JP2003119230A - Curable composition, curable ink, method of printing by using it, and printed matter obtained by using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which can be used for printing with a printing press using an oil-base ink and can give a printed matter having a high gloss and an aesthetic high-grade appearance when used in combination with an overprint varnish curable by actinic radiation. SOLUTION: A curable composition (hybrid curable composition) consisting of a hybrid compound (A) obtained by subjecting a polyol (a), a polybasic acid (b) and a (meth)acrylic acid (c) to esterification, a component (B) comprising a vegetable oil or its fatty acid ester, and a component (C) comprising a (meth) acrylic monomer or oligomer having an ethylenically unsaturated double bond is used for a curable printing material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyol (a).
And a polybasic acid (b) and a (meth) acrylic acid (c) are subjected to an ester reaction to form a hybrid compound (A), vegetable oil or its fatty acid ester (B), and an ethylenically unsaturated double bond ( A curable composition (hybrid curable composition) comprising a (meth) acrylic monomer or a (meth) acrylic oligomer (C), a curable ink (hybrid ink) using the curable composition, and further, after printing the hybrid ink, The present invention relates to a printing method in which an active energy ray-curable overcoat varnish is immediately applied in an uncured state of the ink, and then the active energy ray is irradiated, and the obtained printed matter.

[0002]

2. Description of the Related Art It is said that it imparts an aesthetic high-class feeling and various resistances (rubbing resistance, water resistance, oil resistance, solvent resistance) in the printing of various paper containers, books, posters, calendars, labels, wrapping paper, cards, etc. For the purpose, it has been generally practiced to apply an overcoat varnish, particularly an active energy ray overcoat varnish, after printing the ink. For example, after printing an oil-based ink (oxidation-polymerizable), the ink is dried until it is stacked for several days, and then an active energy ray-curable overcoat varnish is applied (oil-based ink / active energy ray-curable varnish). Off-line system), a method of applying active energy ray curable overcoat varnish immediately after printing the active energy ray curable ink (active energy ray curable ink / active energy ray curable in-line system), etc. Had been taken. However, the former offline
In the case of the system, the work efficiency is poor, and even in the latter case of the in-line system, the cost of the active energy ray-curable ink is high.

Further, the above oil-based ink often uses a volatile hydrocarbon-based ink solvent which is a fraction of mineral oil. However, in recent years, VOCs that have completely eliminated volatile hydrocarbon-based ink solvents from the oil-based inks have been taken into consideration for the environment.
The need for (volatile organic compounds) free ink is increasing. For example, according to Fukuda and Ishii et al. (Journal of the Printing Society of Japan, Vol. 37, No. 5, p. 51), if VOC-free offset printing ink becomes possible, oil for printing ink of 40,000 tons or more will be available. It is said that it will be possible to reduce the amount of solvent.

In order to solve the above-mentioned problems, a coater machine and an active energy ray irradiation device are installed after a multicolor printing machine for oily ink, and an active energy ray curable overcoat varnish is applied immediately after printing the oily ink. Attempts have been made to create glossy prints by curing, but with this method, the gloss gradually decreases, especially when multiple colors of ink are overprinted rather than a single color and thicker. However, there was a problem that deterioration of gloss continued for several days (gloss back), impairing aesthetic luxury and losing commercial value.

On the other hand, in a printing maker having only a multi-color printing machine for oil-based inks, when an in-line system of the above-mentioned active energy ray-curable ink / active energy ray-curable varnish is used, a printed matter is obtained. The active energy ray-curable ink infiltrates and swells in the printing machine rubber rolls and blankets, resulting in poor ink transfer, or when changing the pattern and performing the next printing, the printed pattern traces on the swollen part will appear on the next print. It appears as a thin ghost, detracting from the commercial value of the printed matter. In addition, there are various problems such as the fact that the cleaning liquid for the printing machine cannot be used for oil-based ink, and it can be replaced with a printing rubber roll or blanket that has durability against active energy ray curable ink, or only for active energy ray curable ink. There was a problem that it was necessary to introduce a new multicolor printing machine.

[0006] Therefore, for the above reasons, there is a demand for the development of an ink / varnish system in which gloss back after varnish application is suppressed and printing can be performed without problems on a multicolor printing machine for oil-based inks. .

[0007]

DISCLOSURE OF THE INVENTION The present invention maintains the swelling resistance, washing property, suitability for emulsion printing, good properties such as misting, and low cost of general oil-based printing ink, and immediately after multicolor printing. A curable ink (hybrid ink) that does not cause the gloss back even when an in-line printing method is carried out in which the ink is uncured and coated with an active energy ray-curable overcoat varnish and the active energy ray is irradiated. The present invention relates to a curable composition (hybrid curable composition) for that purpose, a printing method thereof, and a printed matter thereof.

Further, the present invention is to provide a curable ink which does not use any volatile organic compound (VOC) such as a petroleum solvent, and a printed matter which is printed using them. According to the present invention, the V provided by the US Environmental Protection Agency
It becomes possible to limit the thermogravimetric decrement in the OC measurement method, Metalody 24 (measurement of heating residue by heating at 110 ° C. for 1 hour), to 1% or less (excluding water), and to provide VOC-free ink and printed matter. Is possible.

However, the present invention is also applicable as a conventional curable ink containing a volatile organic compound (VOC) such as a petroleum solvent.

[0010]

The present invention provides a polyol (a), a polybasic acid (b) and a (meth) acrylic acid (c).
A curable compound comprising a hybrid compound (A) obtained by reacting with and an ester, a vegetable oil or its fatty acid ester (B), and a (meth) acrylic monomer or (meth) acrylic oligomer (C) having an ethylenically unsaturated double bond. It relates to a composition.

The present invention relates to a curable composition in which the polybasic acid (b) is an aliphatic polybasic acid.

The present invention relates to a curable composition in which the polybasic acid (b) is a cyclic polybasic acid.

The present invention relates to a curable composition further containing a resin (D) having a softening point of 50 to 180 ° C.

[0014] The present invention relates to a curable composition characterized by further containing a metal dryer and / or a radically polymerizable initiator (E).

The present invention relates to a curable ink further containing a colorant (F).

A printing method comprising printing a curable ink on a substrate, applying an active energy ray-curable overcoat varnish in a state where the ink is not cured, and irradiating with an active energy ray. Regarding

The present invention relates to a printed matter obtained by the printing method.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

Hybrid compound (A) in the present invention
Examples of the polyol (a) used in (1) include, as divalent polyols, branched alkyl diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, nepentyl glycol, 2-butyl-2-ethylpropanediol, and trialkyl glycol. Cyclodecane dimethylol, dicyclopentadiene diallyl alcohol copolymer, etc. as trivalent polyols such as trimethylol ethane, trimethylol propane, trimethylol hexane, trimethylol alkanes such as trimethylol octane and glycerin, etc. As, pentaerythritol, diglycerin, ditrimethylolpropane, sorbitan, sorbitol, dipentaerythritol, inositol, tripentaerythritol And the like.

The aliphatic polybasic acid of the present invention includes C4 ~
C36 aliphatic polybasic acids, such as (anhydrous) maleic acid, fumaric acid, oxalic acid, malonic anhydride, (anhydrous) succinic acid,
(Anhydrous) Glutaric acid, adipic acid, sebacic acid, azelaic acid, dodecenyl succinic anhydride, pentadecenyl succinic anhydride, etc., and dimers of unsaturated fatty acids such as linseed oil, tung oil, soybean oil, etc. Examples thereof include dimer acid.
Examples include Tsunodim 216 and Tsunodim 228, which are amanyu fatty acid dimer acids manufactured by Tsukino Food Industry Co., Ltd., and Rusty-Dime DA-200, which is a soybean oil fatty acid dimer manufactured by Kaneda Corporation. Further, as the cyclic polybasic acid, a C8-C40 cyclic polybasic acid such as (anhydrous) phthalic acid,
Isophthalic acid, terephthalic acid, (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) tetrahydrophthalic acid, (anhydrous) hexahydrophthalic acid, (anhydrous) hymic acid (3,6-endomethylene tetrahydrophthalic anhydride Acid), (anhydrous) methylhymic acid (methyl-3,
6 endomethylene tetrahydrophthalic acid), tricyclodecane dicarboxylic acid, maleated rosin, polymerized rosin and the like.

Hybrid compound (A) in the present invention
The esterification reaction of the polyol (a), the polybasic acid (b) and the (meth) acrylic acid (c) for the production of a), polybasic acid (b), (meth) acrylic acid (c), polymerization inhibitor, and catalyst are charged, and air is blown, or a mixture of air and nitrogen or nitrogen is blown, and a solvent such as toluene, MIBK, or cyclohexane is used. Bottom, 8
The reaction is carried out for 10 to 20 hours in the temperature range of 0 to 120 ° C. until the acid value is 20 or less, preferably 15 or less, more preferably 10 or less. Alternatively, a polyol (a), a (meth) acrylic acid (c), a heavy inhibitor, and a catalyst are charged in the order of charging, and after reacting up to an acid value of 20-position under the above conditions, a polybasic acid (b) is charged and further under the above conditions. You can continue the reaction.
After completion of the reaction, the product is washed with water or neutralized with a caustic soda and then washed with water to remove the solvent.

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, trifluoromethyl sulfuric acid and trifluoromethyl acetic acid. Lewis acid or the like is used. In addition, metal complexes such as tetrabutyl zirconate and tetraisopropyl titanate, alkali and alkaline earth metal oxides such as magnesium oxide, calcium oxide and zinc oxide, and metal salt catalysts are also used. The amount of catalyst used is generally 0.1 to
It is 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.

As the polymerization inhibitor, alkylphenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, 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, butyraldoxime, methylethylketoxime, cyclohexanone oxime and the like are used.

Hybrid compound (A) in the present invention
Is a reaction ratio of the polyol (a) with the polybasic acid (b) and the (meth) acrylic acid (c) is 0.5 to 1.5 mol per 1 carboxylic acid group of the polybasic acid (b). Polyol (a)
And (meth) acrylic acid 0.8 to 1.5 times the residual hydroxyl group is used.

Next, the vegetable oil or its fatty acid ester used in the present invention will be explained. First of all, what is vegetable oil?
In triglyceride of glycerin and fatty acid, at least one fatty acid is a triglyceride which is a fatty acid having at least one carbon-carbon unsaturated bond, and typical compounds as such vegetable oils are, asa seed oil and linseed oil. , Eno, oil, deer oil, olive oil, cacao oil, kapok oil, kaya oil, mustard oil, kyounin oil, kiri oil, kukui oil, walnut oil, poppy oil, sesame oil, safflower oil, radish seed oil, soybean oil, large Funga 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, palm oil, peanut oil, dehydrated castor oil, etc. Can be mentioned. More preferred vegetable oils include vegetable oils having an iodine value of at least 100 (the parentheses indicate the iodine value quoted from the Oil and Fat Chemicals Handbook: Nikkan Kogyo Shimbun), asa seed oil (149 or more), Flaxseed oil (170 or more), eno oil (192 or more), deer oil (140 or more), Kapok oil (85-102),
Kaya oil (130 or more), mustard oil (101 or more), kyounin oil (97 to 109), kiri 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), Japanese radish seed oil (98 to 112), soybean oil (117 or more), large fuzi oil (101), corn oil (109 or more), rapeseed oil (97 to 107). ), Niger oil (126 or more), nuka oil (92 to 115), sunflower oil (125 or more), grape seed oil (124 or more), gentou oil (93 to 105), pine seed oil (146 or more),
Cottonseed oil (99-113), peanut oil (84-102),
Dehydrated castor oil (147 or more) is preferably used, and 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 enhanced.

In addition, in the present invention, it is also possible to use regenerated vegetable oil such as tempura oil which is recovered / regenerated after being used for food. The regenerated vegetable oil has a water content of 0.
Oils regenerated with 3% by weight or less, iodine value of 100 or more and acid value of 3 or less are preferable, and water content is 0.3% by weight.
By making the amount below, it becomes possible to remove impurities such as salt content contained in the water, which influence the emulsification behavior of the ink. By further selecting and regenerating vegetable oil having an acid value of 3 or less, it is possible to reduce the acid value of the regenerated vegetable oil and suppress the overemulsification of the ink. . As a method for regenerating the recovered vegetable oil, methods such as filtration, removal of 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 esterifying a saturated or unsaturated fatty acid obtained by hydrolysis of vegetable oil with a saturated or unsaturated alcohol. Liquid at room temperature (20-25 ° C) and normal pressure (101.
Fatty acid monoesters having a boiling point of 200 ° C. or higher at 3 kPa) and specific examples of such fatty acid esters include saturated fatty acid monoesters such as 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, isopropylate 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 the unsaturated fatty acid ester include ethyl oleate, propyl oleate, butyl oleate, allyl oleate, isoamyl oleate, heptyl oleate, 2-ethylhexyl oleate, methyl elaidate, ethyl elaidate, 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. , 2-ethylhexyl linolenate, methyl arachidonate,
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 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, Pentyl docosahexaenoate-hex, Hexyl docosahexaenoate, Hexahexaenoic acid, Docosahexahexaenoic acid, Docosahexahexaenoic acid, Docosahexahexaenoic acid 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 thereof include heptyl ricinoleate and 2-ethylhexyl ricinoleate.

The saturated or unsaturated fatty acid constituting the fatty acid ester in the present invention is, in fact, 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 acid, dehydrated castor oil fatty acid, or fractional fatty acid by fractional distillation thereof is used, and the saturated or Obtained as a mixture of unsaturated fatty acids.

Next, a resin having a softening point of 50 to 180 ° C. will be described. As the resin having a softening point of 50 to 180 ° C. or higher, rosin-modified phenol resin, petroleum resin, alkyd resin, rosin-modified alkyd resin, α, β-ethylenically unsaturated carboxylic acid ester-modified petroleum resin (B-1-1) ,
Examples include α, β-ethylenically unsaturated carboxylic acid modified rosin ester resin, melamine resin, terpene resin, coumarone indene resin, ketone resin, phenol modified petroleum resin, diallyl phthalate resin and the like.

Examples of the rosin-modified phenol resin include phenols such as carboxylic acid, hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, (tertiary) butylphenol, (tertiary) octylphenol, nonylphenol, dodecylphenol, hexylphenol and mixtures thereof, and formaldehyde. Resol or novolac phenolic resin that has been subjected to a condensation reaction with rosin (gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin,
A resin having a weight average molecular weight of 1 to 150,000 obtained by subjecting a maleinized rosin or the like) to a chroman reaction is used in a conventional reaction method. The rosin alkyd resin is obtained by reacting the rosin with a polyol such as glycerin, trimethylolethane, (di) trimethylol propane, (di) pentaerythritol in a conventional manner, and further phthalic anhydride, isophthalic acid, terephthalic acid,
(Anhydrous) trimellitic acid, (anhydrous) succinic acid, (anhydrous)
It is a resin having a weight average molecular weight of 5,000 to 150,000, which is obtained by reacting a polybasic acid such as maleic acid by a conventional method.

The α, β-unsaturated carboxylic acid ester-modified petroleum resin is an acid-modified petroleum resin obtained by modifying a petroleum resin containing a 5-membered ring compound as a constituent with an α, β-ethylenically unsaturated carboxylic acid or an anhydride thereof. Resin and 6 to 6 carbon atoms
Ester-modified petroleum resin obtained by esterifying 20 alkylene dihydric alcohol and / or alkyl or alkenyl trihydric alcohol having 3 to 25 carbon atoms, and further alkyl or alkenyl succinic acid having 4 to 30 carbon atoms or its An ester-modified petroleum resin obtained by an ester reaction using an acid anhydride, further having an alkyl group monohydric alcohol having a saturated or unsaturated double bond having 6 to 20 carbon atoms in the molecule, saturated or unsaturated An example is an ester-modified petroleum resin obtained by an ester reaction using at least one selected from the group consisting of fatty acids and resin acids.

The petroleum resin containing the 5-membered ring compound in the α, β-ethylenically unsaturated ester-modified petroleum resin as a constituent is cyclopentadiene, methylcyclopentadiene, di-pentamer thereof, and a large amount thereof in accordance with a conventional method. And a cyclopentadiene-based monomer alone or a mixture of a cyclopentadiene-based monomer and a copolymerizable co-monomer in the presence of a catalyst or without a catalyst. . Friedel-Crafts type Lewis acid catalysts such as boron trifluoride and its complexes with phenols, ethers, acetic acid and the like are usually used as the catalyst. The copolymerization ratio of the cyclopentadiene-based monomer and the comonomer copolymerizable therewith needs to be at least 5 mol% or more of the cyclopentadiene-based monomer.

Examples of the above comonomer 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,
A mixture of 4-trimethylpentene-1 and 2,4,4-trimethylpentene-2), 1-hexene, 2-hexene, 1-octene, 2-octene, 4-octene, 1-
Olefins having 2 to 10 carbon atoms such as decene, 1,3-
Chain conjugated dienes such as butadiene, 1,3-pentadiene (piperylene), isoprene, 1,3-hexadiene, 2,4-hexadiene, styrene, α-methylstyrene, β-methylstyrene, isopropenyltoluene,
Vinyl aromatics such as p-tert-butylstyrene, p-hydroxystyrene, vinyltoluene and divinylbenzene, indene, methylindene, coumarone (benzofuran), methylcoumarone (2-methylbenzofuran)
Aromatic unsaturated compounds such as

Examples of the α, β-ethylenically unsaturated carboxylic acid or its acid anhydride used in the production of α, β-ethylenically unsaturated carboxylic acid-modified petroleum resin include acrylic acid, methacrylic acid, maleic acid, Examples thereof include maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride, crotonic acid, and 2,4-hexadienonic acid (sorbic acid). These α,
The amount of modification of the β-ethylenically unsaturated carboxylic acid or its acid anhydride can be modified in the range of 1 to 100 mol% with respect to the cyclopentadiene-based monomer in the petroleum resin. The amount is modified in the range of 0.01 to 0.5 mol per 100 g. The optimum modification amount is preferably adjusted so that these unsaturated carboxylic acids and / or their acid anhydrides do not remain. The denaturation temperature is recommended to be 100 ° C or higher and 300 ° C or lower, which is a temperature at which petroleum resin is usually melted, but a range of 150 ° C to 250 ° C is preferably used. These unsaturated carboxylic acids and / or their acid anhydrides can be used alone or in combination in plural at an arbitrary amount ratio.

The alkylene dihydric alcohol having 6 to 20 carbon atoms used in the production of the α, β-ethylenically unsaturated carboxylic acid-modified petroleum resin is required to have a boiling point of at least 150 ° C. or higher at normal pressure. Furthermore, the boiling point is 2
From the viewpoint of reaction, the temperature is preferably 00 ° C. or higher. First, as linear alkylene dihydric alcohol, 1,6-hexanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octane are used. Diol, 1,2-octanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,2-decanediol, 1,12-dodecanediol, 1,2-dodecane Diol, 1,14-tetradecanediol,
1,2-tetradecane diol, 1,16-hexadecane diol, 1,2-hexadecane diol, and the like are the branched alkylene dihydric alcohols, 2-methyl-2,4-pentanediol, 3-methyl-1, 5-pentanediol, 2-methyl-2-propyl-1,3-
Propanediol, 2,4-dimethyl-2,4-dimethylpentanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, dimethyloloctane (Manufactured by Mitsubishi Chemical Corporation), 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2
-Methyl-1,8-octanediol, 2-butyl-2
-Ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, and the like, and as the cyclic alkylene dihydric alcohol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1, Examples include 4-cyclohexanedimethanol, 1,2-cycloheptanediol, tricyclodecanedimethanol, and the like. These dihydric alcohols can be used alone or in combination in any amount ratio.

In addition to the alkylene dihydric alcohol having 6 to 20 carbon atoms, if necessary, ethylene glycol, diethylene glycol, triethylene glycol,
It is also possible to use glycols such as polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and polypropylene glycol together. The amount used is preferably within the range of 50% by weight based on the alkylene dihydric alcohol having 6 to 20 carbon atoms.

The alkyl or alkenyl trihydric alcohol having 3 to 25 carbon atoms used for producing the α, β-ethylenically unsaturated carboxylic acid modified petroleum resin is a straight chain and / or branched chain having 4 to 26 carbon atoms. The aliphatic aldehyde of (1) and a molar excess of (para) formaldehyde can be obtained by a known production method by reacting with an alkali catalyst such as sodium hydroxide or calcium hydroxide. The method for producing a trimethylolalkane or the like from an aliphatic aldehyde and (para) formaldehyde is described in the following publicly known documents, for example, Acta. Chem. Scand. , Volume 16, Volume 4
No. 1062 (1962), J. Amer. Oi
l. Soc. , Vol. 45, No. 7, p. 517 (196
8 years), JP-A-59-13743, JP-A-61-
No. 148134, No. 62-8419, No. 2-207053, No. 4-89442, No. 9-71545, No. 9-715.
46, Japanese Patent Publication No. 4-55414, Japanese Patent Publication No. 4-
No. 55418, Japanese Patent Publication No. 8-2812, and the like.

Specific examples of the alkyl or alkenyl trihydric alcohol having 3 to 25 carbon atoms include 1,1,1
-Trimethylol butane, 1,1,1-trimethylol pentane, 1,1,1-trimethylol hexane, 1,
1,1-trimethylol heptane, 1,1,1-trimethylol octane, 1,1,1-trimethylol nonane, 1,1,1-trimethylol decane, 1,1,1-
Trimethylol undecane, 1,1,1-trimethylol dodecane, 1,1,1-trimethylol tridecane,
1,1,1-trimethylol tetradecane, 1,1,1
-Trimethylol pentadecane, 1,1,1-trimethylol hexadecane, 1,1,1-trimethylol heptadecane, 1,1,1-trimethylol octadecane,
Trimethylol linear alkanes such as 1,1,1-trimethylol nanodecane, 1,1,1-trimethylol-sec-butane, 1,1,1-trimethylol-te
rt-pentane, 1,1,1-trimethylol-ter
t-nonane, 1,1,1-trimethylol-tert-
Tridecane, 1,1,1-trimethylol-tert-
Heptadecane, 1,1,1-trimethylol-2-methyl-hexane, 1,1,1-trimethylol-3-methyl-hexane, 1,1,1-trimethylol-2-ethyl-hexane, 1,1 , 1-trimethylol-3-ethyl-hexane, trimethylol branched alkanes such as 1,1,1-trimethylolisoheptadecane, trimethylolbutene, trimethylolheptene, trimethylolpentene, trimethylolhexene, trimethylol There can be mentioned trimethylolalkenes such as heptene, trimethyloloctene, trimethyloldecene, trimethyloldodecene, trimethyloltridecene, trimethylolpentadecene, trimethylolhexadecene, trimethylolheptadecene, trimethyloloctadecene. . These trihydric alcohols can be used alone or in combination in any amount ratio.

Specific examples of the alkyl or alkenyl succinic acid having 4 to 30 carbon atoms or its acid anhydride used for producing the above ester-modified petroleum resin include butenyl (anhydrous) succinic acid, pentenyl (anhydrous) succinic acid and hexenyl. (Anhydrous) succinic acid, heptenyl (anhydrous) succinic acid, octenyl (anhydrous) succinic acid, nonenyl (anhydrous) succinic acid, decenyl (anhydrous) succinic acid, undecenyl (anhydrous)
Succinic acid, dodecenyl (anhydrous) succinic acid, tridecenyl (anhydrous) succinic acid, tetradecenyl (anhydrous) succinic acid,
Pentadecenyl (anhydrous) succinic acid, hexadecenyl (anhydrous) succinic acid, heptadecenyl (anhydrous) succinic acid,
Octadecenyl (anhydrous) succinic acid, isooctadecenyl (anhydrous) succinic acid, nonadecenyl (anhydrous) succinic acid, eicosadecenyl (anhydrous) succinic acid, poly (3-6) isobutenyl (anhydrous) succinic acid, poly (3-8) ) Butenyl (anhydrous) succinic acid, poly (3-10) propylenyl (anhydrous) succinic acid, 1-methyl-2-pentadecenyl (anhydrous) succinic acid, 1-ethyl-2-tetradecenyl (anhydrous) succinic acid, 1-propyl -2-Tridecenyl (anhydrous) succinic acid, 1-propyl-2-pentadecenyl (anhydrous) succinic acid, 1-hexyl-2-octenyl (anhydrous)
Linear or branched alkenyl group substitution (anhydrous) such as succinic acid, 1-octyl-2-decenyl (anhydrous) succinic acid
Succinic acid is butyl (anhydrous) succinic acid, pentyl (anhydrous) succinic acid, hexyl (anhydrous) succinic acid, heptyl (anhydrous) succinic acid, octyl (anhydrous) succinic acid, nonyl (anhydrous) succinic acid, decyl (anhydrous) Succinic acid, undecyl (anhydrous) succinic acid, dodecyl (anhydrous) succinic acid, tridecyl (anhydrous) succinic acid, tetradecyl (anhydrous) succinic acid, pentadecyl (anhydrous) succinic acid, hexadecyl (anhydrous) succinic acid, heptadecyl (anhydrous) succinic acid Acid, octadecyl (anhydrous) succinic acid, isooctadecyl (anhydrous) succinic acid, nonadecyl (anhydrous) succinic acid, eicosadecyl (anhydrous) succinic acid, 1-methyl-2-pentyl (anhydrous)
Succinic acid, 1-ethyl-2-tetradecyl (anhydrous) succinic acid, 1-propyl-2-tridecyl (anhydrous) succinic acid, 1-propyl-2-pentadecyl (anhydrous) succinic acid, 1-hexyl-2-octyl ( Anhydrous) succinic acid, 1
Mention may be made of linear or branched alkyl group-substituted (anhydrous) succinic acid such as -octyl-2-decyl (anhydrous) succinic acid. These alkyl-substituted or alkenyl-substituted succinic acids or acid anhydrides thereof can be used alone or in combination in any amount ratio.

These alkyl or alkenyl succinic acids or acid anhydrides thereof are described in, for example, JP-A-60-7897.
5, α-olefins, internal olefins, or oligomers such as propylene and butene, and maleic anhydride or maleic acid, as described in JP-A No. 5, JP-A-64-79163 and US Pat. No. 4,328,041. It is obtained by addition reaction with.

The alkyl monohydric alcohol having a saturated or unsaturated double bond having 6 to 20 carbon atoms in the molecule, which is used for producing the above ester-modified petroleum resin, has a boiling point of at least 150 ° C. or higher under normal pressure. Is required,
Furthermore, it is preferable for the reaction that the boiling point is 200 ° C. or higher.

As the monohydric alcohol having a saturated alkyl group, linear alkyl alcohols such as 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-
Octanol, 2-octanol, 3-octanol,
1-nonanol, 2-nonanol, 1-decanol, 2
-Decanol, 1-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1 -Heptadecanol, 1-octadecanol, 1
Examples thereof include nonadecanol and 1-eicosanol. 1 having a branched saturated alkyl group
As the hydric alcohol, 2-propyl-1-pentanol, 2-ethyl-1-hexanol, 4-methyl-3-
Heptanol, 6-methyl-2-heptanol, 2,
4,4-trimethyl-1-pentanol, 3,5,5-
Trimethyl-1-hexanol, 2,6-dimethyl-4
-Heptanol, isononyl alcohol, 3,7-dimethyl-1-octanol, 3,7-dimethyl-3-octanol, 2,4-dimethyl-1-heptanol, 2-
Examples include heptyl undecanol and the like.
In addition, cyclohexanol, cyclohexanemethanol,
Cyclic alcohols such as cyclopentane methylol, dicyclohexyl methanol, tricyclodecane monomethylol, norboneol, and water-added rosin alcohol (trade name: Avitol, manufactured by Hercules Co., Ltd.) can be used.

As the monohydric alcohol having an alkyl group having an unsaturated double bond in the molecule, an alkene group having one unsaturated double bond in the molecule and 2 in the molecule A monohydric alcohol having an alkadiene group having one, an alkatriene group having three unsaturated double bonds in the molecule, and an alkapolyene group having four or more unsaturated double bonds in the molecule, oleyl alcohol, 11
-Hexadecen-1-ol, 7-tetradecen-1-
All, 9-tetradecen-1-ol, 11-tetradecen-1-ol, 7-dodecen-1-ol, 10
-Undecen-1-ol, 9-decen-1-ol,
Citronellol, 3-nonen-1-ol, 1-octen-3-ol, 1-hexen-3-ol, 2-hexen-1-ol, 3-hexen-1-ol, 4-hexen-1-ol, 5-hexen-1-ol, dodecadiene-1-ol, 2,4-dimethyl-2,6-heptadien-1-ol, 3,5,5-trimethyl-2
-Cyclohexen-1-ol, 1,6-heptadien-4-ol, 3-methyl-2-cyclohexene-1-
All, 2-cyclohexen-1-ol, 1,5-hexadiene-3-ol, phytol, 3-methyl-3
-Buten-1-ol, 3-methyl-2-butene-1-
All, 4-methyl-3-penten-1-ol, 3-
Methyl-1-penten-3-ol, 6-methyl-5-
Examples thereof include linear, branched or cyclic unsaturated alkyl group-containing monohydric alcohols such as penten-2-ol, geraniol, rosinol, linanol and α-terpineol. These monohydric alcohols can be used alone or in combination in any amount ratio.

Examples of the saturated or unsaturated fatty acid used in the production of the ester-modified petroleum resin include compounds having a saturated or unsaturated aliphatic group having a boiling point of 150 ° C. or higher at normal pressure and a carboxyl group, Preferable examples are compounds having a saturated or unsaturated aliphatic group having 3 to 25 carbon atoms. Such examples include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecyl acid, lauric acid,
Saturated fatty acids such as tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, crotonic acid, isocrotonic acid, lindelic acid, tzudic acid, myristoleic acid, palmitoleic acid. , Undecyleic acid, oleic acid, elaidic acid, gadrenic acid, gondoic acid, cetrainic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linoelaidic acid, linoleic acid, eleostearic acid, arachidonic acid, sardine acid, herring An unsaturated fatty acid such as an acid may be mentioned. These saturated or unsaturated fatty acids (can be used alone or in combination in any amount ratio.

The resin acid (rosin) used in the production of the above ester-modified petroleum resin includes gum rosin, wood rosin, tall oil rosin, disproportionated rosin, polymerized rosin, and α, β-ethylenically unsaturated carboxylic acid. Acids or their anhydrides, such as fumaric acid, (anhydrous) maleic acid,
Examples thereof include Diels-Alder reaction products with (anhydrous) itaconic acid, (anhydrous) citraconic acid and the like. These resin acids may be used alone or in combination of two or more at any ratio.

The method for producing the above ester-modified petroleum resin is as follows:
An acid-modified petroleum resin, a dihydric alcohol, a trihydric alcohol, a substituted succinic acid or its acid anhydride, a monohydric alcohol, a component selected from a saturated or unsaturated fatty acid and a resin acid are simultaneously charged, and then a heating reaction is started. It is also possible to carry out the reaction in any order. In addition, after producing an adduct body in which a dihydric alcohol or a trihydric alcohol is reacted with a saturated or unsaturated fatty acid or a resin acid in advance, the adduct body is reacted with an acid-modified hydrocarbon resin or other constituent components. It is also possible.

In the esterification reaction of the above ester-modified petroleum resin, a catalyst can be used if necessary. As the catalyst, benzenesulfonic acid, p-toluenesulfonic acid, p-dodecylbenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid and other organic sulfonic acids, sulfuric acid, hydrochloric acid and other mineral acids, trifluoromethyl sulfuric acid,
Examples include trifluoromethyl acetic acid. Furthermore, metal complexes such as tetrabutyl zirconate and tetraisobutyl titanate, metal salt catalysts such as magnesium oxide, magnesium hydroxide, magnesium acetate, calcium oxide, calcium hydroxide, calcium acetate, zinc oxide, zinc acetate, etc. can also be used. is there. These catalysts are usually used in the range of 0.01 to 5% by weight based on the total resin. In order to suppress the coloring of the resin due to the use of a catalyst, hypophosphorous acid, triphenylphosphite, triphenylphosphate, triphenylphosphine, etc. may be used in combination. The weight average molecular weight of the ester-modified petroleum resin that is preferably used is 10,000 to 300,000, preferably 20,000 to 150,000.

The α, β-ethylenically unsaturated carboxylic acid-modified rosin ester resin is a Diels-Alder reaction product of the above-mentioned rosins with α, β-ethylenically unsaturated carboxylic acid or its anhydride, and has C4 to C18. There is a resin prepared by reacting trimethylolalkane or alkene and / or a polyol other than trimethylolalkane or alkene, and the composition ratio thereof is rosin /
The weight ratio of the α, β-ethylenically unsaturated carboxylic acid or the anhydride thereof is 80/20 to 97/3, and the (rosin and the α, β-ethylenically unsaturated carboxylic acid or the anhydride carboxylic acid thereof are (Total molar quantity) / (total molar quantity of hydroxyl groups of C4 to C18 trimethylolalkane or alkene and other polyols) is 1 / 0.5 to 1 /
An example is a resin that is 1.2. In the above reaction, rosin and petroleum resin of C5 and C9 fractions are rosin / C
5, C9 fraction petroleum resin = 10-90 wt% / 90-10
The case of using them together in a weight% ratio can also be exemplified.

Α, β-α, β used in the production of ethylenically unsaturated carboxylic acid-modified rosin ester resin (B-2-1)
Examples of the ethylenically unsaturated carboxylic acid or its anhydride include fumaric acid, maleic acid or its anhydride, itaconic acid, crotonic acid, cinnamic acid, (meth) acrylic acid and the like. Particularly preferred is maleic acid or its anhydride.

The reaction between the rosin and the α, β unsaturated carboxylic acid or its anhydride is a Diels-Alder reaction,
The reaction can be performed by a known method. For example, the reaction temperature is 120 to 300 ° C, preferably 150 to 260 ° C,
The reaction time is 1 to 4 hours. The disproportionated rosin, the rosin of a dimer or higher in the polymerized rosin, and the hydrogenated rosin are unlikely to undergo the Diels-Alder reaction, and the rosin not subjected to such modification is acid-modified by the Diels-Alder reaction. The reaction ratio between the rosin and the α, β-ethylenically unsaturated carboxylic acid or the anhydride thereof is such that the ratio of the number of moles of the rosin / α, the β-ethylenically unsaturated carboxylic acid or the anhydride thereof is The reaction is carried out in the range of 1 or more. α,
When the reaction amount of the β-ethylenically unsaturated carboxylic acid or its anhydride increases, the solubility of the resin in the (meth) acrylate monomer deteriorates.
The weight ratio of α, β-ethylenically unsaturated carboxylic acid or its anhydride is preferably 80/20 to 97/3, and when the amount of α, β-ethylenically unsaturated carboxylic acid or its anhydride is larger than this, the resin is The solubility in the above (meth) acrylate monomer is deteriorated, and if it is too small, an appropriate molecular weight of the resin for printing ink cannot be obtained.

C4 to C1 used for producing α, β-ethylenically unsaturated carboxylic acid modified rosin ester resin (B-2-1)
Trimethylolalkanes or alkenes of 8 are known by using a linear or branched aliphatic aldehyde having 5 to 19 carbon atoms and a molar excess of (para) formaldehyde using an alkali catalyst such as sodium hydroxide or calcium hydroxide. Obtained by the manufacturing method. There are the following known documents for producing trimethylolalkane from aliphatic aldehyde and (para) formaldehyde.

As C4 to C18 trimethylolalkane (alkene), trimethylolbutane (butene), trimethylolheptane (butene), trimethylolpentane (pentene), trimethylolhexane (hexene), trimethylolheptane (heptene), Trimethylol octane (octene), trimethylol decane (decene), trimethylol dodecane (dodecene), trimethylol tridecane (tridecene), trimethylol pentadecane (pentadecene), trimethylol hexadecane (hexadecene), trimethylol heptadecane (heptadecene) , Trimethylol octadecane (octadecene) and the like. The alkyl group or alkenyl group may be of a straight chain type or a branched type of iso-type or tertiary type.

A C4 to C18 trimethylolalkane or alkene is produced by synthesizing an aldehyde having a carbon number higher than that of the trimethylolalkane or alkene and an excess of formaldehyde. For example, trimethylol octane is synthesized by alkali catalysis from normal or isononyl aldehyde or other branched isomers of nonyl aldehyde or a mixture thereof and 4 to 6 mol of excess formaldehyde. To further illustrate, trimethylolheptadecane (heptadecene) is similarly synthesized from normal stearyl aldehyde, isostearyl aldehyde or oleyl aldehyde and excess formaldehyde.

Reaction products of rosins with α, β-ethylenically unsaturated carboxylic acids or their anhydrides, C 4 -C 18
The reaction ratio of trimethylolalkane or alkene is the total molar amount of carboxylic acid of the reaction product of the rosin and the α, β-ethylenically unsaturated carboxylic acid or its anhydride / hydroxyl group of trimethylolalkane or alkene. The total number of moles is 1 / 0.5 to 1 / 1.2, preferably 1
/0.8 to 1/1. Esterification reaction is 180-2
The reaction is carried out at 70 ° C. until the acid value reaches the 20-30 position. A catalyst may be used in this esterification reaction, and as the catalyst, sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid and ethanesulfonic acid, mineral acids such as sulfuric acid and hydrochloric acid, and trifluoromethane. There are methylsulfuric acid, trifluoromethylacetic acid, Lewis acid, etc., and metal complexes such as tetrabutyl zirconate and tetraisopropyl titanate, alkalis such as magnesium oxide, calcium oxide, zinc oxide, oxides of alkaline earth metals, metal salts. Examples thereof include catalysts. These catalysts are used in an amount of 0.01 to 1% by weight based on the total resin and reacted at a temperature of 200 ° C. or higher. However, since the reaction product is easily colored under such conditions, a reducing agent such as hypophosphorous acid, triphenyl phosphite, or triphenyl phosphate may be used in combination.

The α, β-ethylenically unsaturated carboxylic acid-modified rosin ester resin is preferably not a liquid at room temperature but a solid resin from the viewpoint of ink drying property, and preferably has a melting point of 1
It is preferably 20 ° C. or higher. However, if the trimethylolalkane or alkene has more than 8 carbon atoms, the melting point may decrease depending on the molecular weight of the resin. In that case, it is better to use a polyol other than the above-mentioned trimethylolalkane or alkene together. The amount of the polyol other than trimethylolalkane or alkene to be used is 0 to 80% of the total number of moles of hydroxyl groups of all polyols used in the resin including C4 to C18 trimethylolalkane or alkene. good. Especially C
When the number of carbon atoms of the 4- to C18 trimethylolalkane or alkane or alkene of the alkene component exceeds 10, it is preferable to use a polyol having a hydroxyl group molar amount of 10 to 80%.

As the polyol other than the C4 to C18 trimethylolalkane or alkene used in the production of the α, β-ethylenically unsaturated carboxylic acid modified rosin ester resin, dihydric alcohols such as ethylene glycol, diethylene glycol and triethylene can be used. Glycol,
Polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, hexanediol, octanediol, nonanediol, neopentyl glycol, 2-ethylhexyldiol, 2-methyl-2,4-pentanediol, 2 , 2,4-Trimethyl-1,3-pentanediol, 2,4-diethyl-
1,5-Pentanediol, xylene glycol, cyclohexanedimethanol, hydroquinone bis (2-hydroxyethyl) ether, etc., as trihydric or higher alcohol (mono-, di- or tri) glycerin, (mono-, di- or tri) trimethylolethane , (Mono, di or tri) trimethylolpropane, (mono, di or tri)
Examples include trimethylol alkanes, (mono-, di- or tri) pentaerythritol, aliphatic polyhydric alcohols such as sorbitol, tris (2-hydroxyethyl) isocyanurate, inositol, cyclic polyhydric alcohols such as cellulose and the like. . Furthermore, compounds obtained by reacting compounds having active hydrogen such as polyhydric alcohols, polyhydric phenols and amines with alkylene oxides such as ethylene oxide and propylene oxide, for example, bisphenol A diethylene oxide adduct, catechol, resorcin or Examples include diethylene oxide adducts of hydroquinone and triethanolamine. Other polyols to be used in combination are preferably glycerin, trimethylolpropane and pentaerythritol from the viewpoint of proper resin molecular weight, melting point and cost.

The α, β-ethylenically unsaturated carboxylic acid-modified rosin ester resin (B-2-1) is a reaction product of a rosin and an α, β-ethylenically unsaturated carboxylic acid or an anhydride thereof with C 4 -C. In addition to reacting C18 trimethylolalkane or alkene and other polyols, α,
β-ethylenically unsaturated carboxylic acid or its anhydride and C
The reaction product of a 4-C18 trimethylolalkane or alkene and a polyol other than it may be reacted with a rosin, or a rosin, an α, β-ethylenically unsaturated carboxylic acid or an anhydride thereof, a C4 C18 trimethylolalkane or alkene and other polyol may be charged at the same time. When this resin is used for printing ink, acid value is 30 or less, weight average molecular weight is 1
˜200,000 (measured by gel permeation chromatography), and the melting point is preferably 50 to 180 ° C.

Further, as the α, β-ethylenically unsaturated carboxylic acid-modified rosin ester resin, a Diels-Alder reaction product of the above-mentioned rosin and α, β-ethylenically unsaturated carboxylic acid or an anhydride thereof is added with a C5 to C30 monohydric alcohol. An example of the resin is a resin obtained by reacting with a polyol. The rosin / α, β-ethylenically unsaturated carboxylic acid or its anhydride is synthesized according to the above-mentioned synthetic method. Further, the C5 to C30 monohydric alcohols are monohydric long-chain normal, iso, tertiary, hyperbranched isomer alcohols and / or mixtures thereof, and / or their ethoxylates and the like.
Specifically, as linear alkyl alcohols, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1
-Octanol, 2-octanol, 3-octanol, 1-nonanol, 2-nonanol, 1-decanol, 2-decanol, 1-undecanol, 2-undecanol, 1-dodecanol, 2-dodecanol, 1-
Tridecanol, 2-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 2-pentadecanol, 1-hexadecanol, 2
-Hexadecanol, 1-heptadecanol, 2-heptadecanol, 1-octadecanol, 2-octadecanol, 1-nonadecanol, 2-nonadecanol, 1
-Icosanol, oleyl alcohol, geraniol {(CH3) 2C = CH (CH2) 2C (CH3) = CH
CH2 OH} Rinalol {(CH3) 2 C = CH (C
H2) 2C (CH3) (OH) CH = CH2} myrisyl alcohol (C30H61OH) and the like are exemplified.

As the branched alkyl alcohol, 2-propyl-1-pentanol, 2-ethyl-1-hexanol, 4-methyl-3-heptanol, 6-methyl-2.
-Heptanol, 2,4,4-trimethyl-1-hexanol, 2,6-dimethyl-4-heptanol, isononyl alcohol, 3,7 dimethyl-3-octanol,
2,4 dimethyl-1-heptanol, 2-heptyl undecanol, etc. are illustrated.

Alternatively, it may be an alkoxylate of the monohydric alcohol exemplified above. These reactions are addition-reacted by a known method using an alkali catalyst. For example, 1-butanol ethoxylate (C6 H13 OC2 H4 OH), 2-butanol propoxylate (C6 H13 OCH2 CH (O
H) CH3), 1-octanol ethoxylate, 2-
Examples are octanol propoxylate, and the above-mentioned monohydric alcohol ethoxylates and propoxylates. Further included are alkoxylates of alkylphenols having C4 to C20 alkyl groups. These reactions are addition-reacted by a known method using an alkali catalyst. C4 ~
C20 alkylphenols such as butylphenol, amylphenol, octylphenol, nonylphenol, dodecylphenol, hexadecylphenol, nonadecylphenol, ethoxylates such as icosyl (C20H21) phenol and propoxylates are included. Specific examples thereof include octylphenol ethoxylate, nonylphenol ethoxylate, dodecylphenol ethoxylate, and the like. Further, as C5 to C30 fat-reducing alcohols, cyclopentanol, cyclohexanol,
Also included are cyclopentane monomethylol, dicyclopentane monomethylol, tricyclodecane monomethylol, norboneol, terpineol, and water-added rosin alcohol (trade name Abitol, manufactured by Hercules Co., Ltd.).

When the polyol is divalent, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, 1,6-hexanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1 , 10-decanediol, 1,2-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,
2-tetradecanediol, 1,16-hexadecanediol, 1,2-hexadecanediol, neopentyl glycol, 2-ethylhexyldiol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-
Propanediol, 2,4-dimethylpentanediol, 2,2-diethyl-1,3-propanediol,
2,2,4-trimethyl-1,3-pentanediol,
Dimethylol octane (Mitsubishi Chemical), 2-ethyl-1,
3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1. , 5-pentanediol,
2,4-diethyl-1,5-pentanediol, xylene glycol, cyclohexanedimethylol, hydroquinone bis (2-hydroxyethyl) ether, (mono or di or tri) glycerin as a trivalent or higher alcohol, (mono or di or Tri) trimethylol ethane, (mono- or di- or tri) trimethylol propane, (mono- or di- or tri) trimethylol alkane, (mono- or di- or tri) pentaerythritol, aliphatic polyhydric alcohols such as sorbitol, tris (2 Examples include cyclic polyhydric alcohols such as -hydroxyethyl) isocyanurate, inositol, and cellulose. Furthermore, compounds obtained by reacting polyhydric alcohols, polyhydric phenols, amine-based compounds having active hydrogen with alkylene oxides such as ethylene oxide and propylene oxide, for example, bisphenol A diethylene oxide adducts, catechol or resorcin, or Hydroquinone diethylene oxide adduct,
Examples include triethanolamine triethylene oxide adducts. Other polyols to be used in combination are preferably glycerin, trimethylolpropane, pentaerythritol, etc. from the viewpoint of proper resin molecular weight, melting point, and cost.

C 5
The reaction ratio of the -C30 monohydric alcohol and the polyol is the total molar amount of the rosins and the carboxylic acid of the α, β ethylenically unsaturated carboxylic acid or the anhydride thereof / the C5-C30 monohydric alcohol and the polyol. The total molar quantity of hydroxyl groups is 1 / 0.5 to 1 / 1.2, preferably 1
/0.8 to 1 / 1.2. The esterification reaction is 180
The reaction is carried out at ˜270 ° C. until the acid value reaches the 20 to 30th position. A catalyst may be used in this esterification reaction. Examples of the acid 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, trifluoromethyl sulfuric acid, trifluoromethyl acetic acid and Lewis acid. , Further metal complexes such as tetrabutyl zirconate and tetraisopropyl titanate, magnesium oxide,
Examples thereof include alkali oxides such as calcium oxide and zinc oxide, alkaline earth metal oxides, and metal salt catalysts. These catalysts are used in an amount of 0.01 to 1% by weight based on the total resin and reacted at a temperature of 200 ° C. or higher. However, since the reaction product is easily colored under such conditions, a reducing agent such as hypophosphorous acid, triphenyl phosphite, or triphenyl phosphate may be used in combination.

The above-mentioned monohydric alcohol is 5 to 5 in the total resin weight.
40% by weight, preferably 8 to 20% by weight. If the amount of these monohydric alcohols is less than this, the solubility of the resin deteriorates, and if it is more than this, the molecular weight of the resin does not increase appropriately and the melting point of the resin also decreases.

The reaction sequence is as follows: the above rosins and the above α, β ethylenically unsaturated carboxylic acids or their anhydrides)
The above monohydric alcohol and the above polyol may be charged in the reaction product of 1) in the same order or at the same time. Further, the rosin may be reacted with a reaction product of the α, β ethylenically unsaturated carboxylic acid or its anhydride, the monohydric alcohol and the polyol, or the rosin, the α, β ethylenically unsaturated The carboxylic acid or its anhydride, the above monohydric alcohol, and the above polyol may be charged at the same time. When this resin is used as a printing ink, the acid value is 30 or less, the weight average molecular weight is 1 to 200,000 (measured by gel permeation chromatography), and the melting point is 5.
0-180 degreeC is preferable.

The α, β-ethylenically unsaturated carboxylic acid-modified rosin ester resin is a Diels-Alder reaction product of a rosin and an α, β-ethylenically unsaturated carboxylic acid or an anhydride thereof, and a C6 to C60 dihydric alcohol. If necessary, a resin obtained by reacting a trivalent or higher valent polyol may be used. The composition ratio of the rosins / α, β-ethylenically unsaturated carboxylic acid or the anhydride thereof is as described above.

Examples of the C6 to C30 dihydric alcohol include linear 1,6-hexanediol and 1,7-hexanediol.
Heptanediol, 1,8-octanediol, 1,
9-nonanediol, 1,10-decanediol, 1,
14-tetradecanediol, 1,16-hexadecanediol, 1,2-hexanediol in a branched form,
1,5-hexanediol, 2,5-hexanediol, 2-ethylhexyldiol, 1,2-octanediol, 1,2-decanediol, 2-methyl-2,4
-Pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethylpentanediol, 2,2
-Diethyl-1,3-propanediol, 2,2,4-
Trimethyl-1,3-pentanediol, dimethyloloctane (Mitsubishi Chemical Corporation), 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8. -Octanediol, 2
-Butyl-2-ethyl-1,3-propanediol,
2,4-diethyl-1,5-pentanediol, 2,4
-Diethyl-1,5-pentanediol, 1,2-dodecanediol, 1,12-dodecanediol, 1,2-
Examples include tetradecanediol and 1,2-hexadecanediol. Further, a cyclic dimer fatty acid diol consisting of an ester compound of dimer fatty acid and dihydric alcohol or a diol of hydrogenated dimer fatty acid, for example, PESPOL 200 (ester compound of dimer acid and ethylene glycol), PESPOL 211
(Ester compound of dimer acid, adipic acid and ethylene glycol), PESPOL 600 (ester compound of dimer acid and hexanediol), PESPOL 6
01 ((ester compound of dimer acid and hexanediol), PESPOL 602 (ester compound of dimer acid and hexanediol), PESPOL 611 (ester compound of dimer acid and hexanediol),
Examples include PESPOL 900 (ester compound of dimer acid and nonanediol), PESPOL HP-1000 (dimer diol obtained by hydrogenation of dimer acid), and the above-mentioned dimer diol manufactured by Toagosei Co., Ltd. (Mono, di or tri) glycerin, (mono, di or tri) trimethylolethane as trihydric or higher alcohol,
(Mono, di or tri) trimethylol propane, (mono, di or tri) trimethylol alkane, (mono,
Examples thereof include aliphatic polyhydric alcohols such as di- or tri) pentaerythritol and sorbitol, and cyclic polyhydric alcohols such as tris (2-hydroxyethyl) isocyanurate, inositol and cellulose. As the trihydric or higher polyol to be used in combination, glycerin, trimethylolpropane, pentaerythritol and the like are preferable in terms of proper resin molecular weight, melting point and cost.

Reaction products of rosins and α, β-ethylenically unsaturated carboxylic acids or their anhydrides with C6
The reaction ratio of the C30 with the dihydric alcohol and the trihydric or higher polyol is such that the total molar amount of the rosin and the carboxylic acid of the α, β-ethylenically unsaturated carboxylic acid or its anhydride / the above C6 to C60. The total molar quantity of hydroxyl groups in dihydric alcohol and, if necessary, trihydric or higher polyol is 1 /
0.5 to 1 / 1.2, preferably 1 / 0.8 to 1/1.
Set to 2. The esterification reaction is carried out at 180 to 270 ° C. until the acid value reaches the 20 to 30th position. A catalyst may be used in this esterification reaction. Examples of the acid 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, trifluoromethyl sulfuric acid, trifluoromethyl acetic acid and Lewis acid. Further, metal complexes such as tetrabutyl zirconate and tetraisopropyl titanate, alkali oxides such as magnesium oxide, calcium oxide and zinc oxide, alkaline earth metal oxides, metal salt catalysts and the like are exemplified. 0.01 to 1 of these catalysts in all resins
The reaction is carried out at a temperature of 200 ° C. or higher using a weight ratio of 200%. However, under such conditions, the reaction product is easily colored,
Reducing agent hypophosphorous acid, triphenyl phosphite,
Triphenyl phosphate etc. may be used together.

The C6 to C60 dihydric alcohol is 5 to 40% by weight, preferably 8 to 20% by weight, based on the total weight of the resin. If the amount of these dihydric alcohols C6 to C60 and, if necessary, the trihydric or higher polyhydric alcohol is less than this, the solubility with the (meth) acrylate monomer deteriorates, and if more than this, the molecular weight of the resin is proper. It is not preferable because it does not become too large and the melting point of the resin becomes low.

The reaction sequence may be changed by charging the reaction product of the rosin and the α, β-ethylenically unsaturated carboxylic acid or its anhydride with a C6 to C60 dihydric alcohol and a trihydric or higher polyol. , May be charged at the same time. Further, the above α, β-ethylenically unsaturated carboxylic acid or its anhydride may be reacted with the reaction product of the above C6 to C60 dihydric alcohol and, if necessary, a trihydric or higher hydric polyol, or the above rosin, The above α, β-ethylenically unsaturated carboxylic acid or its anhydride), and the above C6 to C
60 dihydric alcohols and, if necessary, trihydric or higher polyols may be charged simultaneously. When this resin is used as a printing ink, an acid value of 30 or less and a weight average molecular weight of 1 to 2
It is preferably 100,000 (measured by gel permeation chromatography), the solubility in a printing ink solvent is 130 ° C. or lower, and the melting point is 100 ° C. or higher, preferably 120 ° C. or higher.

The α, β-ethylenically unsaturated carboxylic acid-modified rosin ester resin is obtained by reacting a Diels-Alder reaction product of a rosin with an α, β-ethylenically unsaturated carboxylic acid or an anhydride thereof with a polyol and a fatty acid. The rosin / α, β-ethylenically unsaturated carboxylic acid or its anhydride can be synthesized according to the above-mentioned synthetic method.

Further, the α, β-ethylenically unsaturated carboxylic acid-modified rosin ester resin is a rosin or α, β-
Even a resin in which the total number of moles of carboxylic acid of ethylenically unsaturated carboxylic acid or its anhydride / the total number of moles of hydroxyl group of the hydroxyl group-containing compound and polyol is 1 / 0.5 to 1/1/2 Good.

As the above-mentioned polyol, in the case of dihydric alcohol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,14-tetradecanediol, 1,16-hexadecanediol,
1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 2-ethylhexyldiol, 1,2-octanediol, 1,2-decanediol, 2-methyl-2,4-pentanediol , 3-
Methyl-1,5-pentanediol, 2-methyl-2-
Propyl-1,3-propanediol, 2,4-dimethylpentanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, dimethyloloctane (Mitsubishi Chemical Company), 2-ethyl-1,3-hexanediol, 2,
5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,
5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,2-dodecanediol, 1,12
-Dodecanediol, 1,2-tetradecanediol,
Examples include 1,2-hexadecanediol and the like. Furthermore,
An ester compound of a dimer fatty acid and a dihydric alcohol, or a diol of a hydrogenated product of a dimer fatty acid,
Cyclic dimer fatty acid diols such as PESPOL 2
00 (dimer acid and ethylene glycol ester compound), PESPOL 211 (dimer acid, adipic acid and ethylene glycol ester compound), PESPOL 600 (dimer acid and hexanediol ester compound), PESPOL 601 ((dimer acid and hexanediol Ester compound), PESPOL 60
2 (ester compound of dimer acid and hexanediol), PESPOL 611 (ester compound of dimer acid and hexanediol), PESPOL 900 (ester compound of dimer acid and nonanediol), PESPOL HP-1000 (dimer by hydrogenation of dimer acid) Examples thereof include dimer diol manufactured by Toagosei Co., Ltd., and the like. For trihydric or higher alcohols,
(Mono, di or tri) glycerin, (mono, di or tri) trimethylolethane, (mono, di or tri)
Aliphatic polyhydric alcohols such as trimethylolpropane, (mono-, di- or tri) trimethylolalkane, (mono-, di- or tri) pentaerythritol, sorbitol, tris (2-hydroxyethyl) isocyanurate, inositol, cyclic rings such as cellulose Examples include polyhydric alcohols. The trihydric polyol to be used is preferably glycerin, trimethylolpropane, pentaerythritol or the like from the viewpoint of proper resin molecular weight, melting point and cost. As fatty acids, saturated or unsaturated, normal or branched C6 to C36 fatty acids such as caproic acid, enanthic 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, eicosic acid and the like. Furthermore, fatty acids of natural oils and fats, 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 , Rapeseed oil fatty acid and the like are exemplified. Further, as fish oil and animal oil fatty acid, squid oil fatty acid, sardine oil fatty acid, saury oil fatty acid,
Examples thereof include cod oil fatty acid, whale oil fatty acid, beef tallow oil fatty acid, lard oil fatty acid, and sheep tallow oil fatty acid. Furthermore, dimer acids of fatty acids such as tung oil dimer fatty acid and linseed oil dimer fatty acid are exemplified.

As a reaction method, rosins and α, β-
The reaction product of the ethylenically unsaturated carboxylic acid or its anhydride is reacted with a polyol and a fatty acid. The reaction ratio is such that the rosins, the α, β-ethylenically unsaturated carboxylic acid or the anhydride thereof, and the fatty acid (the total molar amount of carboxylic acid / the total molar amount of hydroxyl group of the polyol are 1 / 0.5. ~ 1 / 1.2, preferably 1 / 0.8
~ 1 / 1.2. Esterification reaction is 180-270
The reaction is carried out at 0 ° C until the acid value reaches the 20-30 position. A catalyst may be used in this esterification reaction. Examples of the acid 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, trifluoromethyl sulfuric acid, trifluoromethyl acetic acid and Lewis acid. Further, metal complexes such as tetrabutyl zirconate and tetraisopropyl titanate, alkali oxides such as magnesium oxide, calcium oxide and zinc oxide, alkaline earth metal oxides, metal salt catalysts and the like are exemplified. These catalysts are used in an amount of 0.01 to 1% by weight based on the total resin and reacted at a temperature of 200 ° C. or higher. However, since the reaction product is easily colored under such conditions, a reducing agent such as hypophosphorous acid, triphenyl phosphite, or triphenyl phosphate may be used in combination.

Further, as a reaction method, rosins and α, β-
The reaction product of an ethylenically unsaturated carboxylic acid or its anhydride is reacted with a reaction product obtained by previously reacting a polyol and a fatty acid in the same manner as in the above esterification method. The reaction method for reacting the polyol and the fatty acid in advance is the same as the above esterification method. The reaction ratio is the number of moles of fatty acid / the number of moles of hydroxyl group of polyol = 0.
1 to 0.9, preferably 0.2 to 0.5 is good. If the molar ratio of the fatty acid is less than this, the solubility of the finished resin and the solvent for printing ink is poor, and if it is more than the appropriate molecular weight is not reached. The acid value is 10 or less, preferably 5 or less. Compounds of this family are fatty acid esters of sorbitan,
For example, a product manufactured by Kao Corporation, Emazol L-10 (H)
(Sorbitan monolaurate), Emazol P-10
(Sorbitan monopalmitate), Emazol S-10
(Sorbitan monostearate), Emazol S-20
(Sorbitan distearate), Emazole O-15R
(Sorbitan sesquioleate), Emazole O-10
(F) (sorbitan monooleate) and the like are included. Further, the α, β-ethylenically unsaturated carboxylic acid or its anhydride, the polyol and the reaction product may be reacted with the rosin, or the rosin, the α, β
-The ethylenically unsaturated carboxylic acid or its anhydride, the above polyol and the above fatty acid may be charged at the same time.

Fatty acid is 5 to 40% by weight based on the total weight of resin,
It is preferably 8 to 20% by weight. If the amount of these fatty acids is less than this, the solubility in the solvent for printing ink deteriorates, and if it is more than this, the molecular weight of the resin does not increase appropriately and the melting point of the resin also decreases. When using this resin as a printing ink, an acid value of 30 or less and a weight average molecular weight of 1
˜200,000 (measured by gel permeation chromatography), solubility in printing ink solvent is 130 ° C. or lower, melting point is 100 ° C. or higher, preferably 120 ° C. or higher.

Next, the (meth) acrylic monomer or acrylic oligomer having an ethylenically unsaturated double bond will be described. As the (meth) acrylic monomer monomer having an ethylenically unsaturated double bond, as a monofunctional monomer, alkyl (having 1 to 18 carbon atoms) (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl. There are (meth) acrylates, hexyl (meth) acrylates, octyl (meth) acrylates, dodecyl (meth) acrylates, stearyl (meth) acrylates, and also benzyl (meth) acrylates, butylphenol, octylphenol or nonylphenols or alkylphenols such as 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) (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, hydroxypyr Baryl 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 (meta)
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-propanedio- 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 (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, 1,5-hexanediol poly (1-1)
0) Alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct, di (meth) acrylate, 2,5-hexanediol poly (1-10) alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) Adduct di (meth) acrylate, 1,7-heptanediol poly (1-10) alkylene oxide (for example, 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 (for example, 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 (for example, 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 (for example, ethylene oxide, propylene oxide, butylene oxide, etc.)
Adduct di (meth) acrylate, 1,14-tetradecanediol poly (1-10) alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate,
1,2-tetradecanediol poly (1-10) alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, 1,16-hexadecanediol poly (1-10) alkylene oxide (for example, Ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, 1,2-hexadecanediol poly (1-10) alkylene oxide (for example, ethylene oxide, propylene oxide,
Butylene oxide, etc.) adduct di (meth) acrylate, 2-methyl-2,4-pentane poly (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,
Butylene oxide etc.) adduct di (meth) acrylate, 2-methyl-2-propyl-1,3-propanediol poly (1-10) alkylene oxide (eg 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) ,
Butylene oxide, etc.) adduct di (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol poly (1-10) alkylene oxide (for example, 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 (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol poly ( 1-10) alkylene oxide (for example, ethylene oxide, propylene oxide,
Butylene oxide, etc.) adduct di (meth) acrylate, 2-methyl-1,8-octanediol poly (1-
10) Alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol poly (1-10) alkylene oxide (for example, ethylene oxide) , Propylene oxide, butylene oxide, etc.) adduct di (meth)
Acrylate, 2,4-diethyl-1,5-pentanediol poly (1-10) alkylene oxide (for example, 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 (for example, ethylene oxide, propylene oxide, butylene) Oxide) 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 (for example, 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 adduct (for example, 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 bispheno 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,
Butylene oxide, etc.) di (meth) acrylate, bisphenol A tetraethylene oxide adduct dicaprolactonate di (meth) acrylate, bisphenol F tetraethylene oxide adduct dicaprolactonate di (meth) acrylate, and the like. Glycerin tri (meth) acrylate as a trifunctional monomer, glycerin poly (1-10) alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri Methylolpropane 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 Acrylate, trimethylolethane poly (1-10) alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct Ethylene oxide, propylene oxide, butylene oxide, other) tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethylolhexane poly (1-10) alkylene oxide (eg ethylene oxide, propylene oxide, butylene oxide, etc.) tri (Meth) acrylate, trimethyloloctane tri (meth) acrylate, trimethyloloctane poly (1-10) alkylene oxide (eg ethylene oxide, propylene oxide, butylene oxide, etc.) adduct tri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, trihydroxybenzene (pyrogallol, etc.) poly (1-10) alkylene oxide (for example, 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 (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditri Methylol propane poly (1-1
0) Alkylene oxide (eg ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylolpropane tetracaprolactonate, tetra (meth) acrylate, ditrimethylolethane tetra (meth) acrylate, ditrimethylolethane poly (1-10) Alkylene oxide (eg ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylol butane tetra (meth) acrylate, ditrimethylol butane poly (1-10)
Alkylene oxide (eg ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylolhexane tetra (meth) acrylate, ditrimethylolhexane poly (1-10) alkylene oxide (eg ethylene oxide, propylene oxide, butylene oxide) Etc.) tetra (meth) acrylate, ditrimethylol octane tetra (meth) acrylate, ditrimethylol octane poly (1-10) alkylene oxide (for example, 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 (meth Acrylate,
Examples include tripentaerythritol polyalkylene oxide octa (meth) acrylate and the like.

Examples of the (meth) acrylic oligomer include polyols, polybasic acids and esterified products of (meth) acrylic acid, and epoxy acrylate. 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, etc. are used.

Next, as a metal dryer, 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 acid, linseed oil fatty acid, soybean oil fatty acid, dimethylhexanoic acid, 3,
It is possible to use metal salts of organic carboxylic acids such as 5,5-trimethylhexanoic acid and dimethyloctanoic acid, for example, publicly known and used compounds such as calcium, cobalt, lead, iron, manganese, zinc and zirconium salts. In order to accelerate the surface of the printing ink and the internal curing, a plurality of these may be appropriately used in combination.

Next, 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-acrylbenzone, benzyl, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (Irgacure 907: Ciba). Specialty Chemicals Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (Irgacure 369: Ciba Specialty Chemicals Co., Ltd.), benzylmethyl 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-on (Darocur 1116: manufactured by Merck), 4-
(2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 4- (2-acryloyl-
Oxyethoxy) phenyl-2-hydroxy-2-propylketone, diethoxyacetophenone (ZLI333
1: Ciba Specialty Chemicals), Esacure KIP100 (Ramberti), Lucillin 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), CGI1700 (manufactured by Ciba Specialty Chemicals, etc.) are exemplified.

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

Next, as the colorant, an inorganic pigment and an organic pigment can be shown. Examples of inorganic pigments include yellow lead, zinc yellow, navy blue, barium sulfate, cadmium red, titanium oxide, zinc white, rouge, alumina white, calcium carbonate, ultramarine blue, carbon black, graphite, aluminum powder, and red iron oxide. Is a β-naphthol-based, β-oxynaphthoic acid-based, β-oxynaphthoic acid-based anilide-based, acetoacetic acid anilide-based, pyrazolone-based soluble azo pigments, β-naphthol-based, β-oxynaphthoic acid-based anilide-based, Insoluble azo pigments such as acetoacetic anilide monoazo, acetoacetic anilide disazo, and pyrazolone, phthalocyanine pigments such as copper phthalocyanine blue, halogenated (chlorine or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, and metal-free phthalocyanine , Quinacridone , Dioxazine-based, Slene-based (pyrantron, antoanthrone, indanthrone, anthrapyrimidine, flavantron, thioindigo-based, anthraquinone-based, perinone-based, perylene-based, etc.), isoindolinone-based, metal complex-based, quinophthalone-based, etc. 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.
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. 3-8 solvent, Naphthesol H, Alken 56NT, Diadol 13, DIAREN 168, manufactured by Mitsubishi Chemical Corporation, Nissan Chemical Co., Ltd. Examples include Foxochol, Foxochol180 and the like manufactured by Co., Ltd. The solvent for printing ink in which the aromatic component is 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 to 3/0 to 100.
The solvent is a solvent of / 100 to 0, and sometimes an olefin component may be contained. Specifically, AF Solvents 4 to 8, No. 0 Solvents H and I manufactured by Nippon Oil Co., Ltd.
SU Co., Ltd. N-paraffin C14-C18, Idemitsu Kosan Co., Ltd. Supersol LA35, LA38, etc., Exxon Chemical Co., Ltd. Exsol D80, D110, D120,
D130, D160, D100K, D120K, D13
Maggie Sol-40, manufactured by Maggie Bros. Co., Ltd.
44, -47, -52, -60, etc. are illustrated. The aniline point is desired to be 60 to 115 ° C. If a solvent having an aniline point higher than 115 ° C. is used, the dissolving power with the resin used in the ink composition is insufficient, the fluidity of the ink is insufficient, and as a result, the leveling on the printing material is poor and the gloss is low. Only printed matter without Further, an ink using a solvent having an aniline point lower than 60 ° C. has a poor removability of the solvent from the ink film during drying and causes deterioration in drying.

Next, the form of use as the curable composition in the present invention will be described. The curable composition of the present invention is a printing ink or overprint varnish (OP
There is a usage form as varnish). The printing ink is usually used in the form of a lithographic printing ink, but can also be used as a letter printing ink or a flexo ink which is a relief printing method. The usual composition ratios are 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 ethylenically unsaturated double bond 5 to 90% by weight Radical polymerization inhibitor 0.01 to 1% by weight Radical polymerization initiator 0 to 15% by weight Metal dryer 0.1 to 3.0% by weight Other additives 0 to 10% by weight Solvent for printing ink 0 to 40% by weight In producing the curable composition in the 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 can be obtained by heating and mixing at room temperature or up to 120 ° C. In that case, air blowing (or mixing with nitrogen gas), addition of a polymerization inhibitor, addition of an antioxidant, and the like are performed at the same time, if necessary.

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 higher which is effective in the present invention is used, the resin is a vegetable oil or its fatty acid ester. It is effective to use it in the form of a melted or cooked varnish in the temperature range of 180 to 260 ° C. for 0.5 to 3 hours. If necessary, the hybrid compound of the present invention and / or the (meth) acrylic monomer having an ethylenically unsaturated double bond or the (meth) acrylic oligomer may be mixed and used as a varnish.

As the polymerization inhibitor, (alkyl) phenol, hydroquinone, catechol, resorcin, p-
Methoxyphenol, t-butylcatechol, t-butylhydroquinone, 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, butyraldoxime, methylethylketoxime, cyclohexanone oxime and the like are used.

As additives, for example, as anti-friction agents, anti-blocking agents, slip agents, and anti-scratch agents,
Natural waxes such as carnauba wax, wood wax, lanolin, montan wax, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax,
Synthetic waxes such as polytetrafluoroethylene wax, polyamide wax, and silicone compounds can be used.

When the curable composition of the present invention is used as a printing ink, the composition should be a varnish having a viscosity (100 to 200 Pa · s / 25 ° C.) that is easy to use for printing ink. Is desirable. The composition ratio is not limited, but resin / vegetable oil or fatty acid ester thereof / polymerization inhibitor / hybrid compound / (meth) acrylic monomer and / or (meth) acrylic oligomer having an ethylenically unsaturated double bond = 5 to 50 % By weight / 1-40% by weight / 0.01-1% by weight / 10-40% by weight / 0-4
A general composition ratio is 0% by weight.

Furthermore, the varnish can be made into a gel varnish by using a gelling agent. As the gelling agent, an aluminum complex compound can be usually cited. Cyclic aluminum compounds, such as cyclic aluminum oxide octate (Algomer 8 manufactured by Kawaken Fine Chemicals Co., Ltd.)
00), cyclic aluminum oxide stearate (Algomer 1000S manufactured by Kawaken Fine Chemicals Co., Ltd.), aluminum ethylate as aluminum alcoholates, aluminum isopropylate (AIPD manufactured by Kawaken Fine Chemicals Co., Ltd.), aluminum-sec-butyrate (manufactured by Kawaken Fine Chemicals Co., Ltd.). ASPD), aluminum isopropylate-mono-sec-butyrate (AMD manufactured by Kawaken Fine Chemicals Co., Ltd.), aluminum alkyl acetates such as aluminum-di-n-butoxide-ethylacetoacetate (Chem manufactured by Hope Pharmaceuticals).
ope-Al-EB2), aluminum-di-iso-
Butoxide-methylacetoacetate (Chelope-Al-MB12 manufactured by Hope Pharmaceuticals), aluminum-di-iso-butoxide-ethylacetoacetate (Chelope-Al-EB102 manufactured by Hope Pharmaceuticals), aluminum-di-iso-butoxide-ethylacetoacetate (Chemope-Al-EB102). Hope Pharmaceuticals Chelope-Al-EB
2), aluminum-di-iso-propoxide-ethylacetoacetate (Chelope manufactured by Hope Pharmaceutical Co., Ltd.)
-Al-EP12, ALc manufactured by Kawaken Fine Chemicals Co., Ltd.
h), aluminum-tris (acetylacetonate)
(Kawaken Fine Chemical Co., ALCH-TR), Aluminum-Tris (Atylacetoacetate) (Kawaken Fine Chemical Co., Aluminum Chelate-A), Aluminum-bis (ethylacetylacetonate) -monoacetylacetonate (Kawaken Fine Chemical) Aluminum chelate D), aluminum chelate M (Kawaken Fine Chemicals Co., Ltd.), aluminum chelate NB-15 (Hope Pharmaceuticals Co., Ltd.),
Kerope S (Hope Pharmaceuticals) Kerope ACS-2 (Hope Pharmaceuticals, Liquid Oreep AOO (Hope Pharmaceuticals)
, Liquid olepe AOS (made by Hope Pharmaceutical Co., Ltd.) is exemplified. 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 the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of varnish. Other gelling agents include cyclic dipeptides, bisamides such as ethylene bis (12-hydroxyoctadecanoic acid) amide having the property of gelling an organic liquid, Al-Mg-hydroxycaprylate, Al-Mg-hydroxymyristate. , Al
Examples thereof include powdery aluminum-magnesium compounds such as -Mg-hydroxypalmitate and Al-Mg-hydroxybehenate. 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 (above Chattem Chemicals, Inc) is illustrated. Furthermore, tetraisopropyl titanate, tetra n-butyl titanate, tetreoctyl titanate,
Examples include organic titanates such as 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 zirconium butoxide and the like are exemplified. The creation of gel varnish
Usually, 0.1 to 3 parts by weight of a gelling agent is charged to 100 to 2
It is obtained by reacting for 30 minutes to 2 hours in the temperature range of 00 ° C.

The printing ink has 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 Producing printing ink components such as photopolymerization initiator and / or sensitizer, metal dryer, and other additives by using kneader, triple roll, attritor, sand mill, gate mixer, and other kneading meat, mixing and adjusting machines. To be done.

The curable ink comprising the curable composition of the present invention is usually applied to offset printing which uses dampening water, but is also suitably used for waterless printing which does not use dampening water. The curable composition of the present invention is also applied to 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 various packaging such as carton paper, various plastic printed matter, printed matter for stickers / labels, art printed matter, metal printed matter (art printed matter, It is applied to printed matter such as beverage can printed matter and food printed matter such as canned food. For curable ink, UV curable ink, electron beam curable ink, for overcoat varnish, UV curable overcoat varnish, electron beam overcoat varnish, and water-based overcoat varnish. There is also.

Further, in order to further enhance the aesthetic quality and durability of the printed matter using the curable ink of the present invention, the present invention prints the curable ink on a substrate and immediately wets it with an active energy ray curable overcoat. Apply a coat varnish,
It also provides a printing method of irradiating with active energy rays, and a printed matter obtained by the method. Usually, after printing a general oil-based ink that is only oxidatively polymerizable, immediately after applying the active energy ray overcoat varnish in a wet condition and irradiating with the active energy ray, the gloss after several days is measured and the initial gloss is not maintained. The gloss decreases, so-called gloss back occurs, but when the curable ink of the present invention is used, this gloss back is remarkably improved even when the active energy ray-curable overcoat varnish is immediately applied and irradiated with the active energy ray. Therefore, it is possible to provide a printed matter with an aesthetically pleasing appearance. The base material is coated cardboard such as Maricoat, polyethylene coated paper, aluminum coated paper manufactured by Hokuetsu Paper Co., Ltd., Tokubishi art paper manufactured by Mitsubishi Paper Mills Co., Ltd., thin paper coated paper such as high quality paper, synthetic paper, plastic. Films, metal plates, etc. are used.

The present invention will be described in detail below with reference to specific examples. In the examples, “part” means part by weight.

Production Example of Hybrid Compound (HR1) In a four-necked flask equipped with a stirrer, water separation tube and thermometer, 268 parts of trimethylolpropane and 80 parts of toluene were added.
Parts, p-toluenesulfonic acid 10 parts, t-butylhydroquinone part 2, acrylic acid 274 parts, and linseed fatty acid dimer 504 parts were charged, and the temperature was gradually raised to 100 under a nitrogen flow, and the reaction was performed at 110 ° C. for about 12 hours. When the dehydration reaction stopped and the decrease of the acid value became slow from the 35th position, 20 parts of cyclohexane was charged, and the dehydration reaction was continued at reflux, and when the acid value became 10.0 or less, an equal amount was added. After washing with water for 3 times and confirming that the washing water is neutral or close to that with pH test paper, it was desolvated and pumped out. The acid value was 2.2.

Similarly, the compounds shown in Table 1 were reacted to obtain hybrid compounds HR1 to HR7.

[0098]

[Table 1]

Example Resin R1 Synthesis example of rosin phenol resin (synthesis of resol type phenol resin) 206 parts of p-octylphenol, 203 parts of 37% formalin, xylene 250 in a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer.
Part, and while heating with stirring while blowing nitrogen gas, 5
2. Disperse 2.0 parts of calcium hydroxide in 10 parts of water at 0 ° C, add the dispersion and raise the temperature to 95 ° C.
The reaction was carried out for 5 hours. Then, it was cooled, neutralized with sulfuric acid, and washed with water. The resol xylene solution layer and the aqueous layer were separated by standing.
This resol type phenol resin is used as a resole solution.

(Synthesis of rosin phenol resin) Stirrer,
While blowing nitrogen gas into a reflux condenser with a water separator and a four-necked flask with a thermometer, 60 parts of rosin was charged, heated and stirred, and at 40 ° C., 40 parts of resol solution (solid content) was added dropwise for about 2 hours. During the charging, the reaction is performed while collecting water and xylene, and the temperature is raised to 250 ° C after the charging is completed.
Then, 6.0 parts of glycerin was charged and reacted for 12 hours, and the acid value became 25 or less, so it was pumped out. The weight average molecular weight of this resin was 45,000. (Resin R
1) Note) * Resole liquid that reacts with rosin indicates parts by weight of solid content. * The weight average molecular weight was measured by gel permeation chromatography (HLC8020) manufactured by Tosoh Corporation, and polystyrene was used as the standard sample for the calibration curve.

Example Resin R2 α, β Ethylenically unsaturated carboxylic acid ester modified petroleum resin example Dicyclopentadiene resin manufactured by Maruzen Petrochemical Co., Ltd. (Marukalets M510A: dicyclopentadiene / pentadiene = 4/1 weight ratio) 470 parts , 30 parts of maleic anhydride was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer, heated while heating while blowing nitrogen gas, and reacted at 180 ° C. for 3 hours to obtain a maleic anhydride-modified DCPD resin (M
D resin) was obtained. Next, 300 parts of MD resin, 20 parts of butylethylpropanediol (BEPD), a stirrer, a reflux condenser with a water separator, and a flask with a thermometer were charged and heated to 250 ° C. while blowing nitrogen gas.
The reaction was carried out for 3 hours at an acid value of 10 and a melting point of 140 ° C.
Resin R2) was obtained.

Resin Example 3 α, β Ethylenically Unsaturated Carboxylic Acid Modified Rosin Ester Resin-1 Example A four-necked flask equipped with a stirrer, a water separation tube and a thermometer was used to polymerize rosin (80 with Dymarexes manufactured by Rika Hercules Co., Ltd.). % Of dimer rosin) and 7 parts of maleic anhydride are charged and subjected to Diels-Alder reaction at 180 ° C. for 2 hours under a nitrogen stream. Then trimethylol octane 1
8 parts were charged, the temperature was gradually raised and the reaction was carried out at 270 ° C., and the reaction was carried out until the acid value reached 25 or less and then pumped out. The weight average molecular weight of this resin was 65,000. (Resin R3) Resin Example 4 α, β Ethylenically unsaturated carboxylic acid-modified rosin ester resin-2 Polymerization rosin 2 in a four-necked flask equipped with a stirrer, a water separation tube, and a thermometer was used with Rika Hercules Co., Ltd.
93 parts, containing 0% dimeric rosin, 7 maleic anhydride
A portion is charged and the Diels-Alder reaction is performed at 180 ° C. for 2 hours under a nitrogen stream. Then pentaerythritol 1
7.5 parts and 18.5 parts of octylic acid were charged, the temperature was gradually raised and the reaction was carried out at 250 ° C., and the reaction was carried out until the acid value was 25 or less and then pumped. The weight average molecular weight of this resin was 60,000.
(Resin R4) Resin Example 5 α, β Ethylenically unsaturated carboxylic acid-modified rosin ester resin-3 Polymerized rosin 2 in a four-necked flask equipped with a stirrer, a water separation tube, and a thermometer (8 with a dimerecs manufactured by Rika Hercules Co., Ltd.).
92 parts of 0% dimer rosin) and 8 parts of fumaric acid are charged, and a Diels-Alder reaction is carried out at 180 ° C. for 2 hours under a nitrogen stream. Then 2-ethyl-1-hexanol 11
And 9 parts of glycerin were gradually charged, the temperature was gradually raised and the reaction was carried out at 270 ° C., and the reaction was carried out to an acid value of 25 or less and then pumped out. (Resin R5) The weight average molecular weight of this resin was 47,000.

Resin Example 6 Rosin and petroleum resin modified ester resin Stirrer, water separation tube, 53 parts gum rosin in a four-necked flask equipped with a thermometer, Marukalets M510 (petroleum resin manufactured by Maruzen Sekiyu KK) 40 parts, maleic anhydride 7 A portion is charged and the Diels-Alder reaction is performed at 180 ° C. for 2 hours under a nitrogen stream. Thereafter, 17.5 parts of pentaerythritol and 18.5 parts of nonylic acid were charged, the temperature was gradually raised and the reaction was carried out at 250 ° C., and the reaction was carried out to an acid value of 25 or less and then pumped out. The weight average molecular weight of this resin was 45,000. (Resin R6) Resin Example 7 (Synthesis example of rosin alkyd resin) 73.1 parts of rosin was charged into a four-necked flask equipped with a stirrer, a water separation tube, and a thermometer, and pentaerythritol 14.2 at 240 ° C under a nitrogen stream. A part was charged and reacted at 270 ° C. until the acid value was 20 or less. After that, at the same temperature, isophthalic acid 12.
7 parts were gradually charged and reacted until the acid value became 20 or less. The weight average molecular weight of this resin was 65,000.
(Resin R7) Varnish production example (preparation of resin varnish) A four-necked flask equipped with a stirrer, a water separation cooling tube and a thermometer was charged with 35 parts of resin (R1) and 25 parts of linseed oil, and 220 ° C under a nitrogen stream. And keep it at 110 ℃ for 1 hour, then t-BH
Q (tert-butyl hydroquinone) 0.1 part, hybrid compound HR1, 30 parts, and ditrimethylol propane tetraacrylate 9.9 parts were charged, and after stirring for 30 minutes, the viscosity was adjusted to 150 to 200 Pa · s / 25 ° C. and pumped out. (Example varnish V1). Hereinafter, Example Varnish V2 to Example Varnish V5 and Example Varnish V7 were similarly prepared.

(Example varnish V6) Stirrer, water separation cooling tube, 30 parts of resin (R6) in a four-necked flask equipped with a thermometer,
Charge 24.5 parts of soybean oil, heat and dissolve under a nitrogen stream,
After incubating at 220 ℃ for 1 hour, lower the temperature of 160 ℃,
ALCH (Kawaken Fine Chemical Co., Ltd. gelling agent)
After adding 0.5 parts, keep warm at 1901, ℃ for 11 hours
Set to 0 ° C and t-BHQ (tertiary butyl hydroquinone)
0.1 part, hybrid compound HR6, 30 parts trimethylolpropane tripropylene oxide adduct 14.9 parts triacrylate were charged and the viscosity was adjusted to 15 after stirring for 30 minutes.
It was adjusted to 0 to 200 Pa · s / 25 ° C. and pumped out.
(Example varnish V6).

[0105]

[Table 2]

Comparative Example Varnish (V8) Production Example (Oxidative Polymerization Varnish) A four-necked flask equipped with a stirrer, equipped with a water-separating cooling tube and equipped with a thermometer was placed under a nitrogen stream under rosin-modified phenol resin R1.
45 parts, linseed oil 20 parts, AF5 solvent (Nippon Oil Co., Ltd. aroma-free ink solvent) 34.4 parts, ALC
H (Kawaken Fine Chemicals Co., Ltd. gelling agent) 0.5
Part, t-butylhydroquinone 0.1 part, and charged to 20
It melt | dissolved by heating at 0 degreeC for 1 hour. When the viscosity was measured with a cone-plate type viscometer, it was 98 Pa · s / 25 ° C.

Similarly, Comparative Examples Varnishes V9 and V10 were prepared according to the formulations shown in Table 3.

Comparative Example Varnish (V11) Production Example (Active Energy Ray Curing Varnish) A four-necked flask equipped with a stirrer, a water separation cooling tube, and a thermometer was used, and Dap Tote DT170 (Dialuruphthalate manufactured by Tohto Kasei Co., Ltd.) was used. 30 parts of resin, 69.9 parts of ditrimethylolpropane tetraacrylate and 0.1 part of hydroquinone were charged, and the mixture was heated at 100 ° C. for 30 minutes to 1 under an air stream.
Dissolved in time. When the viscosity was measured with a cone-plate type viscometer, it was 152 Pa · s / 25 ° C. Similarly, with the formulations shown in Table 3, Comparative Example Varnishes V11 and V
Twelve created.

[0109]

[Table 3]

Production Example of Curable Ink (Ink 1) 18 parts of Carmine 6B (red pigment manufactured by Toyo Ink Mfg. Co., Ltd.) as a red pigment, 49 parts of varnish V1 and 26.9 parts of ditrimethylolpropane tetraacrylate. , 4'-
2.5 parts of bis (diethylamino) benzophenone (EAB), 2.5 parts of Irgacure 907, 0.1 part of hydroquinone, and 1 part of manganese naphthenate were charged, and a triple roll mill was used to produce by a conventional method.

The ink was prepared to have a tack value of 7 to 8/25 ° C. Inks 2 to 15 with the formulations shown in Tables 4 to 6 below.
Was manufactured. The inks 9, 10, 14, and 15 are examples of electron beam curable inks.

The heat loss of the curable inks 1 to 10 was 0.9% (water content 0.2%), and the heat loss of the curable ink 11 was 5.8% (water content 0.2%). ), The heating decrement of the curable inks 12 to 15 was 10.9% (water content was 0.2%. The measurement method was 110 ° C. for 1 hour at a nitrogen gas flow rate of 100 mL / min. Thermogravimetric measurement was performed under the conditions, and the water content was determined by the Karl Fischer method.

[0113]

[Table 4]

[0114]

[Table 5]

[0115]

[Table 6]

Comparative Example Production Example of Oily Ink (Ink 16) 18 parts of Carmine 6B, 70.9 parts of Varnish V8, AF
5 parts of solvent, 0.1 parts of BHT and 1 part of manganese naphthenate were charged and prepared by a conventional method with a triple roll mill.

The ink was prepared to have a tack value of 7 to 8/25 ° C.

In the same manner, Comparative Example oil-based inks 17 and 18 were manufactured according to the formulations shown in Table 7.

The loss on heating of the comparative oil inks 16 to 18 was 35% (water content 0.2%).

[0120]

[Table 7]

Comparative Example UV-Curable Ink (Ink 19) Carmine 6B 18 parts, Varnish V11 30 parts, Ditrimethylolpropane tetraacrylate 26.9 parts, Dipentaerythritol hexaacrylate 20 parts, 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 with a triple roll mill. The ink was prepared to have a tack value of 7 to 8/25 ° C.

Comparative UV-curable ink 20 was manufactured in the same manner as described below with the formulation shown in Table 7.

Comparative Example Electron Beam Curable Ink (Ink 21) Carmine 6B 18 parts, Varnish V11 35 parts, ditrimethylol propane tetraacrylate 26.9 parts, dipentaerythritol hexaacrylate 20 parts by weight,
Hydroquinone (0.1 part) was charged and prepared by a conventional method with a triple roll mill. The ink has a tack value of 7 to 8/25.
It was adjusted to ℃.

Similarly, Comparative Electron Beam Curable Ink 22 was produced according to the formulation shown in Table 7. The effect of the present invention will be described in a glossback test. (Table 8, Examples 1 to 1
1, Comparative Examples 1 to 9) -In the case of UV irradiation-R was applied to Maricoat paper (Hokuetsu Paper Co., Ltd. coated cardboard).
I tester (simple printer manufactured by Akira Seisakusho Co., Ltd.)
Immediately after color-printing with 0.3cc of ink, wire bar # 3K-Rock sprufer (RK PRINT-
COAT INSTRUMENTS Ltd., UV curable varnish (FDPCA902 varnish: Toyo Ink Mfg. Co., Ltd.)
(Manufactured by K.K.) was applied and irradiated with ultraviolet rays, and the gloss was measured immediately and 72 hours later. An adhesion test was also carried out by peeling cellophane tape. Ultraviolet irradiation is made by USHIO Co., Ltd. irradiation device UVC-2535 (120 W / cm ultra-high pressure mercury ozone uncut lamp, 1 conveyor, conveyor speed 30 m / min)
Conditions) were used. The gloss meter was used under the condition of 60 degrees manufactured by Murakami Color Research Laboratory. —Case of Electron Beam Irradiation— After color-printing under the same conditions as in the case of ultraviolet irradiation, an EB curable varnish (varnish obtained by removing the initiator from FDPCA902) was applied and then immediately irradiated with an electron beam. The electron beam irradiation was carried out at 30 KGy using a low-energy electron beam irradiation apparatus (pressurized voltage: 175 KV, oxygen concentration: 500 ppm, nitrogen-substituted atmosphere) manufactured by ESI, USA.

The above results are summarized in Table 8.

[0126]

[Table 8]

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

Each ink and each raw material were placed on a blanket S7400 manufactured by Kinyosha Co., Ltd., which is generally used for oil-based inks, and the blanket swelling property after 72 hours was measured with a micro gauge. The difference in thickness between the blanket after swelling and the blanket before swelling was divided by the thickness of the blanket before swelling and expressed as a percentage (%). The results are shown in Table 8
Are summarized in. In the table, 0 to 0.5% is good in swelling,
0.6-0.9% swells slightly, but at a practical level,
1.0% or more is defective.

The above results are summarized in Table 9.

[0130]

[Table 9]

Ink washability: After printing each ink with an RI tester, the ink washability was tested with a mineral terpen. The results are summarized in Table 9. In the table, ◯ indicates good detergency, and x indicates poor detergency.

[0132]

As described above, by using the curable composition using the hybrid compound according to the present invention, the swelling resistance, detergency, emulsification suitability, misting suitability, and low cost of the oxidation-polymerizable oil-based ink are reduced. When the active energy ray-curable overcoat varnish is applied while maintaining the property, it is possible to provide a high-quality printed material with glossiness in which gloss back is suppressed.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H113 AA01 AA03 AA04 AA06 BA47                       BC10 CA05 CA11 DA41 FA42                       FA43 FA45 FA48                 4J027 AB02 AB03 AB06 AB07 AB10                       AB12 AB15 AB16 AB17 AB18                       AB19 AB24 AB25 AC03 AC04                       AC07 BA07 BA11 BA20 BA21                       BA26 BA27 BA28 CA29 CA34                       CD08                 4J039 AB04 AB08 AD06 AD18 AD19                       AD21 AE02 AE03 AE05 AE06                       AF01 AF03 AF07 BA02 BA06                       BA13 BA16 BC03 BC19 BC39                       BC49 BC54 BC59 BC60 BE01                       BE12 BE23 BE26 CA04 DA05                       EA04 EA33 EA42 EA47 FA02                       GA01 GA02 GA09 GA25

Claims (8)

[Claims] 1. A polyol (a) and a polybasic acid (b),
A hybrid compound (A) obtained by subjecting a (meth) acrylic acid (c) to an ester reaction, a vegetable oil or a fatty acid ester thereof (B), and a (meth) acrymonomer having an ethylenically unsaturated double bond or (meth) A curable composition comprising an acrylic oligomer (C). 2. The curable composition according to claim 1, wherein the polybasic acid (b) is an aliphatic polybasic acid. 3. The curable composition according to claim 1, wherein the polybasic acid (b) is a cyclic polybasic acid. 4. The curable composition according to claim 1, further comprising a resin (D) having a softening point of 50 to 180 ° C. 5. The curable composition according to any one of claims 1 to 4, further comprising a metal dryer and / or a radical polymerizable initiator (E). 6. The curable ink according to claim 1, further comprising a coloring agent (F). 7. A curable ink according to claim 6 is printed on a substrate, an active energy ray-curable overcoat varnish is applied to the substrate in an uncured state, and the active energy ray is irradiated. A printing method characterized by the above. 8. A printed matter obtained by the printing method according to claim 7.