOCS) such as petroleum-based solvents, and printed matter printed using them. By the present invention, it is possible to limit the thermal weight loss to 1% or less (excluding water) in the VOC measurement method Metyod24 (110 ° C., heating residue measurement by heating for 1 hour) proposed by the US Environmental Protection Agency. Thus, it becomes possible to provide VOC-free ink and printed matter.

In addition, as an environmental measure, petroleum-based components contained in offset ink, soybean oil ink in which part of dry oil is replaced with soybean oil or its modified products, and ink that has cleared ASA (American Soybean Association) certification standards It is also possible to satisfy the required criteria according to the present invention.
However, the present invention can also be applied as a curable ink containing a volatile organic compound (VOCS) such as a conventional petroleum solvent.

That is, the present invention provides esterification of 0.1 to 20% by weight of vegetable oil and / or its fatty acid ester and / or their modified products (A), monobasic acid (B1), polyol (B2), and polybasic acid (B3). Alkyd resin (B) having a softening point of 50 to 180 ° C. having a cyclic structure of 1 to 40% by weight obtained by the reaction, (meth) acrylate monomer of alcohol having 10 to 70% by weight of C1 to C18 alkyl group (C ), An active energy ray-curable printing ink composition containing 1 to 40% by weight of a colorant or extender pigment (D).
The present invention also provides the above active energy ray-curing property wherein the monobasic acid (B1) is 0 to 50% by weight of aliphatic monobasic acid and / or 50 to 100% by weight of aromatic or alicyclic monobasic acid. The present invention relates to a printing ink composition.
The present invention also provides the above active energy ray-curable composition wherein the polybasic acid (B3) is 0 to 50% by weight of aliphatic polybasic acid and 50 to 100% by weight of aromatic and / or alicyclic polybasic acid. The present invention relates to a printing ink composition.
Further, in the present invention, the cyclic polybasic acid contains 1 to 100% by weight of a petroleum resin and / or a cyclic polybasic acid which is a reaction product of a rosin and an α, β-ethylenically unsaturated carboxylic acid or an anhydride thereof. The present invention relates to the active energy ray-curable printing ink composition.
Furthermore, this invention relates to the said active energy ray-curable printing ink composition containing resin with a softening point of 50-180 degreeC other than alkyd resin (B).

In addition, the present invention relates to the active energy ray-curable printing ink composition containing a (meth) acrylate monomer other than the (meth) acrylate monomer (C) or a (meth) acrylate oligomer.
In addition, this invention relates to the said active energy ray-curable printing ink composition containing a radically polymerizable initiator.
In addition, the present invention prints the active energy ray-curable ink composition on a substrate, and applies the active energy ray-curable overcoat varnish or overprint varnish in a state where the printing ink is uncured or cured. Further, the present invention relates to a printing method characterized by irradiating active energy rays.
In addition, the present invention relates to a printed matter obtained by printing the active energy ray-curable printing ink composition.
In addition, the present invention relates to a printed matter obtained by the above printing method.

  As described above, the present invention maintains a good property such as swelling resistance, detergency, emulsification printing suitability, misting, etc. of general oil-based printing ink, and low cost, and after multi-color printing, it is not stacked immediately or immediately. It is possible to provide a glossy high-quality printed matter with the above-mentioned gloss back suppressed even when an inline printing method is applied by applying an active energy ray-curable overcoat varnish and irradiating active energy rays. It becomes.

  The vegetable oil, fatty acid ester thereof, and modified products thereof used in the present invention will be described. First, vegetable oil is triglyceride in which at least one fatty acid is a fatty acid having at least one carbon-carbon unsaturated bond in triglyceride of glycerin and fatty acid. Real oil, linseed oil, eno oil, oil deer oil, olive oil, cacao oil, kapok oil, kayak oil, mustard oil, kyounin oil, kiri oil, kukui oil, walnut oil, poppy oil, sesame oil, safflower oil, radish seed oil , Soybean oil, Daifucho oil, Camellia oil, Corn oil, Rapeseed oil, Niger oil, Nuka oil, Palm oil, Castor oil, Sunflower oil, Grape seed oil, Gentia oil, Pine seed oil, Cottonseed oil, Palm oil, Peanut oil And dehydrated castor oil. Further preferred vegetable oils are vegetable oils having an iodine value of at least 100 or more (in parentheses indicate the oil and fat chemical product manual: the iodine value quoted from the Nikkan Kogyo Shimbun), Asa oil (149 or more), Linseed oil (over 170), Eno oil (over 192), deer oil (over 140), Kapok oil (85-102), kaya oil (over 130), mustard oil (over 101), Kyonin oil (97-109) , Kiri oil (145 or higher), kukui oil (136 or higher), walnut oil (143 or higher), poppy oil (131 or higher), sesame oil (104 or higher), safflower oil (130 or higher), radish seed oil (98 to 112) ), Soybean oil (117 or more), large fusose oil (101), corn oil (109 or more), rapeseed oil (97 to 107), niger oil (126 or more), nuka oil (92 to 1) 5), sunflower oil (125 or more), grape seed oil (124 or more), gentian oil (93 to 105), pine seed oil (146 or more), cottonseed oil (99 to 113), peanut oil (84 to 102), dehydrated Castor oil (147 or more) is preferably used, and more preferably a vegetable oil having an iodine value of 120 or more. By setting the iodine value to 120 or more, it is possible to further improve the drying property by oxidative polymerization of the curable composition.

  In addition, in this invention, the regenerated vegetable oil collect | recovered / regenerated after using for edibles, such as tempura oil, can also be used. The regenerated vegetable oil is preferably an oil that has been regenerated with a water content of 0.3% by weight or less, an iodine value of 100 or more, and an acid value of 3 or less. Impurities that affect the emulsification behavior of the ink, such as contained salt, can be removed, and by regenerating the iodine value as 100 or more, it becomes possible to make the dryness, that is, the oxidative polymerization good, Furthermore, by selecting and regenerating vegetable oil having an acid value of 3 or less, the acid value of the regenerated vegetable oil can be lowered, and overemulsification of the ink can be suppressed. As a method for regenerating the recovered vegetable oil, methods such as filtration, removal of precipitates by standing, and decolorization by activated clay are taken.

  Next, examples of the fatty acid ester in the present invention include fatty acid monoesters obtained by ester reaction of saturated or unsaturated fatty acids obtained by hydrolysis of vegetable oils and saturated or unsaturated alcohols. Fatty acid monoesters which are liquid at ˜25 ° C. and have a boiling point of 200 ° C. or higher at normal pressure (101.3 kPa) are preferred. Specific examples of such fatty acid esters include hexyl butyrate and heptyl butyrate as saturated fatty acid monoesters. Hexyl butyrate, octyl butyrate, butyl caproate, acyl caproate, hexyl caproate, heptyl caproate, octyl caproate, nonyl caproate, propyl enanthate, butyl enanthate, amyl enanthate, hexyl enanthate, heptyl enanthate , Octyl enanthate, caprylic acid , Vinyl caprylate, propyl caprylate, isopropyl caprylate, butyl caprylate, amyl caprylate, hexyl caprylate, heptyl caprylate, octyl caprylate, methyl pelargonate, ethyl pelargonate, vinyl pelargonate, propyl pelargonate, Butyl pelargonate, amyl pelargonate, heptyl pelargonate, methyl caprate, ethyl caprate, vinyl caprate, propyl caprate, isopropyl caprate, butyl caprate, hexyl caprate, heptyl caprate, methyl laurate, lauric acid Examples include ethyl, vinyl laurate, propyl laurate, isopropyl laurate, butyl laurate, isoamyl laurate, hexyl laurate, and 2-ethyl-hexyl laurate. Can.

  As unsaturated fatty acid esters, ethyl oleate, propyl oleate, butyl oleate, allyl oleate, isoamyl oleate, heptyl oleate, 2-ethylhexyl oleate, methyl elaidate, ethyl elaidate, propyl elaidate, Allyl elaidate, butyl elaidate, isobutyl elaidate, tert-butyl elaidate, isoamyl elaidate, 2-ethylhexyl elaidate, methyl linoleate, ethyl linoleate, allyl linoleate, propyl linoleate, isopropyl linoleate , Butyl linoleate, isobutyl linoleate, tert-butyl linoleate, pentyl linoleate, hexyl linoleate, heptyl linoleate, 2-ethylhexyl linoleate, linolenic acid Cyl, ethyl linolenate, allyl linolenate, propyl linolenate, isopropyl linolenate, butyl linolenate, isobutyl linolenate, tert-butyl linolenate, pentyl linolenate, hexyl linolenate, heptyl linolenate, linolenic acid-2- Ethylhexyl, methyl arachidonic acid, ethyl arachidonic acid, allyl arachidonic acid, propyl arachidonic acid, isopropyl arachidonic acid, butyl arachidonic acid, isobutyl arachidonic acid, arachidonic acid-tert-butyl, pentyl arachidonic acid, hexyl arachidonic acid, heptyl arachidonic acid, arachidone 2-ethylhexyl acid, methyl eicosenoate, ethyl eicosenoate, allyl eicosenoate, propyl eicosenoate, isopropyl eicosenoate, butyl eicosenoate, Isobutyl senate, eicenoic acid-tert-butyl, eicosenic acid pentyl, eicosenoic acid hexyl, eicosenoic acid heptyl, eicosenoic acid-2-ethylhexyl, eicosapentaenoic acid methyl, eicosapentaenoic acid ethyl, eicosapentaenoic acid allyl, eicosapentaenoic acid propyl, Isopropyl eicosapentaenoate, butyl eicosapentaenoate, isobutyl eicosapentaenoate, tert-butyl eicosapentaenoate, pentyl eicosapentaenoate, hexyl eicosapentaenoate, heptyl eicosapentaenoate, eicosapentaenoic acid-2-ethylhexyl, methyl erucate, Ethyl erucate, allyl erucate, propyl erucate, isopropyl erucate, butyl erucate, isobutyl erucate, erucic acid-t ert-butyl, pentyl erucate, hexyl erucate, heptyl erucate, 2-ethylhexyl erucate, methyl docosahexaenoate, ethyl docosahexaenoate, allyl docosahexaenoate, propyl docosahexaenoate, isopropyl docosahexaenoate, butyl docosahexaenoate, isobutyl docosahexaenoate , Docosahexaenoic acid-tert-butyl, docosahexaenoate pentyl, docosahexaenoate hexyl, docosahexaenoate heptyl, docosahexaenoate-2-ethylhexyl, methyl ricinoleate, ethyl ricinoleate, allyl ricinoleate, propyl ricinoleate, isopropyl ricinoleate, butyl ricinoleate , Isobutyl ricinoleate, tert-butyl ricinoleate, pentyl ricinoleate, Lumpur hexyl, heptyl ricinoleate, and the like can be exemplified ricinoleic acid 2-ethylhexyl.

