JP2006016508A - Acrylic monomer or active energy radiation curing composition containing the same and printed matter therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic monomer having curability and printability (a range of water volume supplied in printing) similar or superior to those of ditrimethylolpropane tetraacrylate, etc., and capable of being given at a low cost, and to provide an active energy radiation curing composition given by using the monomer and capable of being cured by being irradiated with ultraviolet radiation, electron radiation, etc. <P>SOLUTION: This fatty acid-modified acrylic monomer (C) is obtained by subjecting a polymer mixture (A) in an amount of (a1+a2) mol and a polyol (B) in an amount of b mol to esterification reaction, wherein the polymer mixture (A) is given by together reacting a fatty acid (C<SB>m</SB>H<SB>2m±1</SB>-COOH) and acrylic acid (CH<SB>2</SB>=CH-COOH) and satisfies specific formulae 1 and 2. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyfunctional acrylic monomer having a high curability and a low cost, and an active energy ray-curable composition and printed matter that are cured by ultraviolet rays or electron beams containing the same.

  In recent years, active energy ray-curable printing inks and varnishes have been developed by VOCS (volatile organic compound) free inks that can be used for early printing and processing on various types of paper containers and labels, and eliminates volatile hydrocarbon-based ink solvents. in use. For example, in the case of ultraviolet curable printing ink, printing is performed at a high speed printing speed of 10,000 to 15,000 sheets / hour (3 to 5 sheets / second), so the ultraviolet irradiation time is as short as about 0.2 seconds. Curing printing ink is used. Therefore, in the case of ultraviolet curable printing ink, dipentaerythritol hexaacrylate (hereinafter referred to as DPHA) and ditrimethylolpropane tetraacrylate (hereinafter referred to as DTMP4A), which are polyfunctional acrylic monomers, are mainly used. In particular, DTMP4A, which is tetrafunctional, is inferior to DPHA, which is hexafunctional, in terms of curability, but is relatively lipophilic compared to DPHA, has good emulsification properties even in offset inks that use fountain solution, and is further oxidatively polymerizable It is also used in inks that have the characteristics of both oil-based inks and active energy ray-curable inks (hereinafter referred to as hybrid inks). However, the active energy ray-curable printing ink has also entered the stable growth period after 30 years, and the recent low-growth economic environment, such as the ink, will also become more demanding for cost reduction due to increased cost competition as well as performance. Became. Generally, the cost of active energy ray-curable ink, varnish, etc. is 2 to 3 times that of oil-based ink (ink mainly composed of rosin phenol resin / vegetable oil / petroleum solvent), and cost reduction is required.

DTMP4A is synthesized by acrylation of ditrimethylolpropane di (trimethylolpropane dimer). And ditrimethylolpropane (market price ¥ 600 to 700 / Kg), which is the raw material for the acrylation, is 1/5 to 1/1 / during synthesis of trimethylolpropane (monomer and market price ¥ 200 to 300 / Kg). It is produced by purifying 10 by-products. Pentaelsitol also has a market value of 200 to 300 / Kg. Therefore, compared with these monomer raw materials, the dimer raw material naturally increases in cost, and thus the acrylated product also increases in cost. Therefore, low-cost polyfunctional oligomers and monomers have been demanded.
JP 58-104908 A JP 03-271252 A Japanese Unexamined Patent Publication No. 04-134049

  As a result of intensive studies to improve these disadvantages, the present invention has a low-cost fatty acid-modified acrylic monomer that has the same or better curability and printability (water width) as DTMP4A and can be used for the hybrid ink, It hardened | cured by irradiation of the ultraviolet-ray or electron beam etc. which used it, and came to invent about an active energy ray curable composition.

That is, the present invention is by reaction of fatty acids _{(C m H 2m ± 1 -COOH} ) and acrylic acid _{(CH 2 = CH-COOH)} , multimers represented by (a1 + a2) molar of the formula 1 The present invention relates to a fatty acid-modified acrylic monomer (C) obtained by esterifying a mixture (A) and b mol of a polyol (B).
The multimeric mixture (A) is represented by the formula 1: (a1) CH ₂ ═CH—COO (CH ₂ CH ₂ COO) _k —H
{Wherein k represents 0 or an integer, and the average value k is 0.1 to 3. }
Formula _{2: (a2) C m H} 2m ± 1 -COO (CH 2 CH 2 COO) 2n -H
{In the formula, m represents an integer of 1 to 20, n represents 0 or an integer, and the average value n is 0.1 to 3. } And a mixture with
0.05 ≦ a2 / a1 ≦ 0.5
0.9 ≦ (a1 + a2) /bx≦1.5 Note: x satisfies the number of functional groups of the hydroxyl group of the polyol (B).
The present invention also relates to the above fatty acid-modified acrylic monomer (D), wherein the polyol (B) is selected from pentaerythritol, trimethylolpropane, trimethylolethane, and glycerin.

