JP2002293832A - Hardenable composition, hardenable ink, its printing method and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printed matter giving high gloss and aesthetically high quality by combining with an active energy ray hardenable over print varnish which can be printed by a printer for an oily ink. SOLUTION: It is characterized in that a hardenable composition is used as a hardenable print material, which comprises a hybrid compound having a fatty acid residue and a (meth)acryloyl residue, a vegetable oil or its fatty acid ester and a (meth)acryl monomer or a (meth)acryl oligomer having an ethylenically unsaturated double bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a hybrid compound having both a fatty acid residue and a (meth) acryloyl residue, a vegetable oil or a fatty acid ester thereof, and a (meth) acrylic monomer having an ethylenically unsaturated double bond or A curable composition (hybrid curable composition) comprising a (meth) acrylic oligomer, a curable ink (hybrid ink) using the same, and an active energy ray curable liquid immediately after printing the hybrid ink. The present invention relates to a printing method of applying an overcoat varnish and then irradiating an active energy ray, and a printed matter obtained.

[0002]

2. Description of the Related Art In printing various paper containers, books, posters, calendars, labels, wrapping papers, cards, and the like, aesthetic luxury and various resistances (rub resistance, water resistance, oil resistance, solvent resistance) are imparted. For the purpose, it has been generally practiced to coat an overcoat varnish, particularly an active energy ray overcoat varnish, after printing the ink. For example, a method of printing an oil-based ink (oxidatively polymerizable), stacking the bar until several days after the ink dries, and then applying an active energy ray-curable overcoat varnish (oil-based ink / active energy ray-curable varnish) Off-line system), method of applying active energy ray-curable overcoat varnish immediately after printing active energy ray-curable ink (active energy ray-curable ink / active energy ray-curable varnish in-line system) Had been taken. However, the former offline
In the case of the system, the working efficiency is poor, and in the case of the latter in-line system, there are problems such as the high cost of the active energy ray-curable ink. Further, the above-mentioned oil-based ink often uses a volatile hydrocarbon-based ink solvent which is a mineral oil fraction. However, in recent years, there has been an increasing need for VOC (volatile organic compound) -free inks in which volatile hydrocarbon-based ink solvents are completely eliminated from the oil-based inks in consideration of the environment. For example, according to Fukuda and Ishii, etc. (Journal of the Printing Society of Japan, Vol. 37, No. 5, p. 51), if it becomes possible to make VOC-free offset printing ink, more than 40,000 tons of petroleum oil 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 a multicolor printing machine for oil-based ink, and an active energy ray-curable overcoat varnish is applied immediately after printing the oil-based ink. Attempts have been made to produce glossy prints by curing, but this method gradually reduces the gloss, especially when multiple colors of ink are overprinted from a single color and thick embossed. In addition, there has been a problem that the deterioration of gloss continues for several days (gross back), losing aesthetic luxury and losing commercial value.

On the other hand, in a printing maker having only a multi-color printing machine for oil-based ink, if an attempt is made to obtain a printed matter using the in-line active energy ray-curable ink / active energy ray-curable varnish system described above, The active energy ray-curable ink infiltrates and swells into the rubber roll or blanket of the printing press, causing poor transfer of the ink or changing the design when performing the next print, causing the print pattern trace on the swollen portion to appear on the next print. It appears as a thin ghost, which impairs the commercial value of the printed matter. In addition, there are various problems, such as the inability to use a cleaning fluid for oil-based ink in the printing press.Change to a rubber roll or blanket for printing that has durability for active energy ray-curable ink, or use only for active energy ray-curable ink. There is a problem that it is necessary to introduce a new multicolor printing machine.

[0005] Therefore, for the reasons described above, there is a demand for the development of an ink / varnish system capable of suppressing gloss back after varnish application and printing without problems on a multicolor printer for oil-based ink. .

[0006]

SUMMARY OF THE INVENTION The present invention relates to a general oil-based printing ink, which has good properties such as swelling resistance, detergency, suitability for emulsification printing, misting, etc., and low cost. A curable ink (hybrid ink) that does not cause the above gloss back even when an active energy ray-curable overcoat varnish is applied with a wet and the in-line printing method of irradiating with an active energy ray is performed, and curability for the same. The present invention relates to a composition (hybrid curable composition), a printing method thereof, and a printed material thereof.
Further, the present invention relates to a volatile organic compound (V) such as a petroleum solvent.
It is an object of the present invention to provide a curable ink that does not use any OC) and a printed material printed using the curable ink. According to the present invention, a thermogravimetric weight loss of 1% or less (excluding water) in VOC measurement method Methyod24 (heating residue measurement by heating at 110 ° C. for 1 hour) presented by the U.S. Environmental Protection Agency is provided.
And VOC-free inks and printed matter can be provided. However, the present invention is also applicable as a curable ink containing a volatile organic compound (VOC) such as a conventional petroleum solvent.

[0007]

SUMMARY OF THE INVENTION The present invention provides a hybrid compound obtained by an ester reaction of a polyol (A), a fatty acid (B-1) having 4 to 36 carbon atoms, and (meth) acrylic acid (C). A curable composition comprising: a vegetable oil or a fatty acid ester thereof, and a (meth) acrylic monomer or a (meth) acrylic oligomer having an ethylenically unsaturated double bond. The curable composition is a compound obtained by further subjecting the acid (B-2) to an ester reaction. The present invention further provides a fatty acid (B-1) having 4 to 36 carbon atoms in an amount of 20% by weight to 80% by weight and ( 5% by weight of (meth) acrylic acid
A curable composition containing a hybrid compound consisting of up to 40% by weight; and the present invention further provides a curable composition wherein the fatty acid (B-1) having 4 to 36 carbon atoms is a fatty acid of a drying oil or a semidrying oil. Further, the present invention is a curable composition wherein the vegetable oil or a fatty acid ester thereof is a drying oil or a semi-dry oil, or a fatty acid ester thereof, and the present invention further provides a resin having a softening point of 50 ° C or more. The present invention is a curable composition containing a metal dryer and / or a radical polymerizable initiator, and the present invention is a curable ink containing a colorant. The present invention provides a printing method comprising printing the curable ink on a substrate, immediately applying an active energy ray-curable overcoat varnish in a wet state, and irradiating with an active energy ray. Of printed matter.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Examples of the polyol (A) used for the hybrid compound in the present invention include dihydric polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,
Branched alkyl diols such as nepentyl glycol and 2-butyl-2-ethylpropanediol, tricyclodecane dimethylol, dicyclopentadiene diallyl alcohol copolymer, and the like; trimethylolethane, trimethylolpropane, trimethylolhexane as trivalent polyol , Trimethylolalkanes such as trimethyloloctane and glycerin as tetravalent or higher valent polyols, pentaerythritol, diglycerin,
Examples include ditrimethylolpropane, sorbitan, sorbitol, dipentaerythritol, inositol, and tripentaerythritol. In the present invention,
From the viewpoint of suppressing the blanket swelling, polyols of dimers or more such as diglycerin, ditrimethylolpropane, and dipentaerythritol are preferably used.