  The saturated or unsaturated fatty acid constituting the fatty acid ester in the present invention is actually coconut oil fatty acid, palm oil fatty acid, rapeseed oil fatty acid, soybean oil fatty acid, hydrogenated soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, tall oil. Fatty acids, dehydrated castor oil fatty acids, or fractionated fatty acids by fractional distillation thereof are used, and are obtained as a mixture of the aforementioned saturated or unsaturated fatty acids.

Further, in recent years, soybean oil or fatty acid esters thereof (soybean oil fatty acid alkyl esters such as soybean oil fatty acid ethyl ester and soybean oil fatty acid butyl ester) are exemplified as environmentally friendly types. Furthermore, as a modified product of vegetable oil or its fatty acid, so-called hybrid compounds having both an oil-soluble aliphatic or oil-soluble cyclic compound group and an acryloyl group are exemplified. That is, an esterification reaction with a mixture of a polyol, a cyclic monobasic acid and / or a fatty acid having 4 to 36 carbon atoms, and (meth) acrylic acid for producing a hybrid compound is conducted in a four-necked flask equipped with a stirrer. A mixture of a polyol, a cyclic monobasic acid and / or a fatty acid having 4 to 36 carbon atoms is charged, and the temperature is gradually raised in a nitrogen stream with or without refluxing solvent such as toluene, xylene, anone, cyclohexane, etc. In the range of 260 ° C., the reaction is carried out in the absence of a catalyst or in the presence of a catalyst, so that the acid value (the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample) is 5 or less, preferably 2 or less. Do until. Examples of the polyol include divalent polyols such as branched glycol diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, nepentyl glycol, 2-butyl-2-ethylpropane diol, tricyclodecane dimethylol, dicyclo Trimethylol ethane, trimethylol propane, trimethylol hexane, trimethylol octane and other trimethylol alkanes such as pentadiene diallyl alcohol copolymer as trivalent polyols and glycerin as tetravalent or higher polyols pentaerythritol, diglycerin , Ditrimethylolpropane, sorbitan, sorbitol, dipentaerythritol, inositol, tripentaerythritol, etc. In the present invention, from the viewpoint of suppressing blanket swelling, a dimer or higher polyol such as diglycerin, ditrimethylolpropane, dipentaerythritol is preferably used.
The cyclic monobasic acid of the present invention is benzoic acid, methylbenzoic acid (naphthoic acid), (tertiary) butylbenzoic acid, naphthoic acid, (ortho) benzoylbenzoic acid, naphthenic acid, rosin (gum rosin, tall oil rosin, wood rosin, Examples include disproportionated rosin, hydrogenated rosin) and tricyclodecane monocarboxylic acid. The fatty acid having 4 to 36 carbon atoms is a saturated or unsaturated normal or branched fatty acid having 4 to 36 carbon atoms, such as butyric acid, caproic acid, enanthic acid, octylic acid, pelargonic acid, undecanoic acid, lauric acid, Examples include myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, icosyl acid and the like. Furthermore, fatty acids of natural fats and oils, such as tung oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, coconut oil fatty acid, (dehydrated) castor oil fatty acid, palm oil fatty acid, safflower oil fatty acid, cottonseed oil fatty acid, rice bran oil fatty acid, olive oil fatty acid And rapeseed oil fatty acid. Furthermore, examples of fatty acids derived from fish oil and animal fats include squid oil fatty acid, sardine oil fatty acid, saury oil fatty acid, cod oil fatty acid, whale oil fatty acid, beef tallow oil fatty acid, pork tallow oil fatty acid, and tallow oil fatty acid. Further examples include dimer acids of fatty acids such as tung oil dimer fatty acid and sama oil dimer fatty acid. When these fatty acids having 4 to 36 carbon atoms are unsaturated fatty acids, the resulting hybrid compound becomes a hybrid curable compound having both oxidative polymerization property and active energy ray curable property, and the curable composition of the present invention. When used as, it becomes possible to impart more preferable curing performance. Then, in a temperature range of 80 to 120 ° C., a polymerization inhibitor is charged, then (meth) acrylic acid and a catalyst are charged, and air is blown, or a mixture of air and nitrogen or nitrogen is blown in a solvent such as toluene, MIBK, or cyclohexane. The reaction is continued for 10 to 20 hours in the temperature range of 80 to 120 ° C., and the reaction is continued until the acid value is 20 or less, preferably 15 or less, more preferably 10 or less. Examples of the esterification catalyst include p-toluenesulfonic acid and dodecylbenzene. Sulfonic acids such as sulfonic acid, methanesulfonic acid and ethanesulfonic acid, mineral acids such as sulfuric acid and hydrochloric acid, trifluoromethyl sulfuric acid, trifluoromethyl acetic acid, Lewis acid and the like are used. In addition, metal complexes such as tetrabutyl zirconate and tetraisopropyl titanate, alkalis such as magnesium oxide, calcium oxide, and zinc oxide, oxides of alkaline earth metals, metal salt catalysts, and the like are also used. The amount of catalyst used is generally 0.1 to 5% by weight. Further, since the reaction product may be colored under such conditions, hypophosphorous acid, triphenyl phosphite, triphenyl phosphate, or the like, which is a reducing agent, may be used in combination.

  As polymerization inhibitors, alkylphenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone, nitrosobenzene, 2,5-di- tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino-1,3-dimethylbutylidene) aniline oxide Dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraloxime, methyl ethyl ketoxime, cyclohexanone oxime, and the like are used.

  Furthermore, a hybrid compound obtained by reacting a polyvalent carboxylic acid is obtained by the following method. That is, a polyol and a fatty acid having 4 to 36 carbon atoms are charged into a four-necked flask equipped with a stirrer, and the temperature is gradually increased from 180 ° C. in a nitrogen stream under or without a solvent such as toluene, xylene, or anone. The reaction is carried out in the temperature range of ˜260 ° C. for several hours to make the acid value 5 or less, desirably 2 or less. After cooling, charging polyvalent carboxylic acid at 180 ° C., gradually raising the temperature from 180 ° C., reacting at 230-260 ° C. for several hours, and reacting until the acid value is 5 or less, preferably 2 or less, or A polyol, a fatty acid having 4 to 36 carbon atoms, and a polyvalent carboxylic acid are charged, gradually heated from 180 ° C. under a nitrogen stream in the same solvent or without solvent, and reacted at 230 to 260 ° C. for several hours, The acid value is 5 or less, preferably 2 or less. Thereafter, it is cooled to 120 ° C. or lower, charged with a polymerization inhibitor, (meth) acrylic acid, a catalyst, and blown in air or mixed with air and nitrogen, and in a solvent such as toluene, MIBK, or cyclohexane at 80 to 120 ° C. Examples thereof include a method in which the reaction is continued for 10 to 20 hours in the temperature range and the reaction is continued until the acid value is 20 or less, preferably 15 or less.

  Examples of polyvalent carboxylic acids include maleic acid or its anhydride, succinic acid or its anhydride, adipic acid, sebacic acid, dodecenyl succinic anhydride, pentadecenyl succinic anhydride, etc. Dimer acid such as saturated fatty acid, dimer acid, o-phthalic acid or its anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid or its anhydride, hexahydrophthalic acid or its anhydride, (methyl) hymic acid or Examples thereof include anhydride, tricyclodecanedicarboxylic acid, trimellitic acid or anhydride thereof, pyromellitic acid or anhydride thereof, and polymerized rosin.

  The hybrid compound in the present invention further contains 10 to 80% by weight of cyclic monobasic acid and / or fatty acid having 4 to 36 carbon atoms and 5 to 40% by weight of (meth) acrylic acid. If the amount of the cyclic monobasic acid and / or fatty acid having 4 to 36 carbon atoms is less than 10% by weight, the compatibility with a resin generally used in oil-based inks such as rosin phenol resin is good. When it becomes insufficient and is more than 80% by weight, the curability to the active energy ray is lowered. On the other hand, when the amount of (meth) acrylic acid is less than 5% by weight, the curability for active energy rays is lowered, and when it is more than 40% by weight, the amount of fatty acid modification is reduced and the compatibility with rosin phenol resin is insufficient. It becomes.

  Further, as modified products thereof, epoxidized soybean oil, epoxidized soybean oil acrylic ester (CN 111 manufactured by Sartomer, Evekril 860 manufactured by UCB), epoxidized amaniyu, epoxidized amaniyu acrylic ester, and other epoxidized fatty oils, epoxidized Examples include fatty oil acrylic esters.

  Furthermore, residual hydroxyl groups of transesterification products of polyols such as soybean oil and glycerin, trimethylolpropane and pentaerythritol, or residual hydroxyl groups and trimethylolpropane of esterification products of soybean oil fatty acids and polyols such as glycerin, trimethylolpropane and pentaerythritol Mono or di (meth) acrylic ester, glycerin mono or di (meth) acrylic ester, pentaerythritol di or tri (meth) acrylic ester, diglycerin di or tri (meth) acrylic ester ditrimethylolpropane di or tri (meth) acrylic ester, Residual hydroxyl groups of (meth) acrylic ester compounds such as dipentaerythritol tetra- or penta (meth) acrylic ester are tolylene diisocyanate, isophorone diisocyanate , Soybean oil urethane acrylate ester isocyanate compound reacted and hexamethylene diisocyanate compound and the like.

The alkyd resin (B) having a cyclic structure of the present invention and having a softening point of 50 to 180 ° C. is obtained by an esterification reaction of a monobasic acid (B1), a polyol (B2), and a polybasic acid (B3). The monobasic acid (B1) of the present invention is preferably 0 to 50% by weight of aliphatic monobasic acid and / or 50 to 100% by weight of aromatic or alicyclic cyclic monobasic acid in the monobasic acid (B1). The aliphatic monobasic acid is exemplified by the fatty acid before the esterification of the fatty acid of the vegetable oil or the fatty acid ester. The aromatic monobasic acid is a compound in which a carboxylic acid group is directly bonded to an aromatic compound such as benzene or naphthalene, and other substituents such as an alkyl group may be bonded to the aromatic ring. Specific examples of the aromatic monobasic acid include benzoic acid, methyl benzoic acid, tertiary butyl benzoic acid, naphthoic acid, orthobenzoyl benzoic acid and the like. Examples of the alicyclic monobasic acid include rosins (gum rosin, tall oil rosin, wood rosin, disproportionated rosin, hydrogenated rosin), cyclohexane monocarboxylic acid, tricyclodecane monocarboxylic acid, and the like. The ratio of aromatic monobasic acid to alicyclic cyclic monobasic acid is aromatic monobasic acid / alicyclic cyclic monobasic acid = 0-100 wt% / 100-0 wt%, preferably aromatic monobasic acid / The alicyclic monobasic acid is preferably 20 to 80% by weight / 80 to 20% by weight.

The polyol (B2) of the present invention includes divalent polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, nepentyl glycol, branched alkyl diols such as butyl, ethyl, propane diol, tricyclodecane dimethylol, di Cyclopentadiene diallyl alcohol copolymer, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, hydrogenated catechol, hydrogenated resorcin, hydrogenated hydroquinone, hydrogenated trivalent polyol, glycerin, trimethylolethane, trimethylolpropane , Trimethylolalkanes such as trimethylolhexane and trimethyloloctane, pentaerythritol, diglycerin, ditrimethylolpro as tetravalent or higher polyols Examples thereof include bread, sorbitan, sorbitol, dipentaerythritol, inositol, tripentaerythritol and the like. Glycerin, trimethylolpropane, trimethylolethane and pentaerythritol are preferred for economic reasons.