Further, the present invention provides 1 to 90% by weight of the fatty acid-modified acrylic monomer (D), 1 to 90% by weight of the (meth) acrylic monomer (E), 1 to 50% by weight of a softening point of 50 to 180 ° C. The active energy ray-curable composition comprising (F).
Furthermore, this invention relates to the said active energy ray curable composition containing 1 to 20weight% of vegetable oil or its fatty acid ester.
Furthermore, this invention relates to the printed matter formed by printing the said active energy ray curable composition.

  The acrylic monomer provided by the present invention has excellent curability and printability (water width) and is low in cost, and an active energy ray curable composition using the acrylic monomer is also excellent in cost and performance. It is a thing.

The fatty acid of the present invention is a saturated or unsaturated fatty acid obtained by hydrolysis of vegetable oil, such as acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, oleic acid, elaidic acid, Linoleic acid, linolenic acid, arachidonic acid, eicosanoic acid, erucic acid, docosahexaenoic acid, ricinoleic acid and the like can be exemplified, 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 fractionated fatty acid by fractional distillation thereof is used to obtain a mixture of the above-mentioned saturated or unsaturated fatty acids.

The multimeric mixture (A) represented by Formula 1 and Formula 2 can be obtained by heating acrylic acid and fatty acid at 60 to 150 ° C. If necessary, a catalyst such as sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, tertiary amine, or a solvent or a polymerization inhibitor may be added. The charging ratio of fatty acid and acrylic acid is set to the number of moles of fatty acid / number of moles of acrylic acid = 0.05 to 0.5. If it is less than this range, the effect of the fatty acid is small, and if it is large, the curability of the monomer deteriorates.
When the value of (a1 + a2) / bx is less than 0.9, the hydroxyl group becomes excessive, and when it exceeds 1.5, the acid becomes excessive. When the active energy ray-curable composition is used as a printing ink, the fountain solution is used. The emulsification suitability at the time of printing due to use deteriorates and an appropriate printed matter cannot be produced.
The product after the reaction is a mixture of those represented by the following formulas 1 and 2.
Formula _{1: (a1) CH 2 =} CH-COO (CH 2 CH 2 COO) k -H
{Wherein k represents 0 or an integer, and the average value k is 0.1 to 3. }
Formula _{2: (a2) C m H} 2m ± 1 -COO (CH 2 CH 2 COO) 2n -H
{In the formula, m represents an integer of 1 to 20, n represents 0 or an integer, and the average value n is 0.1 to 3. } And a mixture with
0.05 ≦ a2 / a1 ≦ 0.5
0.9 ≦ (a1 + a2) /bx≦1.5 Note: x satisfies the number of functional groups of the hydroxyl group of the polyol (B).
At this time, the number k and n are controlled repeatedly depending on the heating temperature, the heating time, and the catalyst amount. k is preferably 0.2 to 1, particularly preferably 0.3 to 1.0. n is preferably 0.2 to 1, particularly preferably 0.3 to 1.0.

Examples of the polyol (B) used for the reaction in the multimeric mixture (A) of fatty acid and acrylic acid represented by the above formula 1 include ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolethane, and trimethylol. Examples include propane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, polyester polyol, polyurethane polyol, and the like, or a mixture of two or more thereof. Particularly in the present invention, pentaerythritol, trimethylolpropane, glycerin, particularly pentaerythritol is desirable.

The ester reaction of the fatty acid and acrylic acid multimeric mixture (A) represented by the above formulas 1 and 2 and the polyol (B) can be carried out in accordance with a normal ester reaction. For example, it is carried out while heating and dehydrating at 80 to 120 ° C. in the presence of a suitable catalyst such as sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid and ethanesulfonic acid and a suitable solvent such as cyclohexane and toluene.
When the fatty acid-modified monomer (D) of the present invention is used in an active energy ray-curable composition, it is 1 to 90% by weight, preferably 20 to 70% by weight. When the amount is less than 1% by weight, the effect of the present monomer cannot be exerted. When the amount is more than 90% by weight, the composition is composed of pigments, resins, and other materials, and is not used any more.