The fatty acid having 4 to 36 carbon atoms of the present invention (B-
1) is a saturated or unsaturated normal or branched fatty acid having 4 to 36 carbon atoms, such as butyric acid, caproic acid, enantic acid, octylic acid, pelargonic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, Margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, icosyl (Icosy
l) Acids and the like are exemplified. In addition, fatty acids of natural fats and oils, such as tung oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, coconut oil fatty acids, (dehydrated) castor oil fatty acids, palm oil fatty acids,
Safflower oil fatty acids, cottonseed oil fatty acids, rice bran oil fatty acids,
Olive oil fatty acids, rapeseed oil fatty acids and the like are exemplified. Further, examples of the fatty acids derived from fish oil and animal oils include squid oil fatty acids, sardine oil fatty acids, saury oil fatty acids, cod oil fatty acids, whale oil fatty acids, tallow oil fatty acids, pork oil fatty acids, and sheep oil fatty acids. Further, dimer acids of fatty acids such as tung oil dimer fatty acid and linseed oil dimer fatty acid are also exemplified. When the fatty acid (B-1) having 4 to 36 carbon atoms is an unsaturated fatty acid, the resulting hybrid compound is a hybrid curable compound having both oxidative polymerizability and active energy ray curability, and the present invention When used as a curable composition, it becomes possible to impart more favorable curing performance.

The esterification reaction with the polyol (A), the fatty acid having 4 to 36 carbon atoms (B-1) and the (meth) acrylic acid (C) for producing the hybrid compound in the present invention is carried out by using a stirrer. A polyol (A) and a fatty acid (B-1) are charged into a four-necked flask equipped with a heating method, and the temperature is gradually increased under a nitrogen stream under a refluxing solvent such as toluene, xylene, anone, or cyclohexane or without a solvent. 260
The reaction is carried out in the range of 0 ° C. in the absence or under the presence of a catalyst until the acid value (mg of potassium hydroxide required for neutralizing the acid contained in 1 g of the sample) becomes 5 or less, preferably 2 or less. Do. 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 air and nitrogen are mixed or blown with a solvent such as toluene, MIBK, or cyclohexane. The reaction is continued at a temperature in the range of 80 to 120 ° C. for 10 to 20 hours, and the reaction is continued until the acid value becomes 20 or less, preferably 15 or less, more preferably 10 or less.

Examples of the esterification catalyst 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 the like. Lewis acids and the like are used. In addition, metal complexes such as tetrabutyl zirconate and tetraisopropyl titanate, oxides of alkali and alkaline earth metals such as magnesium oxide, calcium oxide and zinc oxide, and metal salt catalysts are also used. The amount of the catalyst used is generally 0.1 to
5% by weight. Further, since the reaction product may be colored under such conditions, a reducing agent such as hypophosphorous acid, triphenyl phosphite, triphenyl phosphate or the like may be used in combination.

Examples of the polymerization inhibitor include 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, cuperon, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino-1,3-dimethylbutylidene) aniline oxide, Dibutyl cresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime, cyclohexanone oxime and the like are used.

The hybrid compound obtained by further reacting the polycarboxylic acid (B-2) can be obtained by the following method. That is, a polyol (A) and a fatty acid having 4 to 36 carbon atoms (B-1) were charged into a four-necked flask equipped with a stirrer,
Under a solvent such as toluene, xylene or anone or without a solvent, the temperature is gradually raised from 180 ° C under a nitrogen stream to 230-
The reaction is performed for several hours in a temperature range of 260 ° C., and the acid value is 5 or less,
Desirably, it is set to 2 or less. Thereafter, the mixture was cooled, charged with a polycarboxylic acid at 180 ° C., and gradually heated from 180 ° C. to 23
A method in which the reaction is carried out at 0 to 260 ° C. for several hours until the acid value becomes 5 or less, preferably 2 or less, or a polyol (A), a fatty acid having 4 to 36 carbon atoms (B-1), and a polycarboxylic acid. (B-2), and the temperature is gradually increased from 180 ° C. in a nitrogen stream under the same or no solvent as described above, and the mixture is reacted at 230 to 260 ° C. for several hours, and the acid value is 5 or less, preferably 2 or less. To Thereafter, the mixture is cooled to 120 ° C. or lower, charged with a polymerization inhibitor, (meth) acrylic acid, and a catalyst, and blown in with air or a mixture of air and nitrogen under a solvent such as toluene, MIBK, or cyclohexane.
A method in which the reaction is performed in a temperature range of 0 to 120 ° C. for 10 to 20 hours and the reaction is continued until the acid value is reduced to 20 or less, preferably 15 or less can be exemplified.

Examples of the polycarboxylic acid include maleic acid or its anhydride, succinic acid or its anhydride, adipic acid,
Sebacic acid, dodecenyl succinic anhydride, pentadecenyl succinic anhydride and the like, and further, dimer acid which is a dimer of unsaturated fatty acids such as linseed oil, tung oil and the like, o-phthalic acid or anhydride thereof, isophthalic acid, Terephthalic acid, tetrahydrophthalic acid or anhydride, hexahydrophthalic acid or anhydride, (methyl) hymic acid or anhydride, tricyclodecanedicarboxylic acid, trimellitic acid or anhydride, pyromellitic acid or anhydride Products, polymerized rosin and the like.

The hybrid compound according to the present invention contains 10 to 40 fatty acids (B-1) having 4 to 36 carbon atoms in the compound.
% To 80% by weight, 5% by weight of (meth) acrylic acid
40% by weight of the fatty acid (B
If -1) is less than 10% by weight, the compatibility with resins generally used for oil-based inks such as rosin phenol resin becomes insufficient, and if it is more than 80% by weight, curability to active energy rays decreases. I do. On the other hand, if the amount of (meth) acrylic acid is less than 5% by weight, the curability to active energy rays decreases, and if it exceeds 40% by weight, the fatty acid (B-
The modification amount of 1) becomes small, and the compatibility with the rosin phenol resin becomes insufficient.