Further, 0.1 to 30 parts by weight of the polyol (B2) may be used in combination with an epoxy compound. However, if it exceeds 30 parts by weight, the emulsification suitability during offset printing deteriorates, which is not preferable. Examples of the epoxy compound include a bisphenol A type epoxy compound such as Epicoat 828, Epicoat 1001, Epicoat 1004, Epicoat 1007, Epicoat 1009, etc. manufactured by Yuka Shell, and also a diglycidyl ether type polyepoxy compound of bisphenol F and bisphenol S. , Carboxylic acid, cresol, t-butylphenol, octylphenol, nonylphenol, dodecylphenol novolak epoxy compounds, alicyclic epoxy compounds, epoxidized soybean oil, epoxidized linseed oil and the like.

Further, the polybasic acid (B3) comprises 0 to 50% by weight of aliphatic polybasic acid and 50 to 100% by weight of aromatic and / or alicyclic polybasic acid in the polybasic acid (B3).
Aliphatic polybasic acids such as succinic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, dodecenyl succinic anhydride, pentadecenyl succinic acid, succinic anhydride, fumaric acid, (anhydrous) Examples include maleic acid. Further, the cyclic polybasic acid includes an aromatic polybasic acid and an alicyclic polybasic acid. An aromatic polybasic acid or its anhydride is a compound in which two or more carboxylic acid groups are directly bonded to an aromatic compound such as benzene or naphthalene, and part or all of the double bonds of the aromatic ring are hydrogenated. May be. Specific compounds include o-phthalic acid or anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid or anhydride, hexahydrophthalic acid or anhydride, (methyl) hymic acid or anhydride, tri Examples include merit acid or its anhydride, pyromellitic acid or its anhydride, and the like.

The alicyclic polybasic acid includes a cyclic polybasic acid which is a reaction product of petroleum resin and / or rosins and α, β-ethylenically unsaturated carboxylic acid or its anhydride.
The petroleum resin of the present invention can be obtained by subjecting the C5 fraction or C9 fraction obtained by naphtha decomposition to cation, anion or radical polymerization. Petroleum resin containing a C5 fraction is a cyclopentadiene, methylcyclopentadiene, a dimer or pentamer thereof, a cyclopentadiene monomer such as a co-multimer, or a cyclopentadiene monomer. It is obtained by thermally polymerizing a mixture with a polymerizable comonomer in the presence of a catalyst or without a catalyst. As the catalyst, a Friedel-Craft type Lewis acid catalyst, for example, boron trifluoride and its complex with phenol, ether, acetic acid and the like are usually used. The copolymerization ratio of the cyclopentadiene monomer and the comonomer copolymerizable therewith in the hydrocarbon resin of the present invention needs to be at least 5 mol% of the cyclopentadiene monomer. . Examples of the comonomer used include diisobutylene obtained by dimerizing ethylene, propylene, propene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene and isobutylene with an acid catalyst ( 2,4,4-trimethylpentene-1 and 2,4,4-trimethylpentene-2), 1-hexene, 2-hexene, 1-octene, 2-octene, 4-octene, 1-decene, etc. Chain conjugated dienes such as 1,3-butadiene, 1,3-pentadiene (piperylene), isoprene, 1,3-hexadiene, 2,4-hexadiene, styrene, α- Methylstyrene, β-methylstyrene, isopropenyltoluene, p-tert-butylstyrene, p-hydroxystyrene, vinyltoluene, dibi And vinyl aromatics such as nylbenzene, and aromatic unsaturated compounds such as indene, methylindene, coumarone (benzofuran), and methylcoumarone (2-methylbenzofuran). Petroleum resin containing C9 fraction is obtained by the above thermal polymerization of the above vinyl aromatics, aromatic unsaturated compounds and the like.

Below, Maruzen Petroleum Co., Ltd. C5 series Marcarets M510A, Marcarets M845A, Marcarets M905A, Marcarets M100A, Marcarets # 8011, Marcarets T-100A, Marcarets R-100B, Marcarets S100A, Marcarets H505, Marcarets H700F, 25 The Furthermore, Nippon Petrochemical Co., Ltd. Nisseki Neoresin 540, Nisseki Neoresin 580, Nisseki Neoresin EP-80, Nisseki Neoresin EP-110, Nisseki Neoresin EP-140, Nisseki Neoresin PH-105, Nisseki Neoresin NB-90, Nisseki Neopolymer S, Nisseki Neopolymer 80, Nisseki Neopolymer L-90, Nisseki Neopolymer 100, Nisseki Neopolymer 110, Nisseki Neopolymer 120, Nisseki Neopolymer 130, Nisseki Neopolymer E-100, Nisseki Neopolymer E-130, Nisseki Neopolymer E-130S, Nisseki Neopolymer M, Nisseki Neopolymer S-110, Nisseki Neopolymer E-100 Nisseki Neopolymer GS, Japan Examples of the stone neopolymer 170S, TO-90, and TO-100. Further, C5 series quinton 1000 series (1325, 1345, 1500, 1522, 1700), quinton QTN1100, quinton QTN1345H, quinton RI-201 manufactured by Nippon Zeon Co., Ltd. are exemplified. Furthermore, Toho Chemical Co., Ltd. Toho High Resin (# 60, # 90, # 90S, #NX, # 120, # 130, # 140, # 120S, RS-9, RS-21, # 2100, Super # 110, Super # 110T, PA-140), COPEREX2100, etc. are exemplified. Furthermore, ESCOREZ 1100 series, 1200 series, 1300 series, 2000 series, 5000 series, 8000 series, etc. manufactured by Tonex Co., Ltd. are exemplified. In addition, C9 Petcole (hereinafter, grades LX, LX-HS, 100-T, 120, 120HV, 130, 140, 140HM, 140HM3, 150) manufactured by Tosoh Corp., C9 rich C9 / C5 mixed petro Tack (70, 90) etc. are illustrated. Further, C5 Picotac (95, B), Pico Pale 100, C9 modified C5 Hercotac 1149, C9 Endex 155, Crystallex (hereinafter each grade # 1120, 3085, 3100, 5140, F100), Hercolite, manufactured by Hercules Co., Ltd. (Hereinafter each grade # 240, 290) picolastic (hereinafter each grade A5, A75, 100, LC), hydrogenated C9-based Ligalite Y (hereinafter each grade R1010, R1090, R1100, R1125, S5100, R7100) and the like are exemplified. The

  Examples of α, β-ethylenically unsaturated carboxylic acids or acid anhydrides include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride, Examples include crotonic acid and 2,4-hexadienic acid (sorbic acid). The amount of modification of these α, β-ethylenically unsaturated carboxylic acids or acid anhydrides is modified in the range of 1 to 100 mol% with respect to the cyclopentadiene monomer in the hydrocarbon resin used in the present invention. Although possible, it is usually modified in an amount in the range of 0.01 to 0.5 mole per 100 g of the petroleum resin. The optimum amount of modification is desirably adjusted so that these unsaturated carboxylic acids and / or their anhydrides do not remain. The denaturation temperature is usually from 100 ° C. to 300 ° C., which is the temperature at which the petroleum resin melts, but a range of 150 ° C. to 250 ° C. is preferably used. These unsaturated carboxylic acids and / or acid anhydrides thereof can be used alone or in combination of two or more at an arbitrary quantitative ratio.

Examples of the rosins of the present invention include gum rosin, tall oil rosin, wood rosin, disproportionated rosin, water-added rosin, and polymerized rosin. The reaction conditions for the rosins and the α, β-ethylenically unsaturated carboxylic acid or acid anhydride thereof are the same as the reaction conditions for the petroleum resin and α, β-ethylenically unsaturated carboxylic acid or acid anhydride thereof.
Petroleum resins and rosins may be used either alone or in combination.

  The reaction of petroleum resin or rosin with α, β-ethylenically unsaturated carboxylic acid or its anhydride includes Diels-Alder reaction, polymerization reaction, addition reaction of former two double bonds and latter acid, and the like. This reaction may be performed in the presence of an alkyd. For example, esterification of a cyclic monobasic acid and a polyol may be performed, and then a reaction between a petroleum resin or rosin and an α, β-ethylenically unsaturated carboxylic acid or an anhydride thereof may be performed. Another preferred reaction is a reaction between the esterified residual hydroxyl group of a cyclic monobasic acid and a polyol, a petroleum resin or rosin, and an α, β-ethylenically unsaturated carboxylic acid or anhydride thereof, a Diels-Alder reaction, This is a method in which products such as polymerization reaction, addition reaction between the former two double bonds and the latter acid are separately produced and both are ester-reacted. In some cases, all the components constituting the resin may be charged and reacted at once.

The Diels-Alder reaction of petroleum resin or rosin and α, β-ethylenically unsaturated carboxylic acid or its anhydride can be performed by a known method. For example, the reaction temperature is 120 to 300 ° C, preferably 180 to 260 ° C, and the reaction time is 1 to 4 hours. Further, peroxide compounds such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, isopropyl peroxycarbonate, di-t-tertiary butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, azobisisovityronitrile, azobis 2,4 You may superpose | polymerize at 80-120 degreeC by using polymerization initiators, such as azobis compounds, such as a dimethyl valeronitrile, tetramethyl thiuram disulfide, an alkali metal, and oxygen or an oxygen compound. The reaction ratio of petroleum resin or rosin to α, β-ethylenically unsaturated carboxylic acid or anhydride thereof is the number of moles of petroleum resin or rosin / α, β-ethylenically unsaturated carboxylic acid or anhydride thereof. Is reacted in a range of a molar ratio of 0.1 to 10. The weight ratio of petroleum resin or rosins / α, β-ethylenically unsaturated carboxylic acid or anhydride thereof is 66/37 to 97/3, preferably 75/25 to 90/10.

A specific method for synthesizing the resin of the present invention is as follows. An appropriate amount of monobasic acid and polyol is charged into a four-necked flask equipped with a stirrer, and the temperature is raised from 170 ° C. under reflux of the solvent as necessary under a nitrogen stream, and 300 ° C. Preferably, the temperature is gradually raised from 180 ° C. and the reaction is carried out at 230 to 260 ° C. When the acid value becomes 5 or less, it is cooled to 200 ° C. and the polybasic acid or its anhydride and petroleum resin or rosins and α, β -Charge ethylenically unsaturated carboxylic acid. Alternatively, a product obtained by subjecting a petroleum resin or rosin and an α, β-ethylenically unsaturated carboxylic acid to a Diels-Alder reaction at 150 to 250 ° C. is charged in advance, or a polymer obtained by polymerization in advance is charged. Thereafter, the temperature is gradually raised and the reaction is carried out at 230 ° C. to 260 ° C., and when the acid value becomes 15 to 20 or less, the mixture is extracted. Alternatively, when the solvent is refluxed with toluene, xylene, methyl isobutyl ketone or the like, the solvent is removed when the above acid value is reached.

In the esterification reaction according to the present invention, a catalyst is sometimes used, and acidic catalysts such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, sulfonic acid such as methanesulfonic acid, ethanesulfonic acid, sulfuric acid, hydrochloric acid, etc. There are mineral acids, trifluoromethyl sulfuric acid, trifluoromethyl acetic acid, Lewis acids and the like. Further examples include metal complexes such as tetrabutyl zirconate and tetraisopropyl titanate, alkalis such as magnesium oxide, calcium oxide and zinc oxide, oxides of alkaline earth metals, metal salt catalysts and the like. These catalysts are reacted at a temperature of 200 ° C. or more at 0.01 to 1% by weight in the total resin. However, since the reactant is easily colored under such conditions, a reducing agent such as hypophosphorous acid, triphenyl phosphite, triphenyl phosphate, etc. may be used in combination.

The resin of the present invention is non-reactive with active energy rays and has a softening point of 50 to 180 ° C. The acid value of the resin is about 0 to 30, preferably 0 to 20, and the higher the acid value, the better the gel ability with the gelling agent. However, when the acid value is 20 or more, the printing ink is suitable for emulsification during offset printing. May deteriorate because of deterioration. The weight average molecular weight (measured by gel permeation chromatography) of the resin is 1 to 300,000, preferably 20 to 100,000.

Furthermore, you may use together resin with a softening point of 50-180 degreeC other than the said alkyd resin (B). Resins having a softening point of 50 to 180 ° C. other than the alkyd resin (B) having a softening point of 50 to 180 ° C. include rosin-modified phenol resins, petroleum resins, melamine resins, terpene resins, coumarone indene resins, and phenol-modified resins. Examples include petroleum resins and diallyl phthalate resins.
Further, 0 to 10% by weight of a ketone resin obtained by condensation reaction of cyclohexanone, acetophenone or the like with formalin may be used. Examples of the ketone resin include Synthetic Resin CA, Synthetic Resin SK, Synthetic Resin AP, and Synthetic Resin 1201 manufactured by Degussa.

  Furthermore, a polymer resin comprising an aromatic vinyl compound and an α, β unsaturated carboxylic acid ester is exemplified. Aromatic vinyl compounds include styrene, divinylbenzene, vinyltoluene, 1-vinylnaphthalene, 2-vinylnaphthalene, 9-vinylanthracene, 2-vinylphenanthrene, 3-vinylphenanthrene, acenaphthylene, phenyl vinyl ether, o Examples include -cresyl vinyl ether, p-cresyl vinyl ether, α-naphthyl vinyl ether, β-naphthyl vinyl ether, and the like.

Examples of the α, β unsaturated carboxylic acid in the present invention include fumaric acid, maleic acid or its anhydride, itaconic acid, citraconic acid, crotonic acid, cinnamic acid, (meth) acrylic acid and the like.
Examples of the alcohol constituting the α, β unsaturated carboxylic acid ester of the present invention include C1 to C20 aliphatic monohydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, nonanol, decanol, dodecanol, tridecanol, hexa Examples include decanol, octadecanol, icosanol, and allyl alcohol.

In addition, residual hydroxyl compounds in the esterification reaction of C1 to C20 fatty acids and divalent or higher polyols such as ethylene glycol monobutyl ester, propylene glycol monohexyl ester, glycerin or trimethylolpropane dioctylic acid α, β unsaturated carboxylic acid. Examples include acid esters. Furthermore, commercially available fatty acids, other alcohols, phenolic glycidyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-hydroxy as esterified product of α, β unsaturated carboxylic acid -3 phenoxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like.
Furthermore, C5 to C60 cyclic alcohols such as benzyl alcohol, ethylene oxide or propylene oxide of carboxylic acid, ethylene oxide or propylene oxide of cresol, ethylene oxide or propylene oxide of butylphenol, ethylene oxide or propylene oxide of octylphenol, ethylene oxide or propylene oxide of nonylphenol, dodecylphenol Examples include (meth) acrylic acid esters such as ethylene oxide or propylene oxide, alicyclic alcohols such as rosin alcohol (Abitol manufactured by Hercules), tricyclodecane (mono or di) methylol, C5 petroleum resin allyl alcohol copolymer and the like. Furthermore, (meth) acrylic esters such as ethylene glycol monorosin ester, trimethylolpropane or glycerin dirosin ester, pentaerythritol trirosin ester are exemplified. In addition, borneol (bornyl alcohol), isoborneol (isobornyl alcohol), citronellol, pinocamphetol, geraniol, fentil alcohol, nerol, linalool, menthol, terpineol, carpeol, twill alcohol, farnesol, patchouli alcohol, nerolidol And α, β-unsaturated carboxylic acid esters of terpene alcohols such as carotol, casinole lantheol, eudesmol, cedrol, guayol, kesso glycol, phytol, sclareol, manol, hinokiol, ferguinol, totarol.

  The esterification reaction of at least one alcohol compound selected from the above group with an α, β unsaturated carboxylic acid is a conventional method and is generally performed as follows. After adding the above alcohol compound, α, β unsaturated carboxylic acid and polymerization inhibitor to a four-necked flask equipped with a stirrer, thermometer, and cooling separator tube, blown with air, or mixed with air and nitrogen or blown with nitrogen. The reaction is continued in a temperature range of 80 to 120 ° C. for 5 to 20 hours in a solvent such as MIBK or cyclohexane, and the reaction is continued until the acid value is 20 or less, preferably 15 or less, more preferably 10 or less, and the solvent is removed under reduced pressure.

  Examples of esterification catalysts include sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, and ethanesulfonic acid, mineral acids such as sulfuric acid and hydrochloric acid, trifluoromethylsulfuric acid, trifluoromethylacetic acid, and Lewis acid. Is used. In addition, metal complexes such as tetrabutyl zirconate and tetraisopropyl titanate, alkalis such as magnesium oxide, calcium oxide, and zinc oxide, oxides of alkaline earth metals, metal salt catalysts, and the like are also used. The amount of catalyst used is generally 0.1 to 5% by weight. Further, since the reaction product may be colored under such conditions, hypophosphorous acid, triphenyl phosphite, triphenyl phosphate, or the like, which is a reducing agent, may be used in combination.

  Polymerization inhibitors include alkylphenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-hydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone, nitrosobenzene, 2, 5-di-tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino-1,3-dimethylbutyrate Riden) aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraloxime, methyl ethyl ketoxime, cyclohexanone oxime and the like are used.

The polymerization method of the esterified product of an aromatic vinyl compound and an α, β unsaturated carboxylic acid is 60 to 120 ° C., preferably 80 to 100 ° C., using benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, isopropyl peroxycarbonate as a catalyst. Peroxide compounds such as di-t-tert-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, azobis compounds such as azobisisovityronitrile, azobis2,4dimethylvaleronitrile, tetramethylthiuram disulfide, alkali metal and oxygen or oxygen Compounds, metal carbonyls such as triethylboron or tributylboron and oxygen, diethylzinc and oxygen, Cr (CO) 6, Mo (CO) 6, W (CO) 6, Mn (CO) 6, Ni (CO) 6, etc. It is carried out under a thermal polymerization catalyst.

  Examples of the reaction solvent include n-hexane, cyclohexane, ethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethyl acetate, butyl acetate, MEK, MIBK, diisobutyl ketone, cyclohexanone, ethanol, isopropanol, butanol and the like. The solvent is contained as it is or removed under reduced pressure after completion of the reaction. The reaction ratio of the aromatic vinyl compound and the α, β unsaturated carboxylic acid ester is 1 to 99% by weight, preferably 10 to 90% by weight, based on the total amount of the aromatic vinyl compound and the α, β unsaturated carboxylic acid ester. The α, β unsaturated carboxylic acid ester is 1 to 99% by weight, preferably 10 to 90% by weight.

The (meth) acrylate monomer of a polyol having an alkyl group of C1 to C18 is an alkyl (carbon number 1 to 18) (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (monofunctional monomer). Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. Furthermore, as a bifunctional monomer, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalylhydroxypivalate di (meth) acrylate (commonly called manda) di (meth) acrylate, hydroxypivalylhydroxypivalate dicaprolactonate di (meth) Acrylate, hexanediol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tricyclodecane dimethylol dicaprolactone Di (meth) acrylate, bisphenol A tetrapropylene oxide adduct di (meth) acrylate, bisphenol A polyalkylene oxide adduct di (meth) acrylate, bisphenol F tetrapropylene oxide adduct di (meth) acrylate, bisphenol F polyalkylene Oxide adduct di (meth) acrylate, bisphenol S tetraethylene oxide adduct di (meth) acrylate, bisphenol S polyalkylene oxide adduct di (meth) acrylate, water-added bisphenol A tetrapropylene oxide adduct di (meth) acrylate, Water-added bisphenol A polyalkylene oxide adduct di (meth) acrylate, water-added bisphenol F tetrapropylene oxide adduct di (me ) Acrylate, water-added bisphenol F polyalkylene oxide adduct di (meth) acrylate, water-added bisphenol A di (meth) acrylate, water-added bisphenol F di (meth) acrylate, dihydroxybenzene (catechol, resorcin, hydroquinone, etc.) polyalkylene Oxide di (meth) acrylate, alkyldihydroxybenzene polyalkylene oxide di (meth) acrylate, bisphenol A tetraethylene oxide adduct dicaprolactonate di (meth) acrylate, bisphenol F tetraethylene oxide adduct dicaprolactonate di (meta ) Acrylate and the like. As trifunctional monomers, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate, trimethylolethane (meth) Acrylate, trimethylolethane tri (meth) acrylate, trimethylolhexanetri (meth) acrylate, trimethylolhexanetri (meth) acrylate, trimethyloloctanetri (meth) acrylate, trimethyloloctanetri (meth) acrylate, pentaerythritol Examples thereof include hydroxybenzene (such as pyrogallol) polyalkylene oxide adduct triacrylate and the like. Teeth, diglycerin tetra (meth) acrylate, tri (meth) acrylate, diglycerin polyalkylene oxide tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane tetracapro Examples include lactonate tetra (meth) acrylate, ditrimethylolethane tetra (meth) acrylate, and octa (meth) acrylate. Examples thereof include ditrimethylolbutanetetra (meth) acrylate, ditrimethylolhexanetetra (meth) acrylate, ditrimethyloloctanetetra (meth) acrylate, and the like.

Further, an alkylene oxide adduct (meth) acrylate monomer of an aliphatic alcohol compound, particularly an alkylene oxide adduct (meth) acrylate monomer of an aliphatic alcohol compound having an alkylene oxide of C3 to C20 or more is added to the resin, vegetable oil or fatty acid ester thereof. On the other hand, solubility is improved. Alkylene oxide adduct (meth) acrylate monomer of aliphatic alcohol compound Mono- or poly (1-20) alkylene (C2 to C20) oxide adduct of aliphatic alcohol compound (alkylene oxide such as ethylene oxide, propylene oxide, butylene) Oxide, pentylene oxide, hexylene oxide, etc.) mono or poly (1-10) (meth) acrylate. Alkyl (having 1 to 18 carbon atoms) (meth) acrylate as a monofunctional monomer, such as methanol mono or poly (1 to 20) alkylene (C2 to C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene) Oxide) (meth) acrylate, ethanol mono or poly (1-20) alkylene (C2 -C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, butanol mono or poly ( 1-20) Alkylene (C2 to C20) oxide adducts (As alkylene oxides, for example, ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, hexanol mono Or a poly (1-20) alkylene (C2 to C20) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, octanol mono or poly (1-20) alkylene (C2 C20) Oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, dodecanol mono- or poly (1-20) alkylene (C2 to C20) oxide adduct (for example, alkylene oxide as alkylene oxide) Ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, stearyl mono- or poly (1-20) alkylene (C2 -C20) oxide adduct (as alkylene oxide) Tylene oxide, propylene oxide, and poly (1-20) alkylene (C2 to C20) oxide adducts of butylphenol, octylphenol, nonylphenol or dodecylphenol (alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide) (meta ) Acrylate, etc. Furthermore, ethylene glycol mono- or poly (1-20) alkylene (C2 to C20) oxide adducts (alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide) di (meta) as bifunctional monomers ) Acrylate, diethylene glycol mono- or poly (2-20) alkylene (C2 -C20) oxide adducts (alkylene oxides such as ethyl Rene oxide, propylene oxide, butylene oxide) di (meth) acrylate, triethylene glycol poly (2-20) alkylene (C2 to C20) oxide adduct (alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di ( (Meth) acrylate, polyethylene glycol poly (2-20) alkylene (C2 to C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, propylene glycol poly (2-20) Alkylene (C2 to C20) oxide adducts (e.g., ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, dip Lopylene glycol poly (2-20) alkylene (C2 to C20) oxide adducts (e.g., ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, tripropylene glycol poly (2-20) alkylene (C2 as alkylene oxide) ~ C20) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, polypropylene glycol poly (2-20) alkylene (C2-C20) oxide adduct (e.g., alkylene oxide as alkylene oxide) Ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, butylene glycol poly (2-20) alkylene (C2 to C20) oxide adduct (alkylene) For example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, pentyl glycol poly (2-20) alkylene (C2 to C20) oxide adduct (eg, alkylene oxide, ethylene oxide, propylene oxide, butylene oxide) Di (methneopentyl glycol poly (2-20) (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, hydroxypivalyl hydroxypivalate poly (2-20) alkylene (C2 to C20) Oxide adducts (e.g., ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate (commonly called manda) as hydroxy oxide, hydroxypivalyl hydride Xipivalate dicaprolactonate poly (2-20) alkylene (C2 to C20) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,6 hexanediol poly ( 2-20) Alkylene (C2 to C20) oxide adducts (e.g., ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,6 hexanediol poly (2-20) alkylene oxide adduct (alkylene oxide) For example, ethylene oxide, propylene oxide, butylene oxide, etc.) di (meth) acrylate, 1,2-hexanediol di (meth) acrylate, 1,5-hexanediol poly (2-20) alkylene (C2- 20) Oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,5-hexanediol poly (2 to 20) alkylene (C2 to C20) oxide adduct (alkylene oxide as alkylene oxide) For example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,7-heptanediol poly (2-20) alkylene (C2-C20) oxide adduct (alkylene oxide such as ethylene oxide, propylene oxide) , Butylene oxide) di (meth) acrylate, 1,8-octanediol poly (2-20) alkylene (C2-C20) oxide adduct (alkylene oxide such as ethylene oxide, propylene Oxide, butylene oxide) di (meth) acrylate, 1,2-octanediol poly (2 to 20) alkylene (C2 to C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di ( (Meth) acrylate di (meth) acrylate, 1,9-nonanediol poly (2 to 20) alkylene (C2 to C20) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate as alkylene oxide 1,2-decanediol poly (2-20) alkylene (C2 to C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, , 10-decanediol poly (2-20) alkylene (C2 to C20) oxide adducts (eg, alkylene oxide, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-decanediol poly (2 -20) alkylene (C2 -C20) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,12-dodecanediol poly (2-20) alkylene (C2 -C20 as alkylene oxide) ) Oxide adducts (e.g. ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-dodecanediol mono- or poly (1-20) alkylene (C2-C20) oxide Adducts (e.g., ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,14-tetradecanediol poly (2-20) alkylene (C2-C20) oxide adduct (as alkylene oxide) For example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-tetradecanediol poly (2-20) alkylene (C2 to C20) oxide adduct (alkylene oxide such as ethylene oxide, propylene oxide, butylene) Oxide) di (meth) acrylate, 1,16-hexadecanediol mono- or poly (2-20) alkylene (C2 -C20) oxide adduct (alkylene oxide such as ethylene oxide) Id, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-hexadecanediol poly (2-20) alkylene (C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) Di (meth) acrylate, 2-methyl-2,4-pentanediol poly (2-20) alkylene (C2 to C20) oxide adduct (eg alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) Acrylate, 3-methyl-1,5-pentanediol poly (2-20) alkylene (C2 to C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) (Meth) acrylate, 2-methyl-2-propyl-1,3-propanediol poly (2-20) alkylene (C2 to C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (Meth) acrylate, 2,4-dimethyl-2,4-pentanediol poly (2-20) alkylene (C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meta ) Acrylate, 2,2-diethyl-1,3-propanediol mono- or poly (2-20) alkylene (C2 -C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di ( Meta ) Acrylate, 2,2,4-trimethyl-1,3-pentanediol mono- or poly (2-20) alkylene (C2 -C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (Meth) acrylate, dimethyloloctane poly (2-20) alkylene (C2 to C20) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2-ethyl-1, 3-Hexanediol poly (2-20) alkylene (C2 to C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,5-dimethyl-2 as alkylene oxide 5-hexanediol poly (2-20) alkylene (C2 to C20) oxide adduct (e.g. ethylene oxide as alkylene oxide-de, propylene oxide, butylene oxide) di (meth) acrylate, 2-methyl-1,8-O







Kutandiol poly (2-20) alkylene (C2 to C20) oxide adducts (e.g. ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2-butyl-2-ethyl-1,3- Propanediol poly (2-20) alkylene (C2 to C20) oxide adducts (e.g., ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,4-diethyl-1,5-pentanediol as alkylene oxide Examples of the poly (2-20) alkylene (C2 to C20) oxide adduct (alkylene oxide include, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate. Glycerin poly (2-20) alkylene (C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolpropane poly (2-20) as trifunctional monomer Alkylene (C2 to C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolethane poly (2 to 20) alkylene (C2 to C20) oxide adduct (alkylene as alkylene oxide) For example, ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolhexane poly (2-20) alkylene (C2 to C20) oxide Forms (for example, ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethyloloctane poly (2-20) alkylene (C2 to C20) oxide adduct (for example, ethylene oxide, propylene as alkylene oxide) Oxide, butylene oxide) tri (meth) acrylate, trimethyloloctane poly (3-20) alkylene (C2 to C20) oxide adduct (alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, Pentaerythritol poly (2-20) alkylene (C2 to C20) oxide adducts (alkylene oxides such as ethylene oxide, propylene oxide, Oxide) tri (meth) acrylate and the like. Pentaerythritol poly (2-20) alkylene (C2 to C20) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, diglycerin poly (2- 20) Alkylene (C2 to C20) oxide adducts (e.g., ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, diglycerin poly (2-20) alkylene oxide (for example, ethylene oxide, propylene oxide, Butylene oxide, etc.) Adduct tetra (meth) acrylate, ditrimethylolpropane poly (2-20) alkylene (C2 to C20) oxide adduct (as alkylene oxide) For example, ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, ditrimethylolpropane poly (2-20) alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylolpropane tetracarbonate Prolactonate, tetra (meth) acrylate, ditrimethylolethane poly (2-20) alkylene (C2 to C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, ditri Methylolethane poly (2-20) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) La (meth) acrylate, ditrimethylolbutanepoly (2-20) alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) Tetra (meth) acrylate, ditrimethylolhexane poly (2-20) alkylene (C2 to C20) Oxide adducts (e.g. ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) tetra (meth) acrylate, ditrimethylolhexane poly (2-20) alkylene oxide (e.g. ethylene oxide, propylene oxide, butylene oxide) tetra (meta ) Acrylate, ditrimethyloloctane (2-20) alkylene (C2 -C20) oxide adduct (alkylene oxide such as ethylene oxide) , Propylene oxide, butylene oxide) tetra (meth) acrylate, ditrimethyloloctane poly (4-200) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, dipentaerythritol poly (5-20) ) Alkylene (C2 to C20) oxide adducts (e.g., ethylene oxide, propylene oxide, butylene oxide) penta (meth) acrylate, dipentaerythritol poly (2-20) alkylene (C2 to C20) oxide adducts (alkylene oxide) Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide) hexa (meth) acrylate, propylene oxide, butylene oxide Hexa (meth) acrylate, dipentaerythritol hexacaprolactonate poly (2-20) alkylene (C2 to C20) oxide adducts (alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) hexa (meta ) Acrylate, tripentaerythritol poly (2-20) alkylene (C2 -C20) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) hepta (meth) acrylate, tripentaerythritol poly (2-20) ) Alkylene (C2 -C20) oxide adducts (e.g., ethylene oxide, propylene oxide, butylene oxide) octa (meth) acrylate, tripene as alkylene oxide Erythritol poly (2-20) alkylene (C2 to C20) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) hexa (meth) acrylate, tripentaerythritol polyalkylene oxide hepta (meth) acrylate, Pentaerythritol poly (2-20) alkylene (C2 to C20) oxide adduct (As alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide)

Examples of acrylic ester monomers other than acrylic esters of alcohols having a C1-C18 alkyl group include monofunctional monomers such as phenoxyethyl acrylate, cyclohexyl (meth) acrylate, and tricyclodecane monomethylol (meth) acrylate. Furthermore, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di ( (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1 , 7-Heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,2-octanediol di (meth) acrylate di ( Acrylate), 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 1,2-dodecanediol di (meth) Acrylate, 1,14-tetradecanediol di (meth) acrylate, 1,2-tetradecanediol di (meth) acrylate, 1,16-hexadecanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 1, 14-tetradecanediol di (meth) acrylate, 1 , 16-hexadecanediol di (meth) acrylate, urdi (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tricyclodecane dimethylol dicaprolactonate di (meth) acrylate, trifunctional glycerin tri ( Examples thereof include (meth) acrylate and pentaerythritol tri (meth) acrylate. Tetraerythritol tetra (meth) acrylate, pentaerythritol tetracaprolactonate tetra (meth) acrylate, diglycerin tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol polyalkylene oxide hepta (meth) acrylate, and the like.

Further, the varnish can be made into a gel varnish using a gelling agent. As the gelling agent, usually an aluminum complex compound can be mentioned. Cyclic aluminum compounds such as cyclic aluminum oxide octate (Algomer 800 manufactured by Kawaken Fine Chemical Co., Ltd.), cyclic aluminum oxide stearate (Algomer 1000S manufactured by Kawaken Fine Chemical Co., Ltd.), and the like, as aluminum alcoholates, aluminum ethylate, aluminum isopropylate (river AIPD) manufactured by Ken Fine Chemical Co., Ltd., aluminum sec-butylate (ASPD manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum isopropylate mono-sec-butylate (AMD manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum alkyl acetates such as aluminum di-n -Butoxide-ethyl acetoacetate (Chelope-Al-EB2 manufactured by Hope Pharmaceutical), aluminum-di-iso-butoxide Methyl acetoacetate (Chelope-Al-MB12 manufactured by Hope Pharmaceutical), Aluminum-di-iso-butoxide-ethyl acetoacetate (Chelope-Al-EB102 manufactured by Hope Pharmaceutical), Aluminum-di-iso-butoxide-ethyl acetoacetate (Hope Pharmaceutical) (Chelope-Al-EB2), aluminum-di-iso-propoxide-ethyl acetoacetate (Chelope-Al-EP12, manufactured by Hope Pharmaceutical Co., Ltd., ALch manufactured by Kawaken Fine Chemicals), aluminum-tris (acetylacetonate) (Kawaken Fine Chemicals) ALCH-TR), aluminum-tris (acetylacetoacetate) (aluminum chelate A manufactured by Kawaken Fine Chemicals), aluminum-bis (ethylacetylacetonate) ) -Monoacetylacetonate (Aluminum chelate D manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum chelate M (produced by Kawaken Fine Chemical Co., Ltd.), aluminum chelate NB-15 (manufactured by Hope Pharmaceutical Co., Ltd.), Kerope S (manufactured by Hope Pharmaceutical Co., Ltd.) -2 (manufactured by Hope Pharmaceutical Co., Ltd., Liquid Olepe AOO (manufactured by Hope Pharmaceutical Co., Ltd.), Liquid Olipe AOS (manufactured by Hope Pharmaceutical Co., Ltd.) Aluminum stearate (manufactured by Nippon Oil & Fats Co., Ltd.), aluminum oleate, Examples thereof include aluminum naphthonate, aluminum urate, and aluminum acetylacetonate, and these gelling agents are used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of varnish. As a gelling agent, cyclic dipeptides and properties that allow organic liquids to gel Bisamides such as lenbis (12-hydroxyoctadecanoic acid) amide, Al-Mg-hydroxycaprylate, Al-Mg-hydroxymyristate, Al-Mg-hydroxypalmitate, Al-Mg-hydroxybehenate, etc. A powdery aluminum-magnesium compound is exemplified. Further examples include organic titanates such as tetraisopropyl titanate, tetra n-butyl titanate, tertreoctyl titanate, titanium acetylacetonate, titanium octylene glycolate, titanium lactate, and titanium lactate ethyl ester. Furthermore, organic zirconium such as zirconium tetrabutoxide, zirconium acetylacetone, zirconium acetylacetone, zirconium acetylacetone, acetylacetone zirconium butoxide, ethyl acetoacetate butoxide, and the like are exemplified. The preparation of the gel varnish is usually obtained by adding 0.1 to 3 parts by weight of a gelling agent and reacting in a temperature range of 100 to 200 ° C. for 30 minutes to 2 hours.

Radical polymerization initiators can be broadly classified into photocleavage type and hydrogen abstraction type. Examples of the former include benzoin, such as benzoin, benzoin methyl ether, benzoin isopropyl ether, α-acrylobenzoin, benzyl, Irgacure 907 (2-methyl-2-morpholino (4-thiomethylphenyl) propane-1 manufactured by Ciba Specialty Chemicals) -ON), Irgacure 369 (2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone manufactured by Ciba Specialty Chemicals), Irgacure 651 (Benzylmethyl ketal manufactured by Ciba Specialty Chemicals), Irgacure 184 (1-hydroxycyclohexyl phenyl ketone made by Ciba Specialty Chemicals), Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one made by Merck), Darocur 1116 (Merck 1- ( 4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one), 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, ZLI3331 (Ciba Specialty Chemicals 4- (2-acryloyl-oxyethoxy) phenyl-2-hydroxy-2-propylketone, diethoxyacetophenone, Esacure KIP100 (manufactured by Ramberty), Lucillin TPO (manufactured by BASF), BTTB (manufactured by NOF Corporation), CGI1700 (Ciba Specialty Chemicals Co., Ltd. and the like. Examples of the latter include benzophenone, p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4. '-Me Le - diphenyl sulfide,
Aryl ketone initiators such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4 diethylthioxanthone, 2,4 dichlorothioxanthone, acetophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis Examples include (dimethylamino) benzophenone, isoamyl p-dimethylaminobenzoate, dialkylaminoaryl ketone initiators such as p-dimethylaminoacetophenone, thioxanthone, xanthone-based and halogen-substituted polycyclic carbonyl-based initiators. The These can be used alone or in combination. These initiators can be used in the composition in the range of 0.1 to 30% by weight, but preferably in the range of 1 to 15% by weight.

Next, the usage form as a printing ink composition in this invention is demonstrated. The printing ink composition in the present invention is usually used in the form of a lithographic printing ink. In general,
Colorant or extender 1-40% by weight
Resin varnish or resin gel varnish 10-70% by weight
Monomer having a radical polymerizable double bond 10 to 70% by weight
Radical polymerization inhibitor 0.01-1% by weight
Radical polymerizable initiator and / or sensitizer 0-15% by weight
Other additives 0-10% by weight
Is used in the composition consisting of Further, since the resin is solid at room temperature, it is dissolved in a monomer having a radical polymerizable double bond and used as a resin varnish prepared by adding a radical polymerization inhibitor. In order to make the viscosity of the resin varnish easy to produce a printing ink composition (100 to 200 Pa · s), resin / monomer having radical polymerizable double bond / radical polymerization inhibitor = 20 to 50 parts by weight / 80 to The composition ratio is 50 parts by weight / 0.01 to 1 part by weight, and the resin dissolves in an air stream at 80 to 120 ° C. in 30 minutes to 1 hour. Further, in order to obtain a resin gel varnish, 0.1 to 3 parts by weight of a gelling agent is added to the dissolved resin varnish and reacted at 100 to 120 ° C. for 30 minutes to 1 hour.

The printing ink of the present invention comprises a pigment, a resin varnish and / or a gel varnish thereof, a monomer having a radical polymerizable double bond, a radical polymerization inhibitor, a radical polymerizable initiator, and / or a sensitizer between room temperature and 100 ° C. In addition, printing ink composition components such as other additives are produced using kneading, mixing, and adjusting machines such as a kneader, three rolls, an attritor, a sand mill, and a gate mixer.

There are pigments as colorants, and inorganic pigments and organic pigments including extender pigments can be shown. Inorganic pigments such as yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, petal, alumina white, calcium carbonate, ultramarine, carbon black, graphite, aluminum powder, bengara etc. as organic pigments Are soluble azo pigments such as β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid anilide, acetoacetate anilide, pyrazolone, β-naphthol, β-oxynaphthoic acid anilide, Insoluble azo pigments such as acetoacetanilide monoazo, acetoacetanilide disazo and pyrazolone, phthalocyanine pigments such as copper phthalocyanine blue, halogenated (chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine , Quinacridone, geo Polycyclics such as sazine, selenium (pyrantron, anthrone, indanthrone, anthrapyrimidine, flavantron, thioindigo, anthraquinone, perinone, perylene), isoindolinone, metal complex, quinophthalone Various publicly known pigments such as pigments and heterocyclic pigments can be used.
Furthermore, the polymerization inhibitors exemplified above are used.

Furthermore, other additives can be used in the printing ink as required. For example, anti-friction agents, anti-blocking agents, slip agents, anti-scratch agents include carnauba wax, wax, lanolin, montan wax, paraffin wax, microcrystalline wax and other natural waxes, Fischer-Trops wax, polyethylene wax, polypropylene Synthetic waxes such as wax, polytetrafluoroethylene wax, polyamide wax, and silicone compound can be exemplified.

The active energy ray-curable printing ink of the present invention is also applied to offset printing using dampening water, but is also applied to waterless printing that does not use dampening water, that is, dry lithographic printing.
For example, by combining 0.1 to 10% by weight of an organopolysiloxane in a dry lithographic printing ink composition, the poor solubility of this material is utilized, and after printing, the organopolysiloxane appears on the surface of the ink composition. A weak boundary layer that has a very weak binding force at the interface between the ink and the plate, and the organopolysiloxane appears on the surface of the ink composition after printing. In the technical field, it is possible to improve the suitability of dry lithographic printing (ink does not adhere to the non-image area) by forming “WFBL” (Week Fluid Boundary Layer). Examples of the organopolysiloxane of the present invention include dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane. For example, TSF451-10, TSF451-20, TSF451-30, TSF451-50, TSF451-100, TSF451-200, TSF451-300, TSF451-350, TSF451-500, TSF451-1000, TSF451- manufactured by Toshiba Silicon Corporation 3000, TSF451-5000, TSF451-6000, TSF451-1M, TSF451-3M, TSF451-5M, TSF451-6M, TSF451-10M, TSF451-20M, TSF451-30M, TSF451-50M, TSF456-100, TSF456-200, TSF456-1000, TSF456-2000, TSF456-1M, TSF410, TSF411, TSF4421, XF42-A3161, TSF 84, TSF431, YF33-100, YF33-3000, YF33-1M, TSF458-50, TSF433, TSF404, TSF405, TSF4045, TSF451-5A, TSF451-10A, TSF451-50A, TSF451-100A, TSF451-350A, TSF451- 1000A, TSF451-5000A, TSF437, TSF4440, TSF433, TSF404, TSF405, TSF4045, TSF451-5A, TSF451-10A, TSF451-50A, TSF451-100A, TSF451-350A, TSF451-1000A, TSF451-5000A, TSF440, TS TSF433, TSF404, TSF405, TSF4045, TSF4 1-5A, TSF451-10A, TSF451-50A, TSF451- 100A, TSF451-350A, TSF451-1000A, TSF451-5000A, TSF437, TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460, TSF4600, TSF4700, TSF4701 TSF4703, TSF4704, TSF4705, TSF4706, TSF4707, TSF4708, TSF4709, TSF4450, TSF4730, XF42-B0970, FQF501, etc. are illustrated. Further, Pentide A, Pentide H, Pentide M, Pentide Q, Pentide Q-N, Pentide S, Pentide 7, Pentide E-10, Pentide 29, Pentide 31, Pentide 32, Pentide 51, Pentide 54, manufactured by Dow Corning Asia Co., Ltd. Pentide 56, Pentide 57, DCZ-6018, DKQ8-8011, and the like. Furthermore, KF-351, KF-352, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF are used as non-reactive silicone oils manufactured by Shin-Etsu Silicon Co., Ltd. -618, KF-6011, KF-6015, KF-6004, X-22-4272, X-22-4925, X-22-6266, KF-410 as methylstill modified silicone oil, KF-412 as alkyl modified silicone oil KF-413, KF-414, KF-910, X-22-715 as higher fatty acid ester-modified silicone oil, KF-3935 as higher fatty acid-containing silicone oil, FL-5, FL-10, X as fluorine-modified silicone oil -22-821, X-22-822, FL100, etc. It is.

  In the present invention, a printing ink solvent having a boiling point of 200 to 400 ° C. containing a volatile organic compound (VOC) such as a conventional petroleum solvent may be used.

  The printing ink solvent of the present invention includes, for example, Nippon Oil Co., Ltd. No. 1 spindle oil, No. 3-8 Solvent, Naphthezol H, Alkene 56NT, Mitsubishi Chemical Corporation Diadol 13, Dairen 168, Nissan Chemical Co., Ltd. Examples thereof include Foxocol, Foxocol 180 and the like. The printing ink solvent with the aromatic component reduced to 3% or less is a petroleum solvent having the same boiling point range, and the weight ratio of aromatic component / naphthene component / paraffin component is 0-3 / 0-100 / 100- It is a solvent of 0 and sometimes contains an olefinic component. Specifically, AF Solvents 4-8, No. 0 Solvent H manufactured by Nippon Oil Co., Ltd., N-paraffin C14-C18 manufactured by ISU Corporation, Supersol LA35, LA38 manufactured by Idemitsu Kosan Co., Ltd., Exxon Chemical ( Exesol D80, D110, D120, D130, D160, D100K, D120K, D130K, etc., and Maggie Sol-40, -44, -47, -52, -60, etc. manufactured by Maggie Bros. are exemplified. The aniline point is preferably 60 to 115 ° C. If a solvent with an aniline point higher than 115 ° C. is used, the solvent with the resin used in the ink composition will be insufficient and the fluidity of the ink will be insufficient, resulting in poor leveling on the printing medium and gloss. You can only get prints with no. Further, ink using a solvent having an aniline point lower than 60 ° C. is poor in detachment of the solvent from the ink film at the time of drying and causes drying deterioration. Further, in the present invention, there may be used a solvent containing a paraffinic component such as No. 0 solvent, N-paraffin C14-C18 manufactured by ISU Co., Ltd., and an olefinic component such as dialen 168. In particular, the present dry lithographic printing ink composition comprises 1 to 30% by weight of 5 to 1 million, preferably 5 to 150,000 weight average molecular weight resin and 0.1 to 10% by weight of paraffin and olefin solvent. The dry lithographic plate is formed by adjusting the solubility with the material and forming a weak boundary layer "WFBL (Week Fluid Boundary Layer) in this technical field" between the dry lithographic plate and the ink, which has a very weak bonding force due to the solvent. It is possible to improve printability (ink does not adhere to non-image areas).

Furthermore, not only color printing, but also color printing such as yellow, red, indigo, and ink, as well as transparent overprint varnish (commonly called OP varnish) after printing them. Active energy ray-curable printed materials include printed materials for forms, printed materials for various books, printed materials for packaging such as carton paper, various printed materials for plastics, seals, printed materials for labels, printed materials for arts, printed materials for arts (printed arts, printed beverages, cans, etc.) Applied to food prints).

Examples of the present invention and comparative examples will be described below. The present invention is expressed in parts by weight. (Synthesis example of alkyd resin)
Example resin R1
A four-necked flask equipped with a stirrer, equipped with a water separation tube and equipped with a thermometer was charged with 68 parts of benzoic acid, 340 parts of disproportionated rosin, 278 parts of trimethylolpropane, and 50 parts of xylene. When the acid value was reduced to 5 or less by reacting at 4 ° C., cooled to 180 ° C., charged with 315 parts of phthalic anhydride, then gradually heated up and reacted at 230 ° C. for 10 hours, resulting in an acid value of 20. After removing the solvent under reduced pressure at the same temperature, it was pumped out. Resin R1 (weight average molecular weight 57,000 in terms of polystyrene by gel permeation chromatography measurement, softening point 95 ° C.) was obtained.
Similarly, as shown in Table 1, after reacting monobasic acid and polyol, polybasic acid was further reacted to obtain resins of Example resins R2 to R7.
Example Production Example of Resin R8 A four-necked flask equipped with a stirrer, equipped with a water separation tube, equipped with a thermometer, 154 parts isoborneol (isobornyl alcohol), 0.2 part hydroquinone, 20 parts toluene, 86 parts methacrylic acid Then, 2 parts of P-toluenesulfonic acid is charged and reacted under air blowing until the acid value becomes 15 or less at 90 to 115 ° C. Thereafter, 12 parts of a 20% aqueous sodium hydroxide solution is added, neutralized, washed with 200 ml of water three times, and then desolvated under reduced pressure at 90 to 115 ° C. to obtain isoborneol methacrylic ester (isobornyl methacrylate). Next, 150 parts of toluene was charged, and the temperature was raised to 80 ° C. under a nitrogen stream. 50 parts of styrene, 40 parts of the above isoborneol methacrylic ester (isobornyl methacrylate), 5 parts of butyl methacrylate, 5 parts of hydroxypropyl methacrylate, benzoyl peroxide A solution obtained by dissolving 3 parts in advance was added dropwise over 3 hours. Two hours after the completion of the dropwise addition, 0.5 part of benzoyl peroxide was added and the reaction was continued for another 2 hours, and then the solvent was removed and pumped out. (Example resin R8)
Example Production Example of Resin R9 A four-necked flask with a stirrer, a water separator, and a thermometer was equipped with 1000 parts of Marcaretz 510 (C5 petroleum resin manufactured by Maruzen Petroleum) and 80 parts of maleic anhydride at 180 ° C. for 2 hours. It is the reacted polybasic acid. Charge 93 parts of neopentyl glycol and 50 parts of xylene, gradually raise the temperature in a nitrogen stream, react at 230 ° C. for 8 hours, react until the acid value is 10 or less (9.2), remove solvent under reduced pressure at the same temperature, and pump out resin R1 (weight average molecular weight 11,000 in terms of polystyrene by gel permeation chromatography measurement, softening point 115 ° C.) was obtained. (Example resin R9)

表中ＤＡ−１とはあらかじめ重合ロジン３８３部、無水マレイン酸２８部を仕込み１８０℃で２時間ディールスアルダー反応させた多塩基酸、ＤＡ−２はマルカレッツ５１０（丸善石油製Ｃ5系石油樹脂）を３８３部、無水マレイン酸２８部を１８０℃２時間ディールスアルダー反応させた多塩基酸である。
実施例樹脂Ｒ10の製造例
ハイブリッド化合物（Ｒ10）の製造例
攪拌機付き、水分離管付き、温度計付き四つ口フラスコに、大豆油油脂肪酸２６６部、トリメチロールプロパン１３４部、ｐ−トルエンスルフォン酸６部、トルエン４０部を仕込み、窒素気流下で徐々に昇温し、１１０℃で９時間反応させ、酸価が５以下になっｔ、メトキノン０．６部、アクリル酸１３７部を仕込み、窒素容量気流下で１１０℃で反応させた。約７時間後に脱水反応が止まったところで、シクロヘキサン２０部を仕込み、さらに還流にて脱水反応を継続させ、酸価が１０．０になったところで、等量の水で３回水洗し、水洗水がｐＨ試験紙で中性またはそれに近いのを確認した後、脱溶媒して汲み出した。酸価は２．０であった。（実施例樹脂Ｒ10）
（ロジンフェノール樹脂Ｒ11）
先ず下記レゾール型フェノール樹脂を合成する。
（レゾール型フェノール樹脂の合成）
攪拌機、還流冷却器、温度計付４つ口フラスコにｐ−オクチルフェノール２０６部、３７％ホルマリン２０３部、キシレン２５０部を仕込み、窒素ガスを吹き込みながら加熱攪拌し、５０℃で水酸カルシウム２．０部を水１０部に分散させて、その分散液を添加し９５℃に昇温し、同温度で３．５時間反応させた。その後、冷却し、硫酸で中和、水洗した。レゾールキシレン溶液層と水層を静置分離した。このレゾール型フェノール樹脂をレゾ−ル液とする。出来上がったレゾール型フェノール樹脂を使用し下記ロジンフェノ−ル樹脂の合成をする。
（ロジンフェノ−ル樹脂の合成）
攪拌機、水分離器付き還流冷却器、温度計付４つ口フラスコに窒素ガスを吹き込みながら、ロジン６０部を仕込み、加熱攪拌し、２００℃でレゾール液４０部（固形分）を滴下しながら約２時間かけて仕込み、その間水とキシレンを回収しながら反応させ、仕込み終了後、昇温し２５０℃でグリセリン６．０部を仕込み１２時間反応させ、酸価が２５以下になったので汲み出した。
本樹脂の重量平均分子量は４．５万であった。（比較例樹脂Ｒ11）
注）＊ロジンと反応するレゾ−ル液の重量部は１５０℃３０分加熱し蒸発後の固形分の重量部を示す。
＊重量平均分子量は東ソー（株）製ゲルパーミエイションクロマトグラフィ（ＨＬＣ８０２０）で検量線用標準サンプルはポリスチレンで測定した。
で測定した。

In the table, DA-1 is a polybasic acid prepared by previously charging 383 parts of polymerized rosin and 28 parts of maleic anhydride at 180 ° C. for 2 hours, and DA-2 is Marcaretz 510 (C5 petroleum resin manufactured by Maruzen Petroleum). A polybasic acid obtained by reacting 383 parts of maleic anhydride 28 parts with Diels-Alder reaction at 180 ° C. for 2 hours.
Example Production Example of Resin R10 Production Example of Hybrid Compound (R10) A four-necked flask with a stirrer, a water separator, and a thermometer, 266 parts of soybean oil fatty acid, 134 parts of trimethylolpropane, p-toluenesulfonic acid 6 parts and 40 parts of toluene are charged, gradually heated in a nitrogen stream, and reacted at 110 ° C. for 9 hours. The acid value becomes 5 or less, 0.6 parts of methoquinone, and 137 parts of acrylic acid are charged. The reaction was carried out at 110 ° C. under a volume air flow. When the dehydration reaction was stopped after about 7 hours, 20 parts of cyclohexane was added, and the dehydration reaction was continued by refluxing. When the acid value reached 10.0, the water was washed three times with an equal amount of water. Was confirmed to be neutral or close to pH test paper, and then the solvent was removed and pumped out. The acid value was 2.0. (Example resin R10)
(Rosin phenolic resin R11)
First, the following resol type phenol resin is synthesized.
(Synthesis of resol type phenol resin)
A four-necked flask equipped with a stirrer, reflux condenser, and thermometer was charged with 206 parts of p-octylphenol, 203 parts of 37% formalin and 250 parts of xylene, heated and stirred while blowing nitrogen gas, and calcium hydroxide 2.0 at 50 ° C. Parts were dispersed in 10 parts of water, the dispersion was added, the temperature was raised to 95 ° C., and the reaction was carried out at the same temperature for 3.5 hours. Then, it cooled, neutralized with sulfuric acid, and washed with water. The resole xylene solution layer and the aqueous layer were allowed to stand and separate. This resol type phenol resin is used as a resol solution. Using the finished resol type phenol resin, the following rosin phenol resin is synthesized.
(Synthesis of rosin phenol resin)
While blowing nitrogen gas into a four-neck flask with a stirrer, a water separator and a thermometer, charge 60 parts of rosin, heat and stir, and add about 40 parts of a resole solution (solid content) dropwise at 200 ° C. Charged over 2 hours, while allowing water and xylene to be collected while reacting, heated up, heated up at 250 ° C. and charged with 6.0 parts of glycerin for 12 hours, acid value was 25 or less and pumped out .
The weight average molecular weight of this resin was 45,000. (Comparative resin R11)
Note) * The parts by weight of the resor liquid that reacts with rosin is the parts by weight of solids after evaporation at 150 ° C for 30 minutes.
* The weight average molecular weight was measured by gel permeation chromatography (HLC8020) manufactured by Tosoh Corporation and the standard sample for the calibration curve was measured by polystyrene.
Measured with

(Example of resin varnish creation)
Example varnish V1
To make a resin varnish for printing ink, 50 parts of Example resin (R1), 10 parts of Example resin (R10), ditrimethylolpropane tetraacrylate, with a four-necked flask equipped with a stirrer, with a water separation condenser, and with a thermometer 39.9 parts and 0.1 part of tertiary butyl hydroquinone were charged, dissolved in an air stream at 100 ° C. for 30 minutes to 1 hour, sampled and measured for viscosity with a B-type viscometer, 148 Pa · s / It was 25 ° C.
Similarly, Table 2 shows Example varnishes V2 to V6.

(Example varnish V7)
In order to make a resin varnish for printing ink, 45 parts of Example resin (R7) and 15 parts of oil are dissolved at 190 ° C in a four-necked flask with a stirrer, a water separation condenser, and a thermometer. Furthermore, 1 part of aluminum di-iso-propoxide ethyl acetonate manufactured by ALCH (Kawaken Fine Chemical Co., Ltd.) was added and reacted at 190 ° C for 1 hour, then cooled to 100 ° C and neopentyl glycol dipropylene oxide diacrylate 39.4. Parts, tertiary butyl hydroquinone 0.1 part, dissolved in air at 100 ° C. for 30 minutes to 1 hour, sampled and measured for viscosity with a B-type viscometer, 285 Pa · s / 25 ° C. The viscosity increased and the gelation ability was confirmed.

Comparative Example Varnish Comparative Example Varnish (V8) Production Example (Oxidation Polymerized Varnish)
A four-necked flask with a stirrer, a water separation condenser, a thermometer, under a nitrogen stream, 45 parts of rosin-modified phenolic resin R11, 20 parts of oil, AF5 solvent (Aroma Free Ink manufactured by Nippon Oil Co., Ltd.) 34.4 parts of solvent), 0.5 part of ALCH (Kawaken Fine Chemical Co., Ltd. gelling agent) and 0.1 part of t-BHQ (tertiary butyl hydroquinone) were charged and dissolved by heating at 200 ° C. for 1 hour. When the viscosity was measured with a cone plate viscometer, it was 98 Pa · s / 25 ° C.

  In the same manner, Comparative Example varnishes V9 and V10 were prepared according to the formulation shown in Table 3.

Comparative Example Production Example of Varnish (V11) (Active Energy Ray Curing Varnish)
A four-necked flask with a stirrer, a water separation condenser, and a thermometer, 30 parts of Dap Tote DT170 (Dialylphthalate resin manufactured by Tohto Kasei Co., Ltd.), 69.9 parts of ditrimethylolpropane tetraacrylate, 0.1 part of hydroquinone Was dissolved in an air stream at 100 ° C. for 30 minutes to 1 hour. When the viscosity was measured with a cone plate viscometer, it was 152 Pa · s / 25 ° C. Similarly, Comparative Example Varnish V12 was prepared with the formulation shown in Table 3.

Production Example of Curable Ink (Ink 1) 18 parts of Carmine 6B (Red Pigment manufactured by Toyo Ink Co., Ltd.), 44 parts of Varnish V1, CN111 (epoxidized soybean oil acrylic ester manufactured by Kayaku Sartomer) 5 26.9 parts of ditrimethylolpropane tetraacrylate, 2.5 parts of 4,4′-bis (diethylamino) benzophenone (EAB), 2.5 parts of Irgacure 907, t-BHQ (tertiary butyl hydroquinone) 0 .1 part and 1 part of manganese naphthenate were charged and manufactured by a conventional method using a three-roll mill.

  The ink was prepared with a tack value of 7 to 8/25 ° C. Inks 2 to 10 were produced according to the formulations shown in Tables 4 and 5 below. Inks 9 and 10 are examples of electron beam curable inks.

Comparative Example Production Example of Oil-Based Ink (Ink 11) 18 parts of Carmine 6B, 70.9 parts of Varnish V8, 10 parts of AF5 solvent, 0.1 part of t-BHQ (tertiary butyl hydroquinone), 1 part of manganese naphthenate Was prepared by a conventional method using a three-roll mill.
The ink was prepared with a tack value of 7 to 8/25 ° C.

  Similarly, Comparative Example oil-based inks 12 and 13 were produced according to the formulation shown in Table 6 below.

Comparative example UV curable ink (ink 14)
18 parts of Carmine 6B, 30 parts of Varnish V12, 26.9 parts of ditrimethylolpropane tetraacrylate, 20 parts of dipentaerythritol hexaacrylate, 2.5 parts of EAB, 2.5 parts of Irgacure 907, 0.1 part of hydroquinone Was prepared by a conventional method using a three-roll mill. The ink was prepared with a tack value of 7 to 8/25 ° C.

  In the same manner, a comparative ultraviolet curable ink 15 was manufactured according to the formulation shown in Table 6.

Comparative example Electron curable ink (ink 16)
18 parts of Carmine 6B, 35 parts of varnish V11, 26.9 parts of ditrimethylolpropane tetraacrylate, 20 parts by weight of dipentaerythritol hexaacrylate, and 0.1 part of hydroquinone were prepared in a conventional manner using a three-roll mill. . The ink was prepared with a tack value of 7 to 8/25 ° C.
Similarly, a comparative electron beam curable ink 17 was produced according to the formulation shown in Table 5.
The effect of the present invention will be described with a glossback test. (Examples 1-10, Comparative Examples 1-9)
-In case of UV irradiation-
Using a RI tester (a simple printing machine manufactured by Meisei Seisakusho Co., Ltd.) on Maricoat paper (coated cardboard manufactured by Hokuetsu Paper Industries Co., Ltd.) and color-printing at 0.3 cc of ink, wire bar # 3K-lock proof immediately A UV curable varnish (FDPCA902 varnish: manufactured by Toyo Ink Manufacturing Co., Ltd.) was applied with UV light (RKPRINT-COAT INSTRUMENTS Ltd), and the gloss was measured immediately and after 72 hours. In addition, an adhesion test by cellophane tape peeling was also performed. For UV irradiation, an irradiation device UVC-2535 (one 120 W / cm ultra-high pressure mercury ozone uncut lamp, conveyor speed 30 m / min) manufactured by USHIO Co., Ltd. was used. The gloss meter was used under the condition of 60 degrees made by Murakami Color Research Laboratory.
-In the case of electron beam irradiation-
The color was printed under the same conditions as in the case of ultraviolet irradiation, and after EB curable varnish (varnish obtained by removing the initiator from FDPCA902) was applied, electron beam irradiation was performed immediately. For electron beam irradiation, irradiation was performed at 30 KGy using a low energy electron beam irradiation apparatus (pressurized voltage of 175 KV, nitrogen-substituted atmosphere with an oxygen concentration of 500 ppm) manufactured by ESI, USA.

  The above results are summarized in Table 7.

Next, the effect of the present invention will be described with a blanket swelling test.

  Each ink and each raw material were placed on a blanket S7400 manufactured by Kinyo Co., Ltd., which is generally used for oil-based inks, and the blanket swellability after 72 hours was measured with a micro gauge. The difference between the blanket thickness after swelling and the blanket thickness before swelling was divided by the thickness of the blanket before swelling and expressed as a percentage (%). The results are summarized in Table 7. In the table, 0 to 0.5% is well swelled, 0.6 to 0.9% is slightly swollen but practical level, and 1.0% or more is poor.

  The above results are summarized in Table 8.

Ink washability:
After printing each ink with an RI tester, the ink was washed with a mineral turpent. The results are shown in Table 8. In the table, ○ indicates good cleaning properties, and X indicates poor cleaning properties.

Claims (10)

1. Obtained by esterification reaction of 0.1 to 20% by weight of vegetable oil and / or its fatty acid ester and / or modified product thereof (A), monobasic acid (B1), polyol (B2), polybasic acid (B3) Alkyd resin (B) having a softening point of 50 to 180 ° C. having a cyclic structure of ˜40% by weight, (meth) acrylate monomer (C) of alcohol having an alkyl group of C1 to C18 of 10 to 70% by weight, 1 to 40 An active energy ray-curable printing ink composition containing a weight% colorant or extender pigment (D). 2. The active energy ray-curable printing according to claim 1, wherein the monobasic acid (B1) is 0 to 50% by weight of an aliphatic monobasic acid and / or 50 to 100% by weight of an aromatic or alicyclic monobasic acid. Ink composition. 3. The active energy ray curing according to claim 1, wherein the polybasic acid (B3) is 0 to 50% by weight of an aliphatic polybasic acid and 50 to 100% by weight of an aromatic and / or alicyclic polybasic acid. Printing ink composition. The cyclic polybasic acid contains 1 to 100% by weight of a cyclic polybasic acid which is a reaction product of petroleum resin and / or rosin and an α, β-ethylenically unsaturated carboxylic acid or anhydride thereof. The active energy ray-curable printing ink composition according to any one of the above. The active energy ray-curable printing ink composition according to any one of claims 1 to 4, comprising a resin having a softening point of 50 to 180 ° C other than the alkyd resin (B). The active energy ray-curable printing ink composition according to any one of claims 1 to 5, comprising a (meth) acrylate monomer or a (meth) acrylate oligomer other than the (meth) acrylate monomer (C) according to claim 1. The active energy ray-curable printing ink composition according to any one of claims 1 to 6, comprising a radical polymerizable initiator. The active energy ray-curable ink composition according to any one of claims 1 to 7 is printed on a substrate, and the active energy ray-curable overcoat varnish or overprint varnish is applied in a state where the printing ink is uncured or cured. A printing method characterized by being worked and irradiated with active energy rays. A printed matter obtained by printing the active energy ray-curable printing ink composition according to claim 1. A printed matter obtained by the printing method according to claim 8.