Examples of 1 to 90% by weight of (meth) acrylic monomer (E) include monofunctional monomers such as phenoxyethyl acrylate, cyclohexyl (meth) acrylate, and tricyclodecane monomethylol (meth) acrylate. Furthermore, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di ( (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1 , 7-Heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,2-octanediol di (meth) acrylate di (meth) ) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate , Tricyclodecane dimethylol dicaprolactonate di (meth) acrylate, and trifunctional monomers include glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate and the like. Tetraerythritol tetra (meth) acrylate, pentaerythritol tetracaprolactonate tetra (meth) acrylate, diglycerin tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol polyalkylene oxide hepta (meth) acrylate, etc. are exemplified. The (meth) acrylate monomer of the polyol having an alkyl group is an alkyl (carbon number 1-18) (meth) acrylic as a monofunctional monomer. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and isobornyl Examples include (meth) acrylate. Furthermore, as a bifunctional monomer, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalylhydroxypivalate di (meth) acrylate (commonly called manda) di (meth) acrylate, hydroxypivalylhydroxypivalate dicaprolactonate di (meth) Acrylate, hexanediol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tricyclodecane dimethylol dicaprolactone Di (meth) acrylate, bisphenol A tetrapropylene oxide adduct di (meth) acrylate, bisphenol A polyalkylene oxide adduct di (meth) acrylate, bisphenol F tetrapropylene oxide adduct di (meth) acrylate, bisphenol F polyalkylene Oxide adduct di (meth) acrylate, bisphenol S tetraethylene oxide adduct di (meth) acrylate, bisphenol S polyalkylene oxide adduct di (meth) acrylate, water-added bisphenol A tetrapropylene oxide adduct di (meth) acrylate, Water-added bisphenol A polyalkylene oxide adduct di (meth) acrylate, water-added bisphenol F tetrapropylene oxide adduct di (me ) Acrylate, water-added bisphenol F polyalkylene oxide adduct di (meth) acrylate, water-added bisphenol A di (meth) acrylate, water-added bisphenol F di (meth) acrylate, dihydroxybenzene (catechol, resorcin, hydroquinone, etc.) polyalkylene Oxide di (meth) acrylate, alkyldihydroxybenzene polyalkylene oxide di (meth) acrylate, bisphenol A tetraethylene oxide adduct dicaprolactonate di (meth) acrylate, bisphenol F tetraethylene oxide adduct dicaprolactonate di (meta ) Acrylate and the like. As trifunctional monomers, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate, trimethylolethane (meth) Acrylate, trimethylolethane tri (meth) acrylate, trimethylolhexanetri (meth) acrylate, trimethylolhexanetri (meth) acrylate, trimethyloloctanetri (meth) acrylate, trimethyloloctanetri (meth) acrylate, pentaerythritol Examples thereof include hydroxybenzene (such as pyrogallol) polyalkylene oxide adduct triacrylate and the like. Teeth, diglycerin tetra (meth) acrylate, tri (meth) acrylate, diglycerin polyalkylene oxide tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane tetracapro Examples include lactonate tetra (meth) acrylate, ditrimethylolethane tetra (meth) acrylate, and octa (meth) acrylate. Examples thereof include ditrimethylolbutanetetra (meth) acrylate, ditrimethylolhexanetetra (meth) acrylate, ditrimethyloloctanetetra (meth) acrylate, and the like.

Further, an alkylene oxide adduct (meth) acrylate monomer of an aliphatic alcohol compound, particularly an alkylene oxide adduct (meth) acrylate monomer of an aliphatic alcohol compound having an alkylene oxide of C3 to C20 or more is added to the resin, vegetable oil or fatty acid ester thereof. On the other hand, solubility is improved. Alkylene oxide adduct (meth) acrylate monomer of aliphatic alcohol compound Mono- or poly (1-20) alkylene (C2 to C20) oxide adduct of aliphatic alcohol compound (alkylene oxide such as ethylene oxide, propylene oxide, butylene) Oxide, pentylene oxide, hexylene oxide, etc.) mono or poly (1-10) (meth) acrylate. Further, ethylene glycol mono- or poly (1-20) alkylene (C2 to C20) oxide adducts (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, diethylene glycol mono or poly (bifunctional monomer). 2-20) Alkylene (C2 to C20) oxide adducts (e.g., ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,6 hexanediol poly (2-20) alkylene oxide adducts as alkylene oxides (For example, ethylene oxide, propylene oxide, butylene oxide, etc.) Di (meth) acrylate, 1,8-octanediol poly (2-20) alkylene (C2-C20) oxide addition (As alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,9-nonanediol poