JP4511822B2 - Active energy ray-curable dry lithographic printing ink composition, printing method and printed matter thereof - Google Patents

Description

The present invention relates to an ink composition for dry planographic printing that can be cured by irradiation with active energy rays such as ultraviolet rays and electron beams.

There are two methods for lithographic printing: a conventional method that uses the repellency of dampening water and ink, and a method that uses the repellency of silicone rubber and ink. The former is printed using the PS plate and the latter using the waterless plate. . In this waterless lithographic printing, the ink resilience of the silicone rubber is not always sufficient, and therefore it is necessary to use a dedicated ink for dry lithographic printing. In the field of printing using general oil-based inks, practical application has progressed due to improved background resistance and printed matter quality. Furthermore, the oil-based ink often uses a volatile hydrocarbon-based ink solvent that is a mineral oil fraction. However, in recent years, the need for VOC (volatile organic compound) -free inks in which volatile hydrocarbon-based ink solvents are completely eliminated from the oil-based inks has increased due to environmental considerations. For example, according to Fukuda and Ishii et al. (Japan Printing Society Journal, Vol. 37, No. 5, p. 51), if VOC-free offset printing ink can be made, 40,000 tons or more of petroleum for printing ink It is said that the solvent can be reduced.

However, in the field of dry lithographic printing using an active energy ray curable ink, the use of acrylate ester as the main ink component cannot be avoided, and the ink rebound on silicone rubber is inferior to that of general oil-based inks. The ink has to be made extremely high in viscosity, and therefore inevitably has a high tack, so that it is difficult to put it into practical use only in specific fields such as card printing.

When high tack ink is used in fields such as paper container printing and business form printing, various printability problems arise. For example, problems such as paper peeling, ink piling on a blanket or plate (ink or paper dust accumulating), plate / blanket damage resulting from these, and poorly printed prints often occur. . When such troubles occur, the operation of the printing press is greatly reduced, and the amount of waste paper increases, resulting in a very large economic loss. In order to avoid these troubles, it is necessary to add an ink diluent to make the ink low tack, but in that case the ink cohesive force is insufficient and the stain resistance is greatly reduced. The printed matter is soiled and cannot be put to practical use.
Therefore, attempts to mix the components of oil-based ink and active energy ray-curable ink are also known (see, for example, Patent Document 1 and Patent Document 2). Generally, oil-based ink and active energy beam-curable ink are compatible. Is poor, the fluidity is deteriorated, resulting in poor transfer during printing. In general, rosin-modified phenolic resins and vegetable oils or their fatty acid esters, which are oily materials, and (meth) acrylic monomers or (meth) acrylic oligomers having ethylenically unsaturated double bonds with active energy ray curability may be difficult to dissolve. Many.

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

As a result of intensive studies focusing on the drawbacks of the prior art as described above, the present inventors have good soil dirt resistance, no paper peeling, piling, backing (good stackability), etc. In addition, an active energy ray-curable dry lithographic printing ink composition capable of giving good print quality has been developed.

Furthermore, the problem to be solved by the present invention is to provide a curable ink that does not use any volatile organic compound (VOC) such as a petroleum solvent, and a printed matter printed using them. According to the present invention, the thermogravimetric decrement is limited to 1% or less (excluding water) in the VOC measurement method Metyod24 (110 ° C., 1 hour heating residue measurement) proposed by the US Environmental Protection Agency. This makes it possible to provide VOC-free ink and printed matter.
However, the present invention can also be applied as a curable ink containing a volatile organic compound (VOC) such as a conventional petroleum solvent.

  Furthermore, as an environmental measure, the oil-based components contained in offset inks and soybean oil inks in which part of dry oil is replaced with soybean oil or its modified products meet the certification standards of ASA (The American Soybean Association). It is also possible to meet the required standards according to the present invention.

That is, the present invention
1 to 30% by weight of the polymer (a),
1 to 40% by weight of an oil-soluble resin (b) other than (a),
1 to 20% by weight of vegetable oil or fatty acid ester thereof (c),
(Meth) acrylic monomer or (meth) acrylic oligomer (d) having 10 to 70% by weight of ethylenically unsaturated double bond,
0.1 to 10% by weight of organopolysiloxane and 1 to 40% by weight of colorant or extender pigment (e)
In the active energy ray-curable dry lithographic printing ink composition comprising,
The polymer (a) is
Styrene and / or vinyl toluene;
Isoborneol methacrylic ester, borneol acrylic esters, Terupi Ne ol methacrylic esters, one or more selected from butyl methallyl rate and hydroxypropyl methacrylate and
Consists of
Oil-soluble resin (b)
Softening point 50-180 ° C
and
Weight average molecular weight 30,000-150,000
Is
One selected from rosin modified phenolic resin, petroleum resin, α, β-ethylenically unsaturated carboxylic acid ester modified petroleum resin, alkyd resin, rosin modified alkyd resin and α, β-ethylenically unsaturated carboxylic acid modified rosin ester resin More than
It relates the active energy ray-curable dry planographic printing ink composition characterized in that it.
Further, the present invention has an ethylenically unsaturated double bond (meth) acrylic monomer or (meth) acrylic oligomer (d) is, the active energy ray is an alkylene oxide adduct (meth) acrylate of an aliphatic alcohol compound The present invention relates to a curable dry lithographic printing ink composition.
Further, the present invention relates to the active energy ray-curable dry planographic printing ink composition containing 0.1 to 10% by weight of the printing ink solvent.
Further, the present invention relates to the active energy ray-curable dry planographic printing ink composition having a viscosity of 50~100Pa · S / 25 ℃.
Further, the present invention relates to the active energy ray-curable dry lithographic printing ink composition comprising 0.1 to 3 wt% metal drier and / or 0.1 to 15% by weight of a radical polymerization initiator .
In addition, the present invention prints the active energy ray-curable ink composition on a substrate, and applies the active energy ray-curable overcoat varnish or overprint varnish in a state where the printing ink is uncured or cured. Further, the present invention relates to a printing method characterized by irradiating active energy rays.
Further, the present invention relates to printed prints in the active energy ray-curable dry lithographic printing ink composition.
Further, the present invention relates to printed matter obtained by the above printing method.

The present invention relates to a polymer comprising an esterified product of an aromatic vinyl compound and an α, β unsaturated carboxylic acid, a resin having a softening point of 50 to 180 ° C. containing a resin having a weight average molecular weight of 3 to 1,000,000, vegetable oil or its An active energy ray-curable dry lithographic printing ink composition comprising a fatty acid ester, and a (meth) acryl monomer or (meth) acryl oligomer, a colorant or extender pigment, and further paraffin, an olefin solvent, or an organopolysiloxane. By using it, soiling, paper peeling, piling, bar stackability, etc. are improved. Furthermore, after multicolor printing, even if an in-line printing method is performed by applying or printing an active energy ray-curable overcoat varnish or overprint varnish in a bar stack or immediately uncured or cured, and irradiating active energy rays, It is possible to provide a high-quality printed matter with glossiness suppressed with the gloss back.

The present invention will be described in detail below.
As the aromatic vinyl compound in the present invention, styrene, divinylbenzene, vinyltoluene, 1-vinylnaphthalene, 2-vinylnaphthalene, 9-vinylanthracene, 2-vinylphenanthrene, 3-vinylphenanthrene, acenaphthylene, phenyl Examples include vinyl ether, o-cresyl vinyl ether, p-cresyl vinyl ether, α-naphthyl vinyl ether, β-naphthyl vinyl ether and the like.

  Examples of the α, β-unsaturated carboxylic acid in the present invention include fumaric acid, maleic acid or its anhydride, itaconic acid, citraconic acid, crotonic acid, cinnamic acid, (meth) acrylic acid and the like.

Examples of the alcohol constituting the α, β-unsaturated carboxylic acid ester in the present invention include C _{1 to} C ₂₀ aliphatic monohydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, nonanol, decanol, dodecanol, Examples include tridecanol, hexadecanol, octadecanol, icosanol, allyl alcohol and the like.
Furthermore, α, β- of dioctylic acid of C ₁ -C ₂₀ fatty acid and dihydric or higher polyol esterification reaction, for example, ethylene glycol monobutyl ester, propylene glycol monohexyl ester, glycerin or trimethylolpropane. Examples thereof include unsaturated carboxylic acid esters. Furthermore, commercially available fatty acids, other alcohols, phenolic glycidyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-hydroxy as esterified product of α, β unsaturated carboxylic acid -3 phenoxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like.

Further, as C ₅ -C ₆₀ cyclic alcohol, benzyl alcohol, ethylene oxide or propylene oxide of carboxylic acid, ethylene oxide or propylene oxide of cresol, ethylene oxide or propylene oxide of butylphenol, ethylene oxide or propylene oxide of octylphenol, ethylene oxide or propylene oxide of nonylphenol, Examples include ethylene oxide or propylene oxide of dodecylphenol, cycloaliphatic alcohols such as rosin alcohol (Hercules Abitol), tricyclodecane (mono or di) methylol, and (meth) acrylic acid esters such as C5 petroleum resin allyl alcohol copolymer. The Furthermore, (meth) acrylic esters such as ethylene glycol monorosin ester, trimethylolpropane or glycerin dirosin ester, pentaerythritol trirosin ester are exemplified. In addition, borneol (bornyl alcohol), isoborneol (isobornyl alcohol), citronellol, pinocamphetol, geraniol, fentil alcohol, nerol, linalool, menthol, terpineol, carpeol, twill alcohol, farnesol, patchouli alcohol, nerolidol And α, β-unsaturated carboxylic acid esters of terpene alcohols such as carotol, casinole lantheol, eudesmol, cedrol, guayol, kesso glycol, phytol, sclareol, manol, hinokiol, ferguinol, totarol.