Next, the vegetable oil or its fatty acid ester used in the present invention will be described. First, vegetable oil
Among triglycerides of glycerin and fatty acids, triglycerides in which at least one fatty acid has at least one carbon-carbon unsaturated bond are triglycerides. Typical compounds as such vegetable oils are hemp seed oil and linseed oil. , Eno oil, euca deer oil, olive oil, cacao oil, kapok oil, kaya oil, mustard oil, kyonin oil, kiri oil, kukui oil, walnut oil, poppy oil, sesame oil, safflower oil, radish seed oil, soybean oil, large Feng oil, camellia oil, corn oil, rapeseed oil, niger oil, bran oil, palm oil, castor oil, sunflower oil, grape seed oil, gentian oil, pine seed oil, cottonseed oil, coconut oil, peanut oil, dehydrated castor oil, etc. Are listed. Further preferable vegetable oils include vegetable oils having an iodine value of at least 100 or more (parentheses and fats chemical handbook: iodine value quoted from Nikkan Kogyo Shimbun), hemp oil (149 or more), Linseed oil (170 or more), Eno oil (192 or more), Oitika deer oil (140 or more), Kapok oil (85-102),
Kaya oil (130 or more), mustard oil (101 or more), kyounin oil (97-109), tung oil (145 or more), kukui oil (136 or more), walnut oil (143 or more), poppy oil (131 or more), Sesame oil (104 or more), safflower oil (130 or more), radish seed oil (98-112), soybean oil (117 or more), soybean oil (101), corn oil (109 or more), rape oil (97-107) ), Niger oil (126 or more), nuka oil (92-115), sunflower oil (125 or more), grape seed oil (124 or more), gentian oil (93-105), pine seed oil (146 or more),
Cottonseed oil (99-113), peanut oil (84-102),
Dehydrated castor oil (147 or more) is suitably used, and a vegetable oil having an iodine value of 120 or more is more preferable. By setting the iodine value to 120 or more, the drying property of the curable composition by oxidative polymerization can be further improved.

[0017] In addition, in the present invention, regenerated vegetable oil, such as tempura oil, which has been used for food and recovered / regenerated can also be used. The regenerated vegetable oil has a water content of 0.1%.
An oil which has been regenerated with 3% by weight or less, an iodine value of 100 or more and an acid value of 3 or less is preferable, and has a water content of 0.3% by weight.
By doing so, it is possible to remove impurities that affect the emulsification behavior of the ink, such as salts contained in water, and by regenerating the iodine value to 100 or more, the drying property, that is, the oxidative polymerization property is good. The acid value of the regenerated vegetable oil can be reduced by selecting and regenerating a vegetable oil having an acid value of 3 or less, and it is possible to suppress overemulsification of the ink. . As a method of regenerating the recovered vegetable oil, methods such as filtration, removal of a precipitate by standing, and decolorization with activated clay are used.

Next, examples of the fatty acid ester in the present invention include fatty acid monoesters obtained by subjecting a saturated or unsaturated fatty acid obtained by hydrolysis of vegetable oil to an ester reaction with a saturated or unsaturated alcohol. It is liquid at normal temperature (20-25 ° C) and normal pressure (101.
Fatty acid monoesters having a boiling point of 200 ° C. or higher at 3 kPa) are preferred. Specific examples of such fatty acid esters include, as saturated fatty acid monoesters, hexyl butyrate, heptyl butyrate, hexyl butyrate, octyl butyrate, butyl caproate, and caproic acid. Acyl, hexyl caproate, heptyl caproate, octyl caproate, nonyl caproate, propyl enanthate, butyl enanthate, amyl enanthate, hexyl enanthate, heptyl enanthate,
Octyl enanthate, ethyl caprylate, vinyl caprylate, propyl caprylate, isopyryl 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, capric acid Methyl, ethyl caprate, vinyl caprate, propyl caprate, isopropyl caprate, butyl caprate, hexyl caprate, heptyl caprate, methyl laurate, ethyl laurate, vinyl laurate,
Examples thereof include propyl laurate, isopropyl laurate, butyl laurate, isoamyl laurate, hexyl laurate, and 2-ethyl-hexyl laurate.

Examples of unsaturated fatty acid esters include ethyl oleate, propyl oleate, butyl oleate, allyl oleate, isoamyl oleate, heptyl oleate, 2-ethylhexyl oleate, methyl elaidate, ethyl elaidate, and elaidin. Propyl acid, 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, linoleic acid
2-ethylhexyl, methyl linolenate, 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, arachidonic acid methyl,
Ethyl arachidonic acid, allyl arachidonic acid, propyl arachidonic acid, isopropyl arachidonic acid, butyl arachidonic acid, isobutyl arachidonic acid, arachidonic acid-te
rt-butyl, pentyl arachidonic acid, hexyl arachidonic acid, heptyl arachidonic acid, 2-ethylhexyl arachidonic acid, methyl eicosenoate, ethyl eicosenoate, allyl eicosenoate, propyl eicosenoate, isopropyl eicosenoate, butyl eicosenoate, isobutyl eicosenoate Tert-butyl eicosenoate, pentyl eicosenoate, hexyl eicosenoate, heptyl eicosenoate, 2-ethylhexyl eicosenoate, methyl eicosapentaenoate, ethyl eicosapentaenoate, allyl eicosapentaenoate, propyl eicosapentaenoate, eicosapentaenoic acid Isopropyl, butyl eicosapentaenoate, isobutyl eicosapentaenoate, -tert-butyl eicosapentaenoate, eicosapentaenoic acid N-ethyl, hexyl eicosapentaenoate, heptyl eicosapentaenoate, 2-ethylhexyl eicosapentaenoate, methyl erucate, ethyl erucate, allyl erucate, propyl erucate, isopropyl erucate, butyl erucate, isobutyl erucate, erucic acid -Tert-butyl, pentyl erucate,
Hexyl erucate, heptyl erucate, erucic acid-2-
Ethylhexyl, methyl docosahexaenoate, ethyl docosahexaenoate, allyl docosahexaenoate, propyl docosahexaenoate, isopropyl docosahexaenoate, butyl docosahexaenoate, isobutyl docosahexaenoate, -tert-butyl docosahexaenoate, pentyl docosahexaenoate, pentyl docosahexaenoate, hexosahexaenoate hexacoate, docosahexaenoate, docosahexahexate, Acid-2-ethylhexyl, methyl ricinoleate, ethyl ricinoleate, allyl ricinoleate, propyl ricinoleate, isopropyl ricinoleate, butyl ricinoleate,
Isobutyl ricinoleate, -tert-butyl ricinoleate, pentyl ricinoleate, hexyl ricinoleate,
Examples include heptyl ricinoleate and 2-ethylhexyl ricinoleate.

In the present invention, the saturated or unsaturated fatty acid constituting the fatty acid ester is actually a coconut oil fatty acid,
Palm oil fatty acids, rapeseed oil fatty acids, soybean oil fatty acids, hydrogenated soybean oil fatty acids, linseed oil fatty acids, tung oil fatty acids, tall oil fatty acids, dehydrated castor oil fatty acids, or fractionated fatty acids thereof by fractional distillation or the like are used. Obtained as a mixture of unsaturated fatty acids.

Next, a resin having a softening point of 50 ° C. or higher will be described. Resins having a softening point of 50 ° C. or higher include rosin-modified phenol resins, petroleum resins, alkyd resins, rosin-modified alkyd resins, maleic acid-modified rosin ester resins, maleic ester-modified petroleum resins, melamine resins, terpene resins, and cumarone indene Examples thereof include resins, ketone resins, phenol-modified petroleum resins, diallyl phthalate resins, and the like.

Next, the (meth) acrylic monomer or acrylic oligomer having an ethylenically unsaturated double bond will be described. As the (meth) acrylic monomer having an ethylenically unsaturated double bond, alkyl (having 1 to 18 carbon atoms) (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl as monofunctional monomer There are (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate and stearyl (meth) acrylate, and further, benzyl (meth) acrylate, butylphenol, octylphenol or alkylphenol such as nonylphenol or dodecylphenol. Alkylene oxide adduct (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecane monomethylol (meth) Acrylate and the like. Further, as bifunctional monomers, 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, neopentyl glycol di (meth) acrylate, neopentyl glycol poly (1-10) (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, hydroxypyrene Valyl hydroxypivalate di (meth) acrylate (commonly called Manda), hydroxypivalyl hydroxypivalate dicaprolactonate di (meth) acrylate, 1,6 hexanediol di (meth) acrylate,
1,6 hexanediol poly (1-10) alkylene oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) di (meth) acrylate, 1,2-hexanediol di (meth) acrylate, 1,5-hexane Diol di (meth) acrylate, 2,5-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,2-octanediol di (Meth) acrylate di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,2-decanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2- 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, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate, 3-methyl-
1,5-pentanediol di (meth) acrylate, 2
-Methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1,3-propanediol- Rudi (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-hexanediol di (meth) acrylate , 2,5-dimethyl-
2,5-hexanediol di (meth) acrylate, 2
-Methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-
1,5-pentanediol di (meth) acrylate,
1,2-hexanediol poly (1-10) alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, 1,5-hexanediol poly (1-1)
0) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, 2,5-hexanediol poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) Adduct di (meth) acrylate, 1,7-heptanediol poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide,
Butylene oxide etc.) adduct di (meth) acrylate, 1,8-octanediol poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide etc.) adduct di (meth) acrylate, 1,2- Octanediol poly (1
-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.)
Adduct di (meth) acrylate di (meth) acrylate, 1,9-nonanediol poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth)
Acrylate, 1,2-decanediol poly (1-1
0) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, 1,10-decanediol poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) Adduct di (meth) acrylate, 1,2-decanediol poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide,
Butylene oxide etc.) adduct di (meth) acrylate, 1,12-dodecanediol poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide etc.) adduct di (meth) acrylate, 1,2- Dodecanediol poly (1
-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.)
Adduct di (meth) acrylate, 1,14-tetradecanediol poly (1-10) alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate,
1,2-tetradecanediol poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, 1,16-hexadecanediol poly (1-10) alkylene oxide (eg, Ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, 1,2-hexadecanediol poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide,
Butylene oxide etc.) adduct di (meth) acrylate, 2-methyl-2,4-pentanepoly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide etc.) adduct diol di (meth) acrylate, 3- Methyl-1,5-pentanediol poly (1-10) alkylene oxide (for example, ethylene oxide, propylene oxide,
Adduct di (meth) acrylate, 2-methyl-2-propyl-1,3-propanediol poly (1-10) alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di ( Meth) acrylate, 2,4-
Dimethyl-2,4-pentanediol poly (1-10)
Alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, 2,2-diethyl-1,3-propanediol poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide) ,
Adduct di (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol poly (1-10) alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di ( Meth) acrylate, dimethyloloctanedi (meth) acrylate (Mitsubishi Chemical), 2-
Ethyl-1,3-hexanediol poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol poly ( 1-10) alkylene oxides (eg, ethylene oxide, propylene oxide,
Adduct di (meth) acrylate, 2-methyl-1,8-octanediol poly (1-
10) Alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol poly (1-10) alkylene oxide (eg, ethylene oxide) , Propylene oxide, butylene oxide, etc.) adduct di (meth)
Acrylate, 2,4-diethyl-1,5-pentanediol poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate tricyclodecane dimethylol di (meth) Acrylate, tricyclodecane dimethylol dicaprolactonate di (meth) acrylate, bisphenol A tetraethylene oxide adduct di (meth) acrylate, bisphenol A poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene Oxide, etc.) adduct di (meth) acrylate, bisphenol F tetraethylene oxide adduct di (meth)
Acrylate, bisphenol F poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, bisphenol S tetraethylene oxide adduct di (meth) acrylate, bisphenol S poly (1 10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, water-added bisphenol A tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol A poly (1
10) alkylene oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) di (meth) acrylate, water-added bisphenol F
Tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol F poly (1-10) alkylene oxide adduct di (meth) acrylate, water-added bisphenol A di (meth) acrylate, water-added bisphenol F di (meth) acrylate , Dihydroxybenzene (catechol, resorcin, hydroquinone, etc.) poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, alkyldihydroxybenzene poly (1-10) alkylene oxide (For example, ethylene oxide, propylene oxide,
Examples thereof include di (meth) acrylate, butylene oxide, dicaprolactonate di (meth) acrylate, bisphenol A tetraethylene oxide adduct, and dicaprolactonate di (meth) acrylate, bisphenol F tetraethylene oxide adduct. As trifunctional monomers, glycerin tri (meth) acrylate, glycerin poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri Methylol propane poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate, trimethylolethane tri (meth) Acrylate, trimethylolethane poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct Ethylene oxide, propylene oxide, butylene oxide, etc. tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethylolhexane poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) (Meth) acrylate, trimethyloloctanetri (meth) acrylate, trimethyloloctanepoly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct tri (meth) acrylate, pentaerythritol tri (meth) acrylate ) Acrylates, trihydroxybenzenes (such as pyrogallol) poly (1-10) alkylene oxides (eg, ethylene oxide, propylene Oxide, butylene oxide, etc.) adducts tri (meth) acrylate and the like. Pentaerythritol tetra (meth) acrylate, pentaerythritol poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, pentaerythritol tetracaprolactonate tetra (Meta)
Acrylate, diglycerin tetra (meth) acrylate, diglycerin poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, ditri Methylol propane poly (1-1
0) Alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylolpropanetetracaprolactonate, tetra (meth) acrylate, ditrimethylolethanetetra (meth) acrylate, ditrimethylolethanepoly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylolbutanetetra (meth) acrylate, ditrimethylolbutanepoly (1-10)
Alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylolhexanetetra (meth) acrylate, ditrimethylolhexane poly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide) Etc.) tetra (meth) acrylate, ditrimethyloloctanetetra (meth) acrylate, ditrimethyloloctanepoly (1-10) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol poly (1-12) alkylene oxide (for example, ethylene Oxide, propylene oxide, butylene oxide, etc.) adduct penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol poly (1-12) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) hexa (Meth) acrylate, dipentaerythritol hexacaprolactonate hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol poly Alkylene oxide hexa (meth) acrylate, tripentaerythritol polyalkylene oxide hepta (meta Acrylate,
Examples thereof include tripentaerythritol polyalkylene oxide octa (meth) acrylate.