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

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

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

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

  Examples of the reaction solvent include n-hexane, cyclohexane, ethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethyl acetate, butyl acetate, MEK, MIBK, diisobutyl ketone, cyclohexanone, ethanol, isopropanol, butanol and the like. The solvent is contained as it is or removed under reduced pressure after completion of the reaction.

The reaction ratio of the aromatic vinyl compound and the α, β unsaturated carboxylic acid ester is 1 to 99% by weight, preferably 10 to 90% by weight, based on the total amount of the aromatic vinyl compound and the α, β unsaturated carboxylic acid ester. The α, β unsaturated carboxylic acid ester is 1 to 99% by weight, preferably 10 to 90% by weight.
In general, if there are more aromatic vinyl compounds than this, it will be difficult to dissolve in a resin having a vegetable oil or its fatty acid ester or softening point of 50 to 180 ° C, and if it is less, a (meth) acrylic monomer having an ethylenically unsaturated double bond Or it becomes difficult to melt | dissolve with a (meth) acryl oligomer. Furthermore, if the α, β unsaturated carboxylic acid ester is more than this, it will be difficult to dissolve with the (meth) acrylic monomer or (meth) acrylic oligomer having an ethylenically unsaturated double bond, and if it is less, vegetable oil or its fatty acid ester or softening point. However, it becomes difficult to melt | dissolve in resin of 50-180 degreeC or more.

  Generally, vegetable oils or fatty acid esters thereof, which are oily materials, and oil-soluble resins having a softening point of 50 to 180 ° C. and (meth) acrylic monomers or (meth) acrylic oligomers having active energy ray curability are hardly compatible. The polymer of the present invention dissolves in an oil-based vegetable oil or fatty acid ester thereof, an oil-soluble resin having a softening point of 50 to 180 ° C., and a (meth) acryl monomer or (meth) acryl oligomer having ultraviolet and electron beam curability. It plays the role of a compatibilizer for both.

  As the oil-soluble resin (b) having a softening point other than (a) of 50 to 180 ° C., rosin-modified phenol resin, petroleum resin, α, β-ethylenically unsaturated carboxylic acid ester-modified petroleum resin, alkyd resin, rosin ester Resin (rosin modified alkyd resin, α, β-ethylenically unsaturated carboxylic acid modified rosin ester resin), rosin and petroleum resin modified ester resin, melamine resin, terpene resin, coumarone indene resin, ketone resin, phenol modified petroleum resin, Examples include diallyl phthalate resin.

  As rosin-modified phenolic resins, phenols such as carboxylic acid, hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, (tertiary) butylphenol, (tertiary) octylphenol, nonylphenol, dodecylphenol, hexylphenol, and mixtures thereof are condensed with formaldehyde. The reacted resole or novolak phenol resin and a rosin (gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, etc.) are subjected to a chromatization reaction, and a polyol such as glycerin or pentaerythritol or p -Tree having a weight average molecular weight of 1 to 1 million, preferably 3 to 150,000, which has been esterified using an acid catalyst such as toluenesulfonic acid, methanesulfonic acid or sulfuric acid. It includes resins containing, reaction method according to a conventional method. In order to increase the cohesive strength of the dry lithographic ink composition and improve the suitability of the dry lithographic ink, the weight average molecular weight of the rosin modified phenolic resin is polymerized.

In order to increase the molecular weight of the resin of the present invention, it is desirable to increase the ratio of formaldehyde with respect to phenols, particularly during resol synthesis. (For example, 1.5 mol to 4 mol, preferably 2 to 3 mol of formaldehyde per mol of phenol is desirable.) Further, when reacting resoles and rosins, resoles / rosins = 20 to 60/80 to 40 Preferably, resoles / rosins = 40-60 / 60-40 are desirable. Furthermore, (alpha), (beta) -unsaturated carboxylic acid, such as maleic anhydride and a fumaric acid, may be used together 0.1 to 10weight%.

  Further, examples of the petroleum resin include petroleum resins composed of a 5-membered ring compound such as cyclopentadiene (C5 fraction) or a C9 fraction or an α, β-unsaturated carboxylic acid ester-modified petroleum resin. As the α, β-unsaturated carboxylic acid ester resin, an acid-modified petroleum resin obtained by modifying a petroleum resin containing a C5 or C9 fraction with an α, β-ethylenically unsaturated carboxylic acid or its anhydride, 6 to 20 carbon atoms And an ester-modified petroleum resin obtained by subjecting an alkylene dihydric alcohol and / or trimethylol (having 4 to 18 carbon atoms) alkane or alkene to an ester reaction. Examples of the ester-modified petroleum resin include an ester-modified petroleum resin obtained by an ester reaction using an alkyl group having 4 to 30 carbon atoms, an alkenyl succinic acid, or an acid anhydride thereof, and the fat according to the present invention. At least one selected from the group consisting of an aromatic or cyclic monohydric alcohol, a saturated or unsaturated fatty acid described in the present invention and a resin modified with the above rosins or an α, β-ethylenically unsaturated carboxylic acid or anhydride thereof. An ester-modified petroleum resin obtained by further performing an ester reaction using a seed is exemplified.

MARUKAREZ T-100, M890, M845, M510, M905, manufactured by Toho Chemical Co., Ltd. as a petroleum resin comprising a 5-membered ring compound such as cyclopentadiene (C5 fraction) or C9 fraction Corporex # 2100, high resin # 120, # 130 and the like are exemplified.
Examples of these α, β-ethylenically unsaturated carboxylic acids or acid anhydrides thereof described in the present invention are exemplified, and the amount of modification is petroleum resin comprising C5 fraction or C9 fraction used in the present invention. Although it can be modified in the range of 1 to 100 mol% with respect to the monomer, it is usually modified in an amount in the range of 0.01 to 0.5 mol per 100 g of the petroleum resin. The modification temperature is preferably in the range of 150 ° C to 250 ° C.

  Hexanediol, octanediol, nonanediol, etc. as straight chain or branched alkylene dihydric alcohols having 6 to 20 carbon atoms, followed by 2-methyl-pentanediol, 2-methyl-2- Propyl-propanediol, 2,4-dimethylpentanediol, 2,2-diethyl-propanediol, 2,2,4-trimethyl-pentanediol, dimethyloloctane (manufactured by Mitsubishi Chemical Corporation), 2, Examples thereof include 5-dimethyl-hexanediol, 2-methyl-octanediol, 2-butyl-2-ethyl-propanediol, and 2,4-diethyl-pentanediol. Further, if necessary, ethylene glycol or propylene glycol glycols can be used in combination.

Next, specific examples of the succinic acid having 4 to 30 carbon atoms or the alkenyl group or the acid anhydride thereof include octenyl (anhydrous) succinic acid, dodecenyl (anhydrous) succinic acid, pentadecenyl (anhydrous) succinic acid and the like. Mention may be made of linear or branched alkyl group-substituted (anhydrous) succinic acids.
In the esterification reaction, an esterification catalyst can be used as necessary. The weight average molecular weight of the ester-modified petroleum resin suitably used in the present invention is a resin containing a resin having a weight average molecular weight of 1 to 1,000,000, preferably 3 to 150,000, and the reaction method is a conventional method.

Further, the above-mentioned α, β-unsaturated carboxylic acid ester-modified petroleum resin and a resin obtained by esterification reaction with a polyol such as ethylene glycol, glycerin, trimethylol ethane, trimellirol propane, pentaerythritol or the like in an ordinary manner or an excess of polyol. Weight of resin obtained by reacting polybasic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, (anhydrous) trimellitic acid, (anhydrous) succinic acid, and (anhydrous) maleic acid in a conventional manner with the remaining hydroxyl group-containing resin. The average molecular weight is a resin containing a resin having a molecular weight of 1 to 1 million, preferably 3 to 150,000, and the reaction method is a conventional method.

Examples of the rosin ester resins include rosin alkyd resins and α, β-ethylenically unsaturated carboxylic acid-modified rosin ester resins. The rosin alkyd resin is a weight average molecular weight obtained by reacting a Diels Alder reaction product of the rosin or its α, β-ethylenically unsaturated carboxylic acid or its anhydride with the polyol or polybasic acid in a conventional manner. The reaction method is a conventional method using a resin containing a resin having a molecular weight of 1 to 1 million, preferably 3 to 150,000.

  The α, β-ethylenically unsaturated carboxylic acid-modified rosin ester resin is obtained by adding trimethylol (having 4 carbon atoms) to a Diels-Alder reaction product of the above rosins and α, β-ethylenically unsaturated carboxylic acid or its anhydride. To 18) alkanes or alkenes and / or other polyols, and the composition ratio is rosin / α, β-ethylenically unsaturated carboxylic acid or anhydride thereof is 80/20 ˜97 / 3, (total molar quantity of rosins and carboxylic acids of α, β-ethylenically unsaturated carboxylic acids or anhydrides) / (of C4 to C18 trimethylol alkanes or alkenes and other polyols) Examples thereof include a resin having a total molar quantity of hydroxyl groups of 1 / 0.5 to 1 / 1.2. In the above reaction, rosins and petroleum resins for C5 and C9 fractions may be used in combination at a ratio of rosins / C5 and C9 fractions of petroleum resin = 10 to 90% by weight / 90 to 10% by weight. .

  The reaction of rosins with the above α, β-ethylenically unsaturated carboxylic acid or its anhydride is a Diels-Alder reaction and can be carried out by a known method. For example, the reaction temperature is 150 to 260 ° C., and the reaction time is 1 to 4 hours. The trimethylol (having 4 to 18 carbon atoms) alkane or alkene of the present invention is as described above.

  The reaction ratio of a rosin and a reaction product of an α, β-ethylenically unsaturated carboxylic acid or an anhydride thereof with a trimethylol (having 4 to 18 carbon atoms) alkane or alkene is as follows. , β-ethylenically unsaturated carboxylic acid or its reaction product carboxylic acid total molar quantity / trimethylolalkane or alkene hydroxyl group total molar quantity is 1 / 0.8 to 1/1. The esterification reaction is carried out at 180 to 270 ° C. until the acid value reaches 20 to 30 positions. In this esterification reaction, no catalyst is used or the above catalyst is used. These catalysts are used at a temperature of 200 ° C. or more using 0.01 to 1% by weight in the total resin.

Examples of polyols other than trimethylol (having 4 to 18 carbon atoms) alkane or alkene include ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitol and the like. Examples include aliphatic polyhydric alcohols, cyclic polyhydric alcohols such as tris (2-hydroxyethyl) isocyanurate, inositol, and the like. Other polyols used in combination are preferably glycerin, trimethylolpropane, and pentaerythritol from the viewpoint of the appropriate resin molecular weight, melting point, and cost.
When the resin of the present invention is used for printing ink, the reaction method is a conventional method using a resin containing a resin having an acid value of 30 or less and a weight average molecular weight of 1 to 1,000,000, preferably 3 to 150,000.

  Further, as the α, β-ethylenically unsaturated carboxylic acid-modified rosin ester resin, the above-mentioned rosins and the α, β-ethylenically unsaturated carboxylic acid or its anhydride Diels Alder reaction product may be used. A resin obtained by reacting a monohydric alcohol and a polyol is exemplified.

The method for synthesizing rosins / α, β-ethylenically unsaturated carboxylic acid or its anhydride is in accordance with the above synthesis method. Furthermore, the monohydric alcohol of the present invention is used. The polyol is exemplified as the polyol. The reaction ratio of the reaction product of the rosin and the α, β-ethylenically unsaturated carboxylic acid or its anhydride with the monohydric alcohol and polyol is the rosin and the α, β ethylenically unsaturated carboxylic acid or The total molar quantity of the carboxylic acid of the anhydride / the total molar quantity of the monohydric alcohol and the hydroxyl group of the polyol is adjusted to 1 / 0.8 to 1 / 1.2. The esterification reaction is carried out at 180 to 270 ° C. until the acid value reaches 20 to 30 positions. In the esterification reaction, the above catalyst may be used.
When the resin of the present invention is used as a printing ink, the reaction method is a conventional method using a resin containing a resin having an acid value of 30 or less and a weight average molecular weight of 1 to 1,000,000, preferably 3 to 150,000.

Furthermore, a Diels-Alder reaction product of rosins and α, β-ethylenically unsaturated carboxylic acid or its anhydride may be reacted with a polyol and a fatty acid. The method for synthesizing the saturated carboxylic acid or its anhydride is in accordance with the above synthesis method.
The total number of rosins and the α, β-ethylenically unsaturated carboxylic acid or anhydride carboxylic acid) / the total number of hydroxyl groups of the hydroxyl group-containing compound and polyol) is 1 / 0.5 to 1 / 1.2 is preferred.
The said polyol is illustrated as a polyol of this invention. Furthermore, the dimer acid of fatty acids, such as tung oil dimer fatty acid and sweet oil dimer fatty acid.

The reaction ratio in the case of reacting a polyol and a fatty acid with a reaction product of rosins and α, β-ethylenically unsaturated carboxylic acid or anhydride thereof is the rosin, α, β-ethylenically unsaturated carboxylic acid. Or its anhydride and fatty acid of the present invention (total molar quantity of carboxylic acid / total molar quantity of hydroxyl group of the polyol is 1 / 0.5 to 1 / 1.2, preferably 1 / 0.8 to 1/1 The esterification reaction is carried out at 180 to 270 ° C. until the acid value reaches 20 to 30. In this esterification reaction, the above method is used.
When the resin of the present invention is used as a printing ink, the reaction method is a conventional method using a resin containing a resin having an acid value of 30 or less and a weight average molecular weight of 1 to 1,000,000, preferably 3 to 150,000.

Further, 0 to 10% by weight of a ketone resin obtained by condensation reaction of cyclohexanone, acetophenone or the like with formalin may be used. Examples of the ketone resin include Synthetic Resin CA, Synthetic Resin SK, Synthetic Resin AP, and Synthetic Resin 1201 manufactured by Degussa.

Next, the vegetable oil or fatty acid ester (c) used in the present invention will be described. First, vegetable oil is triglyceride in which at least one fatty acid is a fatty acid having at least one carbon-carbon unsaturated bond in triglyceride of glycerin and fatty acid. Real oil, linseed oil, eno oil, oil deer oil, olive oil, cacao oil, kapok oil, kayak oil, mustard oil, kyounin oil, kiri oil, kukui oil, walnut oil, poppy oil, sesame oil, safflower oil, radish seed oil , Soybean oil, Daifucho oil, Camellia oil, Corn oil, Rapeseed oil, Niger oil, Nuka oil, Palm oil, Castor oil, Sunflower oil, Grape seed oil, Gentia oil, Pine seed oil, Cottonseed oil, Palm oil, Peanut oil And dehydrated castor oil. Further preferred vegetable oils are vegetable oils having an iodine value of at least 100 or more (in parentheses indicate the oil and fat chemical product manual: the iodine value quoted from the Nikkan Kogyo Shimbun), Asa oil (149 or more), Linseed oil (over 170), Eno oil (over 192), deer oil (over 140), Kapok oil (85-102), kaya oil (over 130), mustard oil (over 101), Kyonin oil (97-109) , Kiri oil (145 or higher), kukui oil (136 or higher), walnut oil (143 or higher), poppy oil (131 or higher), sesame oil (104 or higher), safflower oil (130 or higher), radish seed oil (98 to 112) ), Soybean oil (117 or more), large fusose oil (101), corn oil (109 or more), rapeseed oil (97 to 107), niger oil (126 or more), nuka oil (92 to 1) 5), sunflower oil (125 or more), grape seed oil (124 or more), gentian oil (93 to 105), pine seed oil (146 or more), cottonseed oil (99 to 113), peanut oil (84 to 102), dehydrated Castor oil (147 or more) is preferably used, and a vegetable oil having an iodine value of 120 or more may be more preferable. By setting the iodine value to 120 or more, it is possible to further improve the drying property by oxidative polymerization of the curable composition.
In recent years, soybean oil or fatty acid esters thereof (eg soybean oil fatty acid alkyl esters such as soybean oil fatty acid ethyl ester and soybean oil fatty acid butyl ester) are exemplified as environmentally friendly types.
Furthermore, epoxidized soybean oil, epoxidized soybean oil acrylic ester (CN111 manufactured by Sartomer, Evecril 860 manufactured by UCB), epoxidized amaniyu, epoxidized amaniacrylic ester, further epoxidized fatty oil, epoxidized fatty oil acrylic ester Is exemplified.

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

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

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

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

  Further, in recent years, soybean oil or fatty acid esters thereof (soybean oil fatty acid alkyl esters such as soybean oil fatty acid ethyl ester and soybean oil fatty acid butyl ester) are exemplified as environmentally friendly types.

  Furthermore, epoxidized soybean oil, epoxidized soybean oil acrylic ester (CN111 manufactured by Sartomer, Evecril 860 manufactured by UCB), epoxidized amaniyu, epoxidized amaniacrylic ester, further epoxidized fatty oil, epoxidized fatty oil acrylic ester Is exemplified.

Furthermore, the esterification reaction product obtained by reacting soybean oil with glycerin, trimethylolpropane, pentaerythritol, etc., and (meth) acrylic acid with the residual hydroxyl group of the ester exchange reaction product of polyol or soy oil fatty acid and glycerin, trimethylolpropane, Examples thereof include an esterification reaction product obtained by reacting (meth) acrylic acid with a residual hydroxyl group of an esterification reaction product with a polyol such as pentaerythritol. Furthermore, residual hydroxyl groups of transesterification products of polyols such as soybean oil and glycerin, trimethylolpropane and pentaerythritol, or residual hydroxyl groups and trimethylolpropane of esterification products of soybean oil fatty acids and polyols such as glycerin, trimethylolpropane and pentaerythritol Mono or di (meth) acrylic ester, glycerin mono or di (meth) acrylic ester, pentaerythritol di or tri (meth) acrylic ester, diglycerin di or tri (meth) acrylic ester ditrimethylolpropane di or tri (meth) acrylic ester, Residual hydroxyl groups of (meth) acrylic ester compounds such as dipentaerythritol tetra- or penta (meth) acrylic ester are tolylene diisocyanate, isophorone diisocyanate , Soybean oil urethane acrylate ester isocyanate compound reacted and hexamethylene diisocyanate compound and the like.

  The (meth) acrylic monomer or acrylic oligomer (d) having an ethylenically unsaturated double bond will be described. As a (meth) acryl monomer monomer having an ethylenically unsaturated double bond, an alkyl (having 2 to 18 carbon atoms) (meth) acrylate as a monofunctional monomer, for example, ethyl (meth) acrylate, butyl (meth) acrylate, There are hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecane monomethylol Examples include (meth) acrylate. Furthermore, as bifunctional monomers, ethylene 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, hydroxypivalyl hydroxypivalate di (meth) acrylate (commonly called manda), hydroxypivalyl Hydroxypivalate dicaprolactonate di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1,8-octanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate, 3-methyl-1,5- Pentanediol di (meth) acrylate, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2- Diethyl-1,3-propanediol di (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, 2-methyl-2,4-pentanedi (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-methyl-2-propyl-1,3-propanediol Di (meth) acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1,3-propanediol di (meth) acrylate, 2,2,4-trimethyl -1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate (Mitsubishi Chemical), 2-ethyl -1,3-hexanediol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate 2,4-diethyl-1,5-pentanediol di (meth) acrylate tricyclodecane dimethylol di (meth) acrylate, tricyclodecane dimethylol dicaprolactonate di (meth) acrylate, bisphenol A tetraethylene oxide addition Di (meth) acrylate, bisphenol F tetraethylene oxide adduct di (meth) acrylate, bisphenol S tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol A tetraethylene oxide adduct di (meth) acrylate, water Pressurized bisphenol F tetraethylene oxide adduct di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, are exemplified. Glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolhexane tri (meth) acrylate as trifunctional monomers , Trimethylol octane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like. Tetraerythritol tetra (meth) acrylate, pentaerythritol tetracaprolactonate tetra (meth) acrylate, diglycerin tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane tetraca Prolactonate, tetra (meth) acrylate, ditrimethylolethane tetra (meth) acrylate, ditrimethylolbutanetetra (meth) acrylate, ditrimethylolhexanetetra (meth) acrylate, ditrimethyloloctanetetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acryl Chromatography, tri pentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, etc. are exemplified.

Further, an alkylene oxide adduct (meth) acrylate monomer of an aliphatic alcohol compound, particularly an alkylene oxide adduct (meth) acrylate monomer of an aliphatic alcohol compound having an alkylene oxide of C _{3 to} C ₂₀ or more is the above resin, vegetable oil or its fatty acid. Solubility to ester is improved. Alkylene oxide adduct (meth) acrylate monomer of aliphatic alcohol compound Mono- or poly (1-20) alkylene (C2 to C20) oxide adduct of aliphatic alcohol compound (alkylene oxide such as ethylene oxide, propylene oxide, butylene) Oxide, pentylene oxide, hexylene oxide, etc.) mono or poly (1-10) (meth) acrylate. Mono- or poly (1-20) alkylene (C2 to C20) oxide adducts (alkylene) of alkyl (having 1 to 18 carbon atoms) (meth) acrylates as monofunctional monomers, such as methanol, ethanol, propanol, butanol, hexanol, octanol Examples of oxides include ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, and poly (1-20) alkylene (C2 to C20) oxide adducts of butylphenol, octylphenol, nonylphenol, or dodecylphenol (eg, ethylene oxide as alkylene oxide). Examples thereof include oxide, propylene oxide, butylene oxide) (meth) acrylate and the like. Furthermore, ethylene or diethylene glycol, propylene glycol or butylene glycol mono- or poly (1 to 20) alkylene (C2 to C20) oxide adducts (alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide) di ( (Meth) acrylate, hydroxypivalyl hydroxypivalate poly (2-20) alkylene (C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, hydroxypivalylhydroxy Pivalate dicaprolactonate poly (2-20) alkylene (C2 to C20) oxide adduct (for example, ethylene oxide as alkylene oxide) Lopylene oxide, butylene oxide) di (meth) acrylate, 1,6 hexanediol poly (2 to 20) alkylene (C2 to C20) oxide adduct (alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meta ) Acrylate is exemplified. Glycerin poly (2-20) alkylene (C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolpropane poly (2-20) as trifunctional monomer Alkylene (C2 to C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolethane poly (2 to 20) alkylene (C2 to C20) oxide adduct (alkylene as alkylene oxide) For example, ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, pentaerythritol poly (2-20) alkylene (C2 to C20) oxide addition (Alkylene oxide de as for example ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate and the like. Pentaerythritol poly (2-20) alkylene (C2 to C20) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, diglycerin poly (2- 20) Alkylene (C2 to C20) oxide adducts (e.g., ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, diglycerin poly (2-20) alkylene oxide (for example, ethylene oxide, propylene oxide, Butylene oxide, etc.) Adduct tetra (meth) acrylate, ditrimethylolpropane poly (2-20) alkylene (C2 to C20) oxide adduct (as alkylene oxide) For example, ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, ditrimethylolpropane poly (2-20) alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylolpropane tetracarbonate Prolactonate, tetra (meth) acrylate, ditrimethylolethane poly (2-20) alkylene (C2 to C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, ditri Methylolethane poly (2-20) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) La (meth) acrylate, dipentaerythritol poly (2-20) alkylene (C2 to C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) hexa (meth) acrylate, propylene oxide, butylene oxide Etc.) Hexa (meth) acrylate, dipentaerythritol hexacaprolactonate poly (2-20) alkylene (C2 -C20) oxide adduct (eg alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) hexa (meth) Acrylates, tripentaerythritol poly (2-20) alkylene (C2 to C20) oxide adducts (e.g., ethylene oxide, propylene oxide as alkylene oxide) , Butylene oxide) hepta (meth) acrylate, tripentaerythritol poly (2-20) alkylene (C2-C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) octa (meth) acrylate, tri Pentaerythritol poly (2-20) alkylene (C2 to C20) oxide adducts (e.g., ethylene oxide, propylene oxide, butylene oxide) hexa (meth) acrylate, tripentaerythritol polyalkylene oxide hepta (meth) acrylate, Tripentaerythritol poly (2-20) alkylene (C2 to C20) oxide adducts (e.g., ethylene oxide, propylene as alkylene oxide) Kisaido, butylene oxide) octa (meth) acrylate and the like.

Further, examples of the (meth) acrylic oligomer include the above polyol, the above polybasic acid and an esterified product of (meth) acrylic acid, and epoxy acrylate.

Furthermore, a hybrid compound (a hybrid compound having both an oil-soluble aliphatic or oil-soluble cyclic compound group and an acryloyl group) may be used. A mixture of a polyol, a cyclic monobasic acid and / or the above fatty acid having 4 to 36 carbon atoms for producing a hybrid compound (an oil-soluble aliphatic or hybrid compound having both an oil-soluble cyclic compound group and an acryloyl group), and (meta ) For esterification reaction with acrylic acid, a four-necked flask equipped with a stirrer is charged with a mixture of polyol, cyclic monobasic acid and / or fatty acid having 4 to 36 carbon atoms, or charged with polyvalent carboxylic acid. , Toluene, xylene, anone, cyclohexane, etc. in a refluxing solvent or in the absence of a solvent, in a nitrogen stream, the temperature is gradually raised and reacted in the range of 80 to 260 ° C with or without a catalyst to give an acid value (sample This is carried out until the number of mg of potassium hydroxide necessary to neutralize the acid contained in 1 g is 5 or less, preferably 2 or less. Examples of the polyol include the above polyols.

The cyclic monobasic acid of the present invention is benzoic acid, methylbenzoic acid (naphthoic acid), (tertiary) butylbenzoic acid, naphthoic acid, (ortho) benzoylbenzoic acid, naphthenic acid, the above rosins, tricyclodecane monocarboxylic acid Etc. are exemplified. Further examples include dimer acid of fatty acid such as tung oil dimer fatty acid, candy oil dimer fatty acid, soybean oil dimer acid, polymerized rosin, dodecenyl succinic anhydride, pentadecenyl succinic anhydride and the like. When these fatty acids having 4 to 36 carbon atoms are unsaturated fatty acids, the resulting hybrid compound becomes a hybrid curable compound having both oxidative polymerization property and active energy ray curable property, and the curable composition of the present invention. When used as, it becomes possible to impart more preferable curing performance. Thereafter, in the temperature range of 80 to 120 ° C., after charging the above polymerization inhibitor, (meth) acrylic acid and the above esterification catalyst are charged, and the above synthesis method is applied.

  Next, as a metal dryer, acetic acid, propionic acid, butyric acid, isopentanoic acid, hexanoic acid, 2-ethylbutyric 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, 3,5,5-trimethylhexa Metal salts of organic carboxylic acids such as Neucic acid and Dimethyloctanoic acid, for example, known and publicly used compounds such as calcium, cobalt, lead, iron, manganese, zinc, zirconium salts can be used. In order to promote curing, these two or more may be used in combination as appropriate. Kill.

  Next, the radical polymerization initiator can be roughly classified into a photocleavage type and a hydrogen abstraction type. Examples of the former include benzoin such as benzoin, benzoin methyl ether, benzoin isopropyl ether, α-acrylobenzoin, benzyl, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (Irgacure 907: Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (Irgacure 369: Ciba Specialty Chemicals), benzylmethyl ketal (Irgacure 651: Ciba Specialty Chemicals) ), 1-hydroxycyclohexyl phenyl ketone (Irgacure 184: manufactured by Ciba Specialty Chemicals), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173: Merck) 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (Darocur 1116: manufactured by Merck & Co.), 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-) Propyl) ketone, 4- (2-acryloyl-oxyethoxy) phenyl-2-hydroxy-2-propylketone, diethoxyacetophenone (ZLI 3331: manufactured by Ciba Specialty Chemicals), Esacure KIP100 (manufactured by Ramberty), lucillin TPO (BASF) Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide (BAPO1: manufactured by Ciba Specialty Chemicals), bis (2,4,6-trimethylbenzoyl) -phenylphosphine Fin oxide (BAPO : Manufactured by Ciba Specialty Chemicals Inc.), manufactured by BTTB (NOF (Ltd.)), CGI1700 (from Ciba Specialty Chemicals, and the like.

  Examples of the latter include benzophenone, p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 2-isopropylthioxanthone , 2,4-dimethylthioxanthone, 2,4 diethylthioxanthone, 2,4 dichlorothioxanthone, aryl ketone initiators such as acetophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dimethylamino) Dialkylaminoaryl ketone initiators such as benzophenone, isoamyl p-dimethylaminobenzoate, p-dimethylaminoacetophenone, thioxanthone, xanthone-based and halogens thereof Polycyclic carbonyl-based initiators such substitution system is illustrated. These can be used alone or in combination. These initiators can be used in the composition in the range of 0.1 to 30% by weight, but preferably in the range of 1 to 15% by weight.

  Next, as a coloring agent, an inorganic pigment and an organic pigment can be shown. Inorganic pigments such as yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, petal, alumina white, calcium carbonate, ultramarine, carbon black, graphite, aluminum powder, bengara etc. as organic pigments Are soluble azo pigments such as β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid anilide, acetoacetanilide, pyrazolone, β-naphthol, β-oxynaphthoic acid anilide, Insoluble azo pigments such as acetoacetanilide monoazo, acetoacetanilide disazo, pyrazolone, phthalocyanine pigments such as copper phthalocyanine blue, halogenated (chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine , Quinacridone , Dioxazine, selenium (pyrantron, anthanthrone, indanthrone, anthrapyrimidine, flavantron, thioindigo, anthraquinone, perinone, perylene, etc.), isoindolinone, metal complex, quinophthalone, etc. Various publicly known and publicly used pigments such as formula pigments and heterocyclic pigments are used.

Furthermore, by combining 0.1 to 10% by weight of the organopolysiloxane in the dry lithographic printing ink composition, the poor solubility of the material is utilized, and the organopolysiloxane appears on the surface of the ink composition after printing. The weak boundary layer that has a very weak binding force at the interface between the ink and the plate, and the organopolysiloxane appears on the surface of the ink composition after printing. In this technical field, it is possible to improve the dry lithographic printing suitability (ink does not adhere to the non-image area) by forming “WFBL (Week Fluid Boundary Layer)”. Examples of the organopolysiloxane of the present invention include dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane. For example, TSF451-10, TSF451-20, TSF451-30, TSF451-50, TSF451-100, TSF451-200, TSF451-300, TSF451-350, TSF451-500, TSF451-1000, TSF451- manufactured by Toshiba Silicon Corporation 3000, TSF451-5000, TSF451-6000, TSF451-1M, TSF451-3M, TSF451-5M, TSF451-6M, TSF451-10M, TSF451-20M, TSF451-30M, TSF451-50M, TSF456-100, TSF456-200, TSF456-1000, TSF456-2000, TSF456-1M, TSF410, TSF411, TSF4421, XF42-A3161, TSF 84, TSF431, YF33-100, YF33-3000, YF33-1M, TSF458-50, TSF433, TSF404, TSF405, TSF4045, TSF451-5A, TSF451-10A, TSF451-50A, TSF451-100A, TSF451-350A, TSF451- 1000A, TSF451-5000A, TSF437, TSF4440, TSF433, TSF404, TSF405, TSF4045, TSF451-5A, TSF451-10A, TSF451-50A, TSF451-100A, TSF451-350A, TSF451-1000A, TSF451-5000, F TSF433, TSF404, TSF405, TSF4045, TSF4 1-5A, TSF451-10A, TSF451-50A, TSF451-100A, TSF451-350A, TSF451-1000A, TSF451-5000A, TSF437, TSF4440,
TSF4441, TSF4445, TSF4446, TSF4452, TSF4460, TSF4600, TSF4700, TSF4701, TSF4702, TSF4703, TSF4704, TSF4705, TSF4706, TSF4707, TSF4708, TSF4709, TSF4450, TSF4730, F4-4 Further, Pentide A, Pentide H, Pentide M, Pentide Q, Pentide Q-N, Pentide S, Pentide 7, Pentide E-10, Pentide 29, Pentide 31, Pentide 32, Pentide 51, Pentide 54, manufactured by Dow Corning Asia Co., Ltd. Pentide 56, Pentide 57, DCZ-6018, DKQ8-8011, and the like.
Furthermore, KF-351, KF-352, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF are used as non-reactive silicone oils manufactured by Shin-Etsu Silicon Co., Ltd. -618, KF-6011, KF-6015, KF-6004, X-22-4272, X-22-4925, X-22-6266, KF-410 as methylstill modified silicone oil, KF-412 as alkyl modified silicone oil KF-413, KF-414, KF-910, X-22-715 as higher fatty acid ester-modified silicone oil, KF-3935 as higher fatty acid-containing silicone oil, FL-5, FL-10, X as fluorine-modified silicone oil -22-821, X-22-822, FL100, etc. It is.
In the present invention, a printing ink solvent having a boiling point of 200 to 400 ° C. containing a volatile organic compound (VOC) such as a conventional petroleum solvent may be used.

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

Next, the usage form as a curable composition in this invention is demonstrated. The active energy ray-curable composition in the present invention is used as a printing ink or overprint varnish (OP varnish). The usual composition ratio is as follows.
* Polymer composed of aromatic vinyl compound and α, β unsaturated carboxylic acid ester
1-40% by weight
* Vegetable oil and / or its fatty acid ester 1-20% by weight
* 50 to 180 ° C softening point resin 1 to 40% by weight
* Monomers or oligomers with ethylenically unsaturated double bonds
10-70% by weight

* Colorant
* Radical polymerization inhibitor
* Radically polymerizable initiator
* Metal dryer
* Other additives
* Solvent for printing ink
* Organopolysiloxane

Furthermore, in order to use as the active energy ray-curable dry lithographic curable ink of the present invention, the viscosity of the ink to be printed using a normal dampening solution is slightly caustic with respect to the viscosity of 20 to 60 Pa · s / 25 ° C. A temperature of 50 to 100 Pa · s / 25 ° C. is desirable from the viewpoint of suitability for dry lithographic printing such as contamination of non-image areas.

Furthermore, when the curable composition of the present invention is used for printing ink, it is desirable to use the composition as a varnish having a viscosity (100 to 300 Pa · s / 25 ° C.) that can be easily applied to printing ink.
In producing the varnish of the present invention, the resin having a softening point of 50 to 180 ° C. and vegetable oil or its fatty acid ester is dissolved or cooked in the temperature range of 180 to 260 ° C. for 0.5 to 3 hours and then cooled to 180 ° C. Thereafter, a polymer of an aromatic vinyl compound and an α, β unsaturated carboxylic acid is charged, and after 30 minutes of dissolution, a polymerization inhibitor is further added to the (meth) acryl monomer or (meth) acryl oligomer having an ethylenically unsaturated double bond. While charging, it is dissolved at 80 to 120 ° C. and used in the form of a varnish having a viscosity of 50 to 300 Pa · S / sec. If necessary, the varnish can be used as a varnish in a form in which the hybrid compound of the present invention is mixed. In producing the curable composition of the present invention, in that case, air blowing, nitrogen gas, addition of a polymerization inhibitor, or addition of an antioxidant, etc. are simultaneously performed as necessary.