Examples of the (meth) acrylic oligomer include polyols, esterified products of polybasic acids and (meth) acrylic acids, and epoxy acrylates. As the polyol and polybasic acid, those already exemplified in the present application are used.For example, as the polyol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc., and as the polybasic acid, phthalic anhydride,
Isophthalic acid, succinic acid, maleic acid and the like are used.

Next, acetic acid, propionic acid, butyric acid, isopentanoic acid, hexanoic acid, 2-
Ethyl butyric acid, naphthenic acid, octylic acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, secanoic acid , Tall oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, dimethylhexanoic acid, 3,
Metal salts of organic carboxylic acids such as 5,5-trimethylhexanoic acid and dimethyloctanoic acid, and known and publicly known compounds such as calcium, cobalt, lead, iron, manganese, zinc and zirconium salts can be used. A plurality of these can be used in combination as appropriate in order to promote the curing of the printing ink surface and the inside.

Next, examples of the radical polymerization initiator can be roughly classified into a photocleavable type and a hydrogen abstraction type. Examples of the former include benzoin, such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and α-acrylbenzoin, benzyl, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (Irgacure 907: Chiba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (Irgacure 369: Ciba Specialty Chemicals), benzyl methyl ketal (Irgacure 651:
Ciba Specialty Chemicals), 1-hydroxycyclohexyl phenyl ketone (Irgacure 184:
Ciba Specialty Chemicals), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173: Merck), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-
1-one (Darocur 1116: manufactured by Merck), 4-
(2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 4- (2-acryloyl-
Oxyethoxy) phenyl-2-hydroxy-2-propyl ketone, diethoxyacetophenone (ZLI333
1: Ciba Specialty Chemicals), Esacure KIP100 (Rumberty), Lucirin TPO
(Manufactured by BASF), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide (BAPO1: manufactured by Ciba Specialty Chemicals), bis (2,4,6-trimethylbenzoyl)
-Phenylphosphine oxide (BAPO2: manufactured by Ciba Specialty Chemicals), BTTB (manufactured by NOF Corporation), and CGI1700 (manufactured by Ciba Specialty Chemicals).

Examples of the latter include benzophenone, p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, methyl benzoylbenzoate,
Aryl ketones such as 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4 diethylthioxanthone, 2,4 dichlorothioxanthone, and acetophenone Initiators, dialkylamino aryl ketone initiators such as 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone, isoamyl p-dimethylaminobenzoate, p-dimethylaminoacetophenone, and thioxanthone And xanthone-based and halogen-substituted polycyclic carbonyl-based initiators. These can be used alone or in an appropriate combination. These initiators can be used in the composition in the range of 0.1 to 30% by weight, preferably in the range of 1 to 15% by weight.

Next, examples of the colorant include inorganic pigments and organic pigments. Inorganic pigments such as yellow lead, zinc yellow, navy blue, barium sulfate, cadmium red, titanium oxide, zinc white, red iron oxide, alumina white, calcium carbonate, ultramarine blue, carbon black, graphite, aluminum powder, red iron oxide, etc. Are soluble azo pigments such as β-naphthol type, β-oxynaphthoic acid type, β-oxynaphthoic acid type anilide type, acetoacetic anilide type, pyrazolone type, β-naphthol type, β-oxynaphthoic acid anilide type, Insoluble azo pigments such as acetoacetic anilide monoazo, acetoacetic anilide disazo and pyrazolone, phthalocyanine pigments such as copper phthalocyanine blue, halogenated (chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, and metal-free phthalocyanine , Quinacridone , Dioxazine-based, sulene-based (pyranthrone, anthantrone, indanthrone, anthrapyrimidine, flavantron, thioindigo-based, anthraquinone-based, perinone-based, perylene-based, etc.), isoindolinone-based, metal complex-based, quinophthalone-based polycyclic Various publicly known pigments such as formula pigments and heterocyclic pigments are used.

In the present invention, a conventional boiling point of 200 to 40 containing a volatile organic compound (VOC) such as a petroleum solvent is used.
A printing ink solvent at 0 ° C. may be used. The printing ink solvent of the present invention is, for example, No. 1 spindle oil manufactured by Nippon Oil Co., Ltd., No. 3 to No. 8 solvent, naphthesol H, alkene 5
6NT, Diadoll 13, Diamond 168 manufactured by Mitsubishi Chemical Corporation, F-Oxocall, F-Oxocall 180 manufactured by Nissan Chemical Co., Ltd. are exemplified. The printing ink solvent in which the aromatic component is reduced to 3% or less is a petroleum solvent having the same boiling point range and a weight ratio of aromatic component / naphthene component / paraffin component of 0 to 3/0 to 100/100 to 100%. 0 solvent,
It is a solvent that sometimes contains an olefinic component. Specifically, AF Solvent 4 manufactured by Nippon Oil Co., Ltd.
No. 8,0 Solvent H, N-paraffin C14-C18 manufactured by ISU Corporation, Supersol LA3 manufactured by Idemitsu Kosan Co., Ltd.
5. Exol D8 of Exxon Chemical Co., Ltd.
0, D110, D120, D130, D160, D10
Maggisol-40, -44, -47, -52, -6 manufactured by Maggie Brothers, such as 0K, D120K, and D130K.
0 and the like are exemplified. The aniline point is preferably from 60 to 115 ° C. If a solvent having an aniline point higher than 115 ° C. is used, the solvent for the ink used in the ink composition will be insufficient, and the fluidity of the ink will be insufficient. You can only get prints without any. On the other hand, an ink using a solvent having an aniline point lower than 60 ° C. has poor releasability of the solvent from the ink film during drying and causes drying deterioration.

Next, the form of use as the curable composition in the present invention will be described. The curable composition according to the present invention comprises a printing ink or an overprint varnish (OP
Varnish). The printing ink is usually used in the form of a lithographic printing ink, but it can also be used as a relief printing ink, which is a relief printing ink. The usual composition ratio is as follows. Colorant 0 to 30% by weight Resin 0 to 40% by weight Vegetable oil and / or fatty acid ester thereof 5 to 90% by weight Hybrid compound 5 to 90% by weight Monomer having an ethylenically unsaturated double bond 5 to 90% by weight Radical polymerization inhibition 0.01-1% by weight Radical polymerizable initiator 0-15% by weight Metal dryer 0.1-3.0% by weight Other additives 0-10% by weight Solvent for printing ink 0-40% by weight

In producing the curable composition of the present invention, the hybrid compound of the present invention, a vegetable oil or a fatty acid ester thereof, and a (meth) acrylic monomer or (meth) acrylic oligomer having an ethylenically unsaturated double bond are used. , At room temperature or by heating and mixing up to 120 ° C. In this case, if necessary, air blowing (or mixing with nitrogen gas), addition of a polymerization inhibitor, addition of an antioxidant, and the like are simultaneously performed.

When a resin is further added to the curable composition of the present invention, particularly when a resin having a softening point of 50 ° C. or more, which is effective in the present invention, is used, the resin may be a vegetable oil or a fatty acid ester thereof. It is effective to use the varnish in the form of a melted or cooked varnish in a temperature range of 180 to 260 ° C. for 0.5 to 3 hours. If necessary, the varnish can be used as a varnish in a form in which the hybrid compound of the present invention and / or a (meth) acrylic monomer or (meth) acrylic oligomer having an ethylenically unsaturated double bond are mixed.

As the polymerization inhibitor, (alkyl) phenol, 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, cuperon, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino-1,3-
(Dimethylbutylidene) aniline oxide, dibutyl cresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime, cyclohexanone oxime and the like are used.

Examples of the additives include anti-friction agents, anti-blocking agents, slipping agents, and anti-scratch agents.
Natural waxes such as carnauba wax, wood wax, lanolin, montan wax, paraffin wax, microcrystalline wax, Fischer-Trops wax, polyethylene wax, polypropylene wax,
Synthetic waxes such as polytetrafluoroethylene waxes, polyamide waxes, and silicone compounds can be used.

Further, when the curable composition of the present invention is used for printing ink, the composition should be made into a varnish having a viscosity (100 to 200 Pa · s / 25 ° C.) which can be easily applied to printing ink. Is desirable. Although the composition ratio is not limited, resin / vegetable oil or its fatty acid ester / polymerization inhibitor / hybrid compound / (meth) acrylic monomer and / or (meth) acrylic oligomer having an ethylenically unsaturated double bond = 5 to 50 % By weight / 1 to 40% by weight / 0.01 to 1% by weight / 10 to 40% by weight / 0 to 4%
0% by weight is a general composition ratio.

Furthermore, the varnish can be made into a gel varnish by using a gelling agent. Examples of the gelling agent include an aluminum complex compound. Cyclic aluminum compounds, for example, cyclic aluminum oxide octate (Algomer 8 manufactured by Kawaken Fine Chemical Co., Ltd.)
00), cyclic aluminum oxide stearate (Algomer 1000S manufactured by Kawaken Fine Chemical Co., Ltd.), etc., as aluminum alcoholates, aluminum ethylate, aluminum isopropylate (AIPD manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum-sec-butylate (Kawaken Fine Chemical Co., Ltd.) ASPD), aluminum isopropylate-mono-sec-butyrate (AMD manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum alkyl acetates such as aluminum-di-n-butoxide-ethylacetoacetate (Chel manufactured by Hope Pharmaceutical Co., Ltd.)
ope-Al-EB2), aluminum-di-iso-
Butoxide-methyl acetoacetate (Chope-Al-MB12 manufactured by Hope Pharmaceutical Co., Ltd.), aluminum-di-iso-butoxide-ethyl acetoacetate (Chopepe-Al-EB102 manufactured by Hope Pharmaceutical Co., Ltd.), aluminum di-iso-butoxide-ethyl acetoacetate ( Hope Pharmaceutical Chlope-Al-EB
2), aluminum di-iso-propoxide-ethyl acetoacetate (Chopepe manufactured by Hope Pharmaceutical Co., Ltd.)
-Al-EP12, ALc manufactured by Kawaken Fine Chemical Co., Ltd.
h), aluminum-tris (acetylacetonate)
(ALCH-TR manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum-tris (acetylacetoacetate) (aluminum chelate-A manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum-bis (ethyl acetylacetonate) -monoacetylacetonate (Kawaken Fine Chemical Co., Ltd.) Aluminum Chelate D), Aluminum Chelate M (Kawaken Fine Chemical), Aluminum Chelate NB-15 (Hope Pharmaceutical),
Kelop S (Hope Pharmaceutical) Kelop ACS-2 (Hope Pharmaceutical, Liquid Olive AOO (Hope Pharmaceutical)
And liquid olive AOS (Hope Pharmaceutical Co., Ltd.). Examples of the aluminum soap include aluminum stearate (manufactured by NOF Corporation), aluminum oleate, aluminum naphthonate, aluminum urate, and aluminum acetylacetonate. These gelling agents are used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the varnish. As other gelling agents, cyclic dipeptides, bisamides such as ethylenebis (12-hydroxyoctadecanoic acid) amide, which can gel an organic liquid, Al-Mg-hydroxycaprylate, Al-Mg-hydroxymyristate , Al
Powdered aluminum-magnesium compounds such as -Mg-hydroxypalmitate and Al-Mg-hydroxybehenate are exemplified. AIP, ASB, AIE
-M, ASE-M, OAO, OAO-EF, OAO-H
T, Cyco-Gel, Ketalin, Ketalin-II, Ketalin
-III, TRI-HLP-49, P-95, KHD, A
TC-30, OASMS, OAS / 607, ALAC,
AO-L47 (Chattem Chemicals, Inc.) is exemplified. Further, tetraisopropyl titanate, tetra n-butyl titanate, tetreoctyl titanate,
Organic titanates such as titanium acetylacetonate, titanium octylene glycolate, titanium lactate, and titanium lactate ethyl ester are exemplified. Further, organic zirconium such as zirconium-tetrabutoxide, zirconium acetylacetone, zirconium acetylacetone, zirconium acetylacetone, acetylacetone zirconium butoxide, and ethyl zirconium butoxide acetoacetate are exemplified. The preparation of gel varnish is
Usually, 0.1 to 3 parts by weight of the gelling agent is charged and 100 to 2 parts by weight.
It is obtained by reacting in a temperature range of 00 ° C. for 30 minutes to 2 hours.

The printing ink is used at a temperature between room temperature and 100 ° C.
Colorant, varnish and / or gel varnish thereof, hybrid compound of the present invention, vegetable oil or fatty acid ester thereof, (meth) acrylic monomer or (meth) acrylic oligomer having ethylenically unsaturated double bond, radical polymerization inhibitor, radical polymerization Manufactures printing ink components such as sensitizing initiators and / or sensitizers, metal dryers, and other additives using kneaders, three rolls, attritors, sand mills, gate mixers, and other meat, mixing, and adjusting machines. Is done.

The curable ink comprising the curable composition of the present invention is generally applied to offset printing using a fountain solution, but is also suitably used for waterless printing without using a fountain solution. Further, the curable composition of the present invention is also applied to an overprint varnish (commonly called OP varnish). The curable composition and the curable ink of the present invention include printed matter for forms, printed matter for various books, printed matter for packaging such as carton paper, various printed matter for plastic, printed matter for seal / label, art printed matter, metal printed matter (art printed matter, It is applied to printed matter such as printed matter of a beverage can and food printed matter such as a can. For curable inks, UV curable inks and electron beam curable inks, and for overcoat varnishes, UV curable overcoat varnishes and electron beam overcoat varnishes, and also used as aqueous overcoat varnishes There is also.

Further, in the present invention, in order to further enhance the aesthetic luxuriousness and durability of a printed material using the curable ink of the present invention, the curable ink is printed on a base material, and the active energy curable ink is immediately wetted. Apply a coat varnish,
A printing method for irradiating active energy rays and a printed matter obtained by the method are also provided. After printing a general oil-based ink that is usually only oxidatively polymerizable, immediately apply an active energy ray overcoat varnish in a wet state, and when irradiating with active energy rays, measure the gloss after several days. Although gloss reduction, so-called gloss back occurs, when the curable ink of the present invention is used, even when the active energy ray-curable overcoat varnish is immediately applied and irradiated with active energy rays, the gloss back is significantly improved. Thus, it is possible to provide a printed material having a high-grade aesthetic feeling. The base material is coated paperboard such as maricoat, polyethylene coated paper and aluminum coated paper manufactured by Hokuetsu Paper Co., Ltd., thin paper coated paper such as Tokishi Art Paper manufactured by Mitsubishi Paper Mills Co., Ltd., high quality paper, synthetic paper, plastic Films, metal plates and the like are used.

Hereinafter, the present invention will be described in detail with reference to specific examples. In the examples, "parts" indicates parts by weight.

Production Example of Hybrid Compound (HR2) In a four-necked flask equipped with a stirrer, a water separation tube and a thermometer, 532 parts of linoleic acid, 250 parts of ditrimethylolpropane, and 70 parts of toluene were charged into a four-neck flask under a nitrogen stream. At 230 ° C. for 7 hours, and cooled to 110 ° C. when the acid value became 5 or less.
Parts, p-toluenesulfonic acid 9 parts, acrylic acid 151
The reaction was carried out under a gas flow such as nitrogen / air. After about 8 hours, when the dehydration reaction stopped, 20 parts of cyclohexane was charged, and the dehydration reaction was further continued at reflux. When the acid value reached 15.0, washing was carried out three times with an equal amount of water, and then washed with water. Was confirmed to be neutral or close to pH test paper, and then desolvated and pumped out. The acid value was 8.2.

The reaction was carried out in the same manner as shown in Table 1 to obtain hybrid compounds HR1 to HR7.

[0042]

[Table 1]

Production Example of Varnish (V1) A rosin-modified phenol resin R1 was placed in a four-necked flask equipped with a stirrer, a water separation cooling tube and a thermometer under a nitrogen stream.
35 parts of (resin having a weight average molecular weight of 45,000 and an acid value of 22 produced from gum rosin, glycerin and p-tert-octylphenol type resole) and 25 parts of linseed oil were charged and heated at 220 ° C. for 1 hour. Thereafter, the temperature was lowered, and at 110 ° C., 0.1 part of hydroquinone and 30 parts of HR1 were added.
Parts, 1 part of ditrimethylolpropane tetraacrylate
0 parts, in order, and heated at 100 ° C. for 1 hour under an air stream. When viscosity was measured with a cone plate type viscometer,
108 Pa · s / 25 ° C. Similarly, varnishes (V1 to V7) were prepared in the same manner as shown in Table 2 below.

[0044]

[Table 2]

Comparative Example Production Example of Varnish (V8) (Oxidation Polymerization Varnish) A rosin-modified phenolic resin R1 was placed in a four-necked flask equipped with a stirrer, a water separation cooling tube, and a thermometer under a nitrogen stream.
45 parts, linseed oil 20 parts, AF5 solvent (Nippon Oil Co., Ltd. aroma-free ink solvent) 34.4 parts, ALC
H (Kelling Fine Chemical Co., Ltd. gelling agent) 0.5
And 0.1 part of 2,6-ditert-butyl-4-methyltoluene were charged and dissolved by heating at 200 ° C. for 1 hour. When the viscosity was measured with a cone plate type viscometer, 98 Pa
・ S / 25 ° C. Similarly, Comparative Examples Varnishes V9 and V10 were prepared according to the formulations shown in Table 3 below.

Comparative Example Production example of varnish (V11) (active energy ray-curable varnish) Dap tote DT170 (Dialul phthalate manufactured by Toto Kasei Co., Ltd.) Resin) 30 parts, 69.9 parts of ditrimethylolpropane tetraacrylate, and 0.1 part of hydroquinone were charged, and were heated at 100 ° C. for 30 minutes to 1 under an air stream.
Dissolved in time. It was 152 Pa · s / 25 ° C. when the viscosity was measured with a cone-plate viscometer. Similarly, the varnishes of Comparative Examples V11 and V
12 was created.

[0047]

[Table 3]

Production Example of Curable Ink (Ink 1) 18 parts of carmine 6B (red pigment manufactured by Toyo Ink Mfg. Co., Ltd.) as red pigment, 49 parts of varnish V1, 10 parts of dipentaerythritol hexaacrylate, 10 parts of trimethylolpropane 16.9 parts of triacrylate and 2.5 parts of 4,4′-bis (diethylamino) benzophenone (EAB)
Parts, 2.5 parts of Irgacure 907, 0.1 part of hydroquinone, and 1 part of manganese naphthenate were charged.
Manufactured in a conventional manner with LUMIL. The ink has a tack value of 7.
８8 / 25 ° C. Inks 2 to 15 were manufactured according to the formulations shown in Tables 4 and 5 below. The inks 9, 10, 1
Reference numerals 4 and 15 are examples of electron beam curable inks. Incidentally, the heat decrement of the curable inks 1 to 10 was 0.9% (moisture 0.2%), and the heat decrement of the curable ink 11 was 5.8%.
(Moisture 0.2%), and the heat loss of the curable inks 12 to 15 was 10.9% (moisture 0.2%). Gas flow 10
Thermogravimetry was performed under the condition of 0 mL / min. The water content was determined by the Karl Fischer method.

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

Comparative Example Production Example of Oil Ink (Ink 11) 18 parts of carmine 6B, 70.9 parts of varnish V8, AF
10 parts of 5 solvents, 0.1 part of BHT, and 1 part of manganese naphthenate were charged, and prepared by a conventional method using a three-roll mill. The ink was adjusted to a tack value of 7 to 8/25 ° C.
In the same manner, in the same manner as in Comparative Example Oil-based ink 1 having the formulation shown in Table 6,
2, 13 were produced. In addition, the comparative example oil-based inks 11-13
Was 35% (moisture 0.2%).

Comparative Example Production Example of Oil-based Ink (Ink 16) 18 parts of carmine 6B, 70.9 parts of varnish V8, AF
10 parts of 5 solvents, 0.1 part of BHT, and 1 part of manganese naphthenate were charged, and prepared by a conventional method using a three-roll mill. The ink was adjusted to a tack value of 7 to 8/25 ° C.
In the same manner, in the same manner as in Comparative Example Oil-based ink 1 having the formulation shown in Table 6,
7, 18 were produced. In addition, the comparative example oil-based ink 16-18
Was 35% (moisture 0.2%).

[0054]

[Table 6]

Comparative Example Ultraviolet curable ink (ink 14) 18 parts of carmine 6B, 30 parts of varnish V11, 26.9 parts of ditrimethylolpropane tetraacrylate, 20 parts of dipentaerythritol hexaacrylate, EA
2.5 parts of B, 2.5 parts of Irgacure 907 and 0.1 part of hydroquinone were charged and prepared by a conventional method using a three-roll mill. The ink was adjusted to a tack value of 7 to 8/25 ° C. In the same manner, comparative UV-curable ink 15 was produced according to the formulation shown in Table 6.

Comparative Example Electron beam 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,
0.1 part of hydroquinone was charged and prepared by a conventional method using a three-roll mill. The ink has a tack value of 7 to 8/25.
C. In the same manner, comparative electron beam curable ink 17 was produced in the same manner as shown in Table 6.

Comparative Example Ultraviolet curable ink (ink 19) 18 parts of carmine 6B, 30 parts of varnish V11, 26.9 parts of ditrimethylolpropane tetraacrylate, 20 parts of dipentaerythritol hexaacrylate, EA
2.5 parts of B, 2.5 parts of Irgacure 907 and 0.1 part of hydroquinone were charged and prepared by a conventional method using a three-roll mill. The ink was adjusted to a tack value of 7 to 8/25 ° C. In the same manner, comparative UV-curable inks 20 were manufactured according to the formulations shown in Table 6.

Comparative Example Electron Curable Ink (Ink 21) 18 parts of carmine 6B, 35 parts of varnish V11, 26.9 parts of ditrimethylolpropane tetraacrylate, 20 parts by weight of dipentaerythritol hexaacrylate,
0.1 part of hydroquinone was charged and prepared by a conventional method using a three-roll mill. The ink has a tack value of 7 to 8/25.
C. In the same manner, comparative electron beam curable ink 22 was produced according to the formulation shown in Table 6.

The effect of the present invention will be described with reference to a gloss back test. (Examples 1 to 11 and Comparative Examples 1 to 9) -In the case of UV irradiation- R is applied to a maricoat paper (coated cardboard manufactured by Hokuetsu Paper Co., Ltd.).
Using an I tester (simple printing machine manufactured by Mei Seisakusho Co., Ltd.)
Immediately after printing with 0.3 cc ink, wire bar # 3K-Rock Sprue (RK PRINT-
UV curable varnish (FDCPA902 varnish: Toyo Ink Manufacturing Co., Ltd.) with COAT INSTRUMENTS Ltd.
Co., Ltd.) was applied and irradiated with ultraviolet light, and the gloss was measured immediately and after 72 hours. In addition, an adhesion test by cellotape (registered trademark) peeling was also performed. UV irradiation, USHIO Corporation
UVC-2535 (1 high-pressure mercury ozone uncut lamp, 120 W / cm, conveyor speed 30
m / min). The gloss meter was used under the conditions of 60 degrees manufactured by Murakami Color Research Laboratory Co., Ltd.

-In the case of electron beam irradiation-Color printing was performed under the same conditions as in the case of ultraviolet irradiation, and an EB-curable varnish (varnish obtained by removing the initiator from FDPCA902) was applied, and then immediately irradiated with an electron beam. Regarding electron beam irradiation, irradiation was performed at 30 KGy using a low energy electron beam irradiation apparatus manufactured by ESI Corporation in the United States (a pressurized voltage of 175 KV and an oxygen concentration of 500 ppm in a nitrogen-substituted atmosphere). Table 7 summarizes the above results.

[0061]

[Table 7]

Next, the effects of the present invention will be described by a blanket swelling test. Each ink and each raw material were placed on a blanket S7400 manufactured by Kyoyosha Co., Ltd., which is generally used for oil-based ink, and the blanket swellability after 72 hours was measured with a micro gauge. The difference between the thickness of the blanket after swelling and the thickness of the blanket before swelling was divided by the thickness of the blanket before swelling, and expressed as a percentage (%). The results are summarized in Table 8. In the table, 0 to 0.5% swells well, and 0.6 to 0.9% swells slightly, but practical level, and 1.0% or more is bad. Table 8 summarizes the above results.

[0063]

[Table 8]

Ink washability: After printing each ink with an RI tester, the washability of the ink was tested with a mineral turpentine. The results are summarized in Table 8. In the table, ○ indicates good washability and X indicates poor washability.

[0065]

As described above, by using the curable composition using the hybrid compound according to the present invention, the swelling resistance, washability, emulsification suitability, misting suitability, and low cost of the oxidatively polymerizable oil-based ink are obtained. When an active energy ray-curable overcoat varnish is applied while maintaining the properties, it is possible to provide a glossy high-quality printed matter in which gloss back is suppressed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 2/44 C08F 2/44 B 2/50 2/50 283/01 283/01 C09D 11/10 C09D 11 / 10 F term (reference) 2H113 AA03 AA04 AA06 BC00 DA41 FA10 FA42 FA43 4J011 PA03 PA07 PA43 PA44 PA83 PA85 PA87 PA88 PB25 PC02 PC08 QA03 QA12 QA13 QA22 QA23 QA24 QB14 SA01 SA21 SA31 SA51 SA64 SA04 UA01 AB01 AB03 BA20 BA21 BA23 BA25 BA26 BA28 CC05 CC06 CD08 4J039 AB03 AD20 AD21 BC01 BC19 BC20 BE01 BE24 BE27 CA04 CA06 DA05 EA04 EA38 EA39 EA40 FA01 FA02 GA01 GA02 GA25 4J100 AL02P AL03P AL04P AL05P AL08P AL08Q AL60P AL60P AL10PAL63P AL60P AL60Q AL61P JA07

Claims (10)

[Claims] 1. A hybrid compound obtained by subjecting a polyol (A), a fatty acid (B-1) having 4 to 36 carbon atoms to a (meth) acrylic acid (C) to an ester reaction, a vegetable oil or a fatty acid ester thereof, And a curable composition comprising a (meth) acrylic monomer or (meth) acrylic oligomer having an ethylenically unsaturated double bond. 2. The curable composition according to claim 1, wherein the hybrid compound is a compound obtained by further subjecting a polyvalent carboxylic acid (B-2) to an ester reaction. 3. A hybrid compound comprising 10 to 80% by weight of a fatty acid (B-1) having 4 to 36 carbon atoms and 5 to 40% by weight of (meth) acrylic acid (C). 3. The curable composition according to claim 1, wherein: 4. The curable composition according to claim 1, wherein the fatty acid (B-1) having 4 to 36 carbon atoms is a fatty acid of a drying oil or a semidrying oil. 5. The curable composition according to claim 1, wherein the vegetable oil or a fatty acid ester thereof is a drying oil and / or a semi-drying oil, or a fatty acid ester thereof. 6. The curable composition according to claim 1, further comprising a resin having a softening point of 50 ° C. or higher. 7. The curable composition according to claim 1, further comprising a metal dryer and / or a radical polymerizable initiator. 8. The curable ink according to claim 1, further comprising a coloring agent. 9. A method comprising printing the curable ink according to claim 8 on a substrate, immediately applying an active energy ray-curable overcoat varnish in a wet state, and irradiating with an active energy ray. Printing method. 10. A printed matter obtained by the printing method according to claim 9.