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

  Further, the varnish can be made into a gel varnish using a gelling agent. As the gelling agent, usually an aluminum complex compound can be mentioned. Aluminum alcoholates such as aluminum isopropylate (AIPD manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum isopropylate-mono-sec-butylate (AMD manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum alkyl acetates such as aluminum di-iso-butoxide-ethylacetate Acetate (Chelope-Al-EB2 manufactured by Hope Pharmaceutical), Aluminum-di-iso-propoxide-ethylacetoacetate (Chelope-Al-EP12 manufactured by Hope Pharmaceutical Co., Ltd., ALch manufactured by Kawaken Fine Chemical Co.), Aluminum-Tris (acetylacetonate) (ALCH-TR manufactured by Kawaken Fine Chemical Co., Ltd.), Aluminum-Tris (Atylacetoacetate) (Aluminum Chelate manufactured by Kawaken Fine Chemical Co., Ltd.), A Miniumu - bis (ethyl acetylacetonate) - mono acetylacetonate (manufactured by Kawaken Fine Chemicals Co., Ltd. aluminum chelate D), (manufactured by Kawaken Fine Chemicals Co., Ltd.) aluminum chelate M, liquid Oripu AOS (manufactured by Hope Pharmaceutical Co., Ltd.) are 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. The preparation of the gel varnish is usually obtained by adding 0.1 to 3 parts by weight of a gelling agent and reacting in a temperature range of 100 to 200 ° C. for 30 minutes to 2 hours.

  The printing ink is a colorant, a varnish and / or its gel varnish, a hybrid compound of the present invention, a vegetable oil or a fatty acid ester thereof, a (meth) acrylic monomer having an ethylenically unsaturated double bond or ( Components for printing inks such as (meth) acrylic oligomers, radical polymerization inhibitors, radical polymerizable initiators and / or sensitizers, metal dryers, and other additives, kneaders, three rolls, attritors, sand mills, gate mixers, etc. Manufactured using a kneaded meat, mixing and adjusting machine.

  The curable ink comprising the curable composition of the present invention is usually applied to offset printing using fountain solution, but is also preferably used for waterless printing without using fountain solution. Moreover, the curable composition of this invention is applied also to overprint varnish (commonly called OP varnish). The curable composition and the curable ink of the present invention include foam prints, various book prints, various packaging prints such as carton paper, various plastic prints, seal / label prints, art prints, metal prints (art prints, Applied to printed matter such as beverage can printed matter, food printed matter such as canned food). For curable inks, UV curable inks and electron beam curable inks. For overcoat varnishes, UV curable overcoat varnishes, electron beam overcoat varnishes, and water based overcoat varnishes. There is also.

  Furthermore, in order to further enhance the aesthetic luxury and durability of the printed material using the curable ink of the present invention, the present invention prints the curable ink on the base material, and immediately wets the active energy ray-curable overcoat varnish. The present invention also provides a printing method for coating and irradiation with active energy rays, and a printed matter obtained by the method. After printing general oil-based inks that are usually only oxidatively polymerizable, immediately apply wet active energy ray overcoat varnish and irradiate with active energy rays.If gloss is measured after several days, the initial gloss is not maintained. The so-called gloss back that reduces gloss 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 material with an aesthetic luxury. The base materials are Hokuetsu Paper Co., Ltd. Maricoat, Polyethylene Coated Paper, Coated Cardboard such as Aluminum Coated Paper, Mitsubishi Paper Co., Ltd. Special Ryobi Art Paper, Thin Paper Coated Paper such as Fine Paper, Synthetic Paper, Plastic A film, a metal plate or the like is used.

Next, the present invention will be described with reference to specific examples. In the examples, “parts” means parts by weight.
Production Example of Polymer Compound (Polymer P1) In a four-necked flask equipped with a stirrer, equipped with a water separation tube and equipped with a thermometer, 154 parts of isoborneol (isobornyl alcohol), 0.2 part of hydroquinone, 20 parts of toluene, meta 86 parts of acrylic acid and 2 parts of P-toluenesulfonic acid are charged and allowed to react under air blowing until the acid value is 15 to 15 ° C. Thereafter, 12 parts of a 20% aqueous sodium hydroxide solution is added, neutralized, washed with 200 ml of water three times, and then desolvated under reduced pressure at 90 to 115 ° C. to obtain isoborneol methacrylic ester (isobornyl methacrylate). Next, 150 parts of toluene was charged, and the temperature was raised to 80 ° C. under a nitrogen stream. 50 parts of styrene, 40 parts of the above isoborneol methacrylic ester (isobornyl methacrylate), 5 parts of butyl methacrylate, 5 parts of hydroxypropyl methacrylate, benzoyl peroxide A solution obtained by dissolving 3 parts in advance was added dropwise over 3 hours. Two hours after the completion of the dropwise addition, 0.5 part of benzoyl peroxide was added and the reaction was continued for another 2 hours, and then the solvent was removed and pumped out. (Example polymer P1)
Similarly, (polymers P1 to P5) were synthesized with the compositions shown in Table 1. Borneol acrylic ester (bornyl acrylate) was obtained by equimolar reaction of borneol and acrylic acid, and terpineol methacrylic ester was obtained by equimolar reaction of terpineol and methacrylic acid by the same reaction operation method as that of isoborneol methacrylic ester.

Example of resin having a softening point of 50 to 180 ° C. (hereinafter, resin example) 1
(Resin Example R1)
Synthesis example 1 of rosin phenol resin
(Synthesis of resol type phenol resin)
A four-necked flask equipped with a stirrer, reflux condenser and thermometer was charged with 150 parts of p-tertiarybutylphenol, 203 parts of 37% formalin and 250 parts of xylene, heated and stirred while blowing nitrogen gas, and calcium hydroxide 2 at 50 ° C. 0.0 part was dispersed in 10 parts of water, the dispersion was added, the temperature was raised to 95 ° C., and the mixture was reacted at the same temperature for 3.5 hours. Then, it cooled, neutralized with sulfuric acid, and washed with water. The resole xylene solution layer and the aqueous layer were allowed to stand and separate. This resol type phenol resin is used as a resol solution.

(Synthesis of rosin phenol resin)
While blowing nitrogen gas into a four-neck flask with a stirrer, a water separator and a thermometer, 57 parts of rosin and 3 parts of maleic anhydride were charged and stirred with heating. ) Is added over a period of about 2 hours while reacting while collecting water and xylene, and after completion of the addition, the temperature is raised and 8.0 parts of glycerin is added at 250 ° C. and reacted for 12 hours. Because it became, it was pumped out.
The weight average molecular weight of this resin was 150,000. (Resin R1)
Note) * The parts by weight of the resor liquid that reacts with rosin is the parts by weight of solids after evaporation at 150 ° C for 30 minutes.
* The weight average molecular weight was measured by gel permeation chromatography (HLC8020) manufactured by Tosoh Corporation and the standard sample for the calibration curve was measured by polystyrene.

Synthesis example 2 of rosin phenol resin
(Synthesis of resol type phenol resin)
A four-necked flask equipped with a stirrer, reflux condenser, and thermometer was charged with 206 parts of p-octylphenol, 203 parts of 37% formalin and 250 parts of xylene, heated and stirred while blowing nitrogen gas, and calcium hydroxide 2.0 at 50 ° C. Parts were dispersed in 10 parts of water, the dispersion was added, the temperature was raised to 95 ° C., and the reaction was carried out at the same temperature for 3.5 hours. Then, it cooled, neutralized with sulfuric acid, and washed with water. The resole xylene solution layer and the aqueous layer were allowed to stand and separate. This resol type phenol resin is used as a resol solution.

(Synthesis of rosin phenol resin)
While blowing nitrogen gas into a four-neck flask with a stirrer, water separator and thermometer, while charging 60 parts of rosin, heat and stir, 40 parts of resole at 200 ° C. (40 parts is solid content equivalent) In the meantime, the reaction is carried out while collecting water and xylene, and after the completion of the addition, the temperature is raised and 6.0 parts of glycerin is added at 250 ° C. and reacted for 12 hours. As it became, we pumped out.
The weight average molecular weight of this resin was 45,000. (Resin R2)
Note) * The parts by weight of the resor liquid that reacts with rosin is the parts by weight of solids after evaporation at 150 ° C for 30 minutes.
* The weight average molecular weight was measured by gel permeation chromatography (HLC8020) manufactured by Tosoh Corporation and the standard sample for the calibration curve was measured by polystyrene.
(Example resin R3)
Examples of α, β-ethylenically unsaturated carboxylic acid ester-modified petroleum resins: Maruzen Petrochemical Co., Ltd. dicyclopentadiene resin (Marcaretz M510A: dicyclopentadiene / pentadiene = 4/1 weight ratio) 470 parts, maleic anhydride 30 parts The mixture was charged into a stirrer, a reflux condenser, and a flask equipped with a thermometer, heated with heating while blowing nitrogen gas, and reacted at 180 ° C. for 3 hours to obtain a maleic anhydride-modified DCPD resin (MD resin). Next, 300 parts of MD resin, 13 parts of neopentyl glycol, charged in a stirrer, reflux condenser with water separator, flask with thermometer, heated with heating while blowing nitrogen gas, reacted at 250 ° C. for 3 hours. A resin (resin R3) having an acid value of 10, a melting point of 140 ° C., and a weight average molecular weight (hereinafter referred to as Mw) of 105,000 in gel permeation chromatography (hereinafter referred to as GPC) was obtained.

Resin Example R4
α, β Ethylenically unsaturated carboxylic acid-modified rosin ester resin stirrer, water separation tube, polymerized rosin in a four-necked flask with thermometer (including 80% dimer rosin by Ryuka Hercules Co., Ltd.) Then, 8 parts of maleic anhydride is charged and subjected to Diels-Alder reaction at 180 ° C. for 2 hours under a nitrogen stream. Thereafter, 18.5 parts of pentaerythritol and 9.0 parts of octylic acid were charged, the temperature was gradually raised, the reaction was carried out at 250 ° C., the reaction was carried out to an acid value of 25 or less and pumped out. The weight average molecular weight of this resin was 11 million. (Resin R4)

Resin Example R5
Rosin and petroleum resin-modified ester resin A four-necked flask equipped with a stirrer, a water separator, and a thermometer was charged with 53 parts of gum rosin, 40 parts of Marcaretz M510 (manufactured by Maruzen Petroleum Co., Ltd.) and 8 parts of maleic anhydride under a nitrogen stream. At 180 ° C. for 2 hours. Thereafter, 18.5 parts of pentaerythritol and 9.5 parts of nonyl acid were charged, the temperature was gradually raised, the reaction was carried out at 250 ° C., the reaction was carried out to an acid value of 25 or less and pumped out. The weight average molecular weight of this resin was 115,000. (Resin R 5)

Resin Example 6 (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 15.2 parts of pentaerythritol was charged at 240 ° C. under a nitrogen stream and reacted at 270 ° C. to an acid value of 20 or less. Thereafter, 14.7 parts of isophthalic acid was gradually added at the same temperature and reacted until the acid value became 20 or less. The weight average molecular weight of this resin was 115,000. (Resin R6)

Production Example of Hybrid Compound (HR1) A four-necked flask with a stirrer, a water separation tube, and a thermometer was charged with 266 parts of soybean oil fatty acid, 134 parts of trimethylolpropane, 6 parts of p-toluenesulfonic acid, and 40 parts of toluene. Charge, gradually raise the temperature in a nitrogen stream, react at 110 ° C. for 9 hours, charge the acid value to 5 or less, 0.6 parts of methoquinone, 137 parts of acrylic acid, and at 110 ° C. in a nitrogen capacity stream Reacted. When the dehydration reaction was stopped after about 7 hours, 20 parts of cyclohexane was added, and the dehydration reaction was continued by refluxing. When the acid value reached 10.0, the water was washed three times with an equal amount of water. Was confirmed to be neutral or close to pH test paper, and then the solvent was removed and pumped out. The acid value was 2.0.

Production Example of Hybrid Compound (HR2) 287 parts of rosin, 134 parts of trimethylolpropane, and 40 parts of toluene were charged into a four-necked flask equipped with a stirrer, a water separation tube, and a thermometer, and gradually heated under a nitrogen stream. The mixture was reacted at 270 ° C. for 7 hours. When the acid value became 5 or less, it was cooled to 110 ° C., and 0.6 parts of methoquinone, 6 parts of p-toluenesulfonic acid and 137 parts of acrylic acid were added, The reaction was performed at 110 ° C. When the dehydration reaction stopped after about 8 hours, 20 parts of cyclohexane was added, and the dehydration reaction was continued by refluxing. When the acid value reached 10.0, the water was washed three times with an equal amount of water. Was confirmed to be neutral or close to pH test paper, and then the solvent was removed and pumped out. The acid value was 4.0.

Example of varnish production (creation of resin varnish)
A four-necked flask equipped with a stirrer, a water separation condenser, and a thermometer was charged with 20 parts of resin (R1), 7 parts of resin (R2), and 15 parts of soybean oil fatty acid butyl ester. At 20 ° C., 20 parts of Example polymer P1 was charged and stirred for 30 minutes, and then 110 ° C., 0.1 part of t-BHQ (tertiary butyl hydroquinone) and 39.9 parts of ditrimethylolpropane tetraacrylate were added and stirred for 30 minutes. It adjusted to 150-200 Pa.s / 25 degreeC and pumped out (Example varnish V1). Hereinafter, Example varnish V2 and Example varnishes V4 to V5 were similarly prepared.

(Example varnish V3)
In a four-necked flask equipped with a stirrer, water separation condenser and thermometer, 27 parts of resin (R6) and 15 parts of soybean oil are charged, heated and dissolved under a nitrogen stream, kept at 190 ° C for 1 hour, and then heated to 160 ° C. After adding 18 parts of Example polymer (P3) and 0.5 part of ALCH (Geling agent manufactured by Kawaken Fine Chemical Co., Ltd.), the mixture was kept at 190 ° C. for 1 hour, and then the formulation of Example varnish V3 in Table 2 was used. According to the contents, it was prepared by the operation procedure of Example varnish V1. (Example varnish V3).

Comparative Example Varnish Comparative Example Varnish (V 6 ) Production Example (Oxidation Polymerized Varnish)
In a four-necked flask with a stirrer, water separation condenser, thermometer, and nitrogen gas, under a nitrogen stream, 30 parts of Hiretsu TR105 (weight average molecular weight 150,000 with rosin-modified phenol resin manufactured by Hoshiko Chemical Co., Ltd.), rosin-modified phenol 15 parts of resin R2, 20 parts of sesame oil, 3 parts of AF5 solvent (Aroma Free Ink Solvent, Nippon Oil Co., Ltd.), 0.5 part of ALCH (Geling Agent, Kawaken Fine Chemical Co., Ltd.), t -0.1 part of BHQ (tertiary butyl hydroquinone) was charged and dissolved by heating at 200 ° C for 1 hour. When the viscosity was measured with a cone plate viscometer, it was 115 Pa · s / 25 ° C.

Similarly, in the formulation shown in Table 3 to prepare a Comparative Example varnish V 7.

Comparative Example Production Example of Varnish (V 8 ) (Active Energy Ray Curing Varnish)
A four-necked flask with a stirrer, a water separation condenser, and a thermometer, 30 parts of Dap Tote DT170 (Dialylphthalate resin manufactured by Tohto Kasei Co., Ltd.), 69.9 parts of ditrimethylolpropane tetraacrylate, 0.1 part of hydroquinone Was dissolved in an air stream at 100 ° C. for 30 minutes to 1 hour. When the viscosity was measured with a cone plate viscometer, it was 152 Pa · s / 25 ° C.
Similarly, in the formulation shown in Table 3 to prepare a comparative example varnish V 9.

Production Example of Curable Ink (Ink 1) 18 parts of Carmine 6B (Red Pigment made by Toyo Ink Co., Ltd.) as a red pigment, 50 parts of Varnish V1, CN111 (epoxidized soybean oil acrylic ester made by Kayaku Sartomer Co., Ltd.) ) 5 parts, Dialen 168 (Mitsubishi Chemical Corporation olefin solvent) 6 parts, ditrimethylolpropane tetraacrylate 15.9 parts, 4,4'-bis (diethylamino) benzophenone (EAB) 2.5 parts, 2.5 parts of Irgacure 907 and 0.1 parts of t-BHQ (tertiary butyl hydroquinone) were charged and produced in a conventional manner using a three-roll mill.

  The ink viscosity was adjusted to 60 Pa · s / 25 ° C., tack value (water temperature of roll in incometer 30 ° C., room temperature 25 ° C.), flow (parallel plate viscometer 25 ° C. with constant load spread) ), The tack value was 8.0 / 25 ° C., and the flow was 18.5. Inks 2 to 5 were produced according to the formulation shown in Table 4 below. Ink 5 is an example of electron beam curable ink.

Comparative Example Production Example of Oil-based Ink (Ink 6) 18 parts of Carmine 6B, 70.9 parts of Varnish V 6 , 4 parts of AF5 solvent (solvent manufactured by Nippon Petrochemical Co., Ltd.), 6 parts of Dialen 168, t- BHQ (tertiary butyl hydroquinone) 0.1 part and manganese naphthenate 1 part were charged and prepared by a conventional method using a three-roll mill.

The ink viscosity was adjusted to 60 Pa · s / 25 ° C., and the tack value and flow were measured. The tack value was 7.5 / 25 ° C. and flow 19.
Similarly, Comparative Example Oil-based Ink 7 was produced according to the formulation shown in Table 5.

Comparative example UV curable ink (ink 8)
Carmine 6B 18 parts, Varnish V 8 30 parts, ditrimethylolpropane tetraacrylate 26.9 parts, dipentaerythritol hexaacrylate 20 parts, EAB 2.5 parts, Irgacure 907 2.5 parts, hydroquinone 0.1 Part, TSF451-100 (Toshiba Silicon Co., Ltd. organopolysiloxane) was charged in 1.5 parts, and prepared in a conventional manner with a three roll mill. The ink viscosity was adjusted to 60 Pa · s / 25 ° C., and the tack value and flow were measured. The tack value was 14.5 / 25 ° C. and the flow was 13.8.

Comparative Example Electron curable ink (ink 9)
18 parts of Carmine 6B, 35 parts of a varnish V 9, 26.9 parts of ditrimethylolpropane tetraacrylate, 20 parts by weight of dipentaerythritol hexaacrylate, 0.1 parts of hydroquinone, TSF451-100 (manufactured by Toshiba Silicon Co. Oruganopori 1.5 parts of (siloxane) was charged and prepared by a conventional method using a three-roll mill. The ink viscosity was adjusted to 60 Pa · s / 25 ° C., and the tack value and flow were measured. The tack value was 13.8 / 25 ° C. and flow 16. It shows in Table 6 below.

本発明の効果を乾式平版印刷試験で説明する。（表７）
小森コポレーション（株）製リスロンＬ２２６の印刷機を使用し東レ（株）製乾式平版（商品名ＨＧ２）印刷速度１２０００枚／時で各インキを王子製紙（株）製ＯＫトップコート紙（６２．５Ｋg）に印刷し、東芝（株）製紫外線照射装置１２０Ｗ／cmメタハラランプ３灯で照射し６０００枚棒積みし、地汚れ発生温度、紙剥け、パイリング、棒積み性を以下の要領で確認した。
地汚れ発生版面温度：印刷機温度を常温（２５℃）から徐々に昇温し乾式版面温度を測定し、版面温度と非画線部の汚れが生じなくなった温度で温度が高い程良好の結果を示す。
紙剥け：印刷時にブランケットに紙の一部が張り付き紙の表面が剥ける現象。
パイリング：版やブランケットにインキや紙粉が堆積する状態。
棒積み性：上記６０００枚印刷後下部の印刷物が乾燥不良のによる裏付き現象。
尚、参考実施例インキ５、比較例インキ９は電子線硬化性インキ組成物であり、印刷中の印刷物を抜き取り、５ｃｍ＊４ｃｍにカットし、その後電子線照射については、東洋インキ製造（株）製Ｍin-ＥＢ超小型・超低加速電圧電子線照射装置（加圧電圧２０〜６０ＫＶ、酸素濃度２００ppm の窒素置換した雰囲気）を用い３０ＫＧy で照射した。その後２０枚に１０Ｋgの荷重（１パレットの平均的印刷物の荷重５００g／ｃｍ2）をかけ１日後の裏付き度合い。
本発明の効果を、グロスバック試験にて説明する。（参考実施例１、５、実施例１〜４、比較例６〜９）
−紫外線照射の場合−
マリコート紙（北越製紙（株）製コートボール紙）にＲＩテスター（明製作所（株）製簡易印刷機）を使用し、インキ盛り０．３ccで展色刷りした後、直ちにワイヤーバー＃３Ｋ−ロックスプルーファ（ＲＫ ＰＲＩＮＴ−ＣＯＡＴ ＩＮＳＴＲＵＭＥＮＴＳ Ｌｔｄ）で、紫外線硬化性ニス（ＦＤＰＣＡ９０２ワニス：東洋インキ製造(株)製）を塗工、紫外線照射し、直後と７２時間後に光沢を測定した。またセロハンテープ剥離による密着試験も実施した。紫外線照射は、東芝（株）製紫外線照射装置（１２０Ｗ／cm超高圧水銀オゾンノーカットランプ１灯、コンベヤースピード３０m ／min の条件）を使用した。光沢計は村上色彩研究所（株）製６０度の条件で使用した。
−電子線照射の場合−
紫外線照射の場合と同条件で展色刷りし、ＥＢ硬化性ニス（ＦＤＰＣＡ９０２から開始剤を除いたニス）を塗工後、直ちに電子線照射した。電子線照射については、東洋インキ製造（株）製Ｍin-ＥＢ超小型・超低加速電圧電子線照射装置（加圧電圧２０〜６０ＫＶ、酸素濃度２００ppm の窒素置換した雰囲気）を用い３０ＫＧy で照射した。

The effect of the present invention will be described with a dry lithographic printing test. (Table 7)
Using a Lilithon L226 printing machine manufactured by Komori Corporation, each ink was supplied to Toray Industries, Ltd., dry planographic plate (trade name HG2) at a printing speed of 12,000 sheets / hour, and Oki Paper Co., Ltd. OK Top Coat Paper (62. 5Kg), irradiated with 3 lamps of 120W / cm Meta-Harahara lamp manufactured by Toshiba Corp., and stacked 6000 sheets, and confirmed the scumming temperature, paper peeling, piling, and stackability as follows. .
Stain generation plate surface temperature: Gradually raise the printing press temperature from room temperature (25 ° C) and measure the dry plate surface temperature. The higher the temperature at the plate surface temperature and the temperature at which the non-image area is not stained, the better results. Indicates.
Paper peeling: A phenomenon in which a part of paper sticks to a blanket and the surface of the paper peels off during printing.
Piling: Ink or paper dust is deposited on the plate or blanket.
Stackability: Backing phenomenon due to poor drying of the printed matter at the bottom after printing 6000 sheets.
In addition, Reference Example Ink 5 and Comparative Example Ink 9 are electron beam curable ink compositions, and the printed matter during printing is extracted and cut into 5 cm * 4 cm, and then the electron beam irradiation is performed by Toyo Ink Manufacturing Co., Ltd. Irradiation was performed at 30 KGy using a Min-EB ultra-compact and ultra-low acceleration voltage electron beam irradiation apparatus (pressurized voltage 20-60 KV, nitrogen-substituted atmosphere with an oxygen concentration of 200 ppm). Then, a load of 10 kg (the load of an average printed material on one pallet 500 g / cm @ 2) was applied to 20 sheets, and the degree of backing after 1 day.
The effect of the present invention will be described with a glossback test. ( Reference Examples 1 and 5, Examples 1 to 4 , Comparative Examples 6 to 9)
-In case of UV irradiation-
Using a RI tester (a simple printing machine manufactured by Meisei Seisakusho Co., Ltd.) on Maricoat paper (coated cardboard manufactured by Hokuetsu Paper Co., Ltd.) and color-printing at 0.3 cc of ink, wire bar # 3K-lock proof immediately A UV curable varnish (FDPCA902 varnish: manufactured by Toyo Ink Manufacturing Co., Ltd.) was applied with UV light (RK PRINT-COAT INSTRUMENTS Ltd), and the gloss was measured immediately and after 72 hours. In addition, an adhesion test by cellophane tape peeling was also performed. For the ultraviolet irradiation, an ultraviolet irradiation apparatus (120 W / cm ultra high pressure mercury ozone uncut lamp, condition of conveyor speed 30 m / min) manufactured by Toshiba Corporation was used. The gloss meter was used under the condition of 60 degrees made by Murakami Color Research Laboratory.
-In the case of electron beam irradiation-
The color was printed under the same conditions as in the case of ultraviolet irradiation, and after EB curable varnish (varnish obtained by removing the initiator from FDPCA902) was applied, electron beam irradiation was performed immediately. For electron beam irradiation, irradiation was performed at 30 KGy using a Min-EB ultra-compact and ultra-low acceleration voltage electron beam irradiation device (pressurized voltage 20-60 KV, nitrogen-substituted atmosphere with an oxygen concentration of 200 ppm) manufactured by Toyo Ink Manufacturing Co., Ltd. .

  The above results are summarized in Table 7.

Claims (8)

1 to 30% by weight of the polymer (a),
1 to 40% by weight of an oil-soluble resin (b) other than (a),
1 to 20% by weight of vegetable oil or fatty acid ester thereof (c),
(Meth) acrylic monomer or (meth) acrylic oligomer (d) having 10 to 70% by weight of ethylenically unsaturated double bond,
0.1 to 10% by weight of organopolysiloxane and 1 to 40% by weight of colorant or extender pigment (e)
In the active energy ray-curable dry lithographic printing ink composition comprising,
The polymer (a) is
Styrene and / or vinyl toluene;
Isoborneol methacrylic ester, borneol acrylic esters, Terupi Ne ol methacrylic esters, one or more selected from butyl methallyl rate and hydroxypropyl methacrylate and
Consists of
Oil-soluble resin (b)
Softening point 50-180 ° C
and
Weight average molecular weight 30,000-150,000
Is
One selected from rosin modified phenolic resin, petroleum resin, α, β-ethylenically unsaturated carboxylic acid ester modified petroleum resin, alkyd resin, rosin modified alkyd resin and α, β-ethylenically unsaturated carboxylic acid modified rosin ester resin More than
An active energy ray-curable dry lithographic printing ink composition characterized by Having an ethylenically unsaturated double bond (meth) acrylic monomer or (meth) acrylic oligomer (d) is an alkylene oxide adduct of an aliphatic alcohol compound (meth) according to claim 1 active energy ray-curable according acrylate Dry lithographic printing ink composition. Claim 1 or 2 active energy ray-curable dry planographic printing ink composition according containing 0.1 to 10% by weight of the printing ink solvent. The active energy ray-curable dry lithographic printing ink composition according to any one of claims 1 to 3 , having a viscosity of 50 to 100 Pa · S / 25 ° C. The active energy ray-curable dry lithographic printing ink composition according to any one of claims 1 to 4 , comprising 0.1 to 3% by weight of a metal dryer and / or 0.1 to 15% by weight of a radically polymerizable initiator. The active energy ray-curable ink composition according to any one of claims 1 to 5 is printed on a substrate, and the active energy ray-curable overcoat varnish or the overprint varnish is applied in a state where the printing ink is uncured or cured. A printing method characterized by being worked and irradiated with active energy rays. Claim 1-5 printed prints the active energy ray-curable dry planographic printing ink composition according to any one. A printed matter obtained by the printing method according to claim 6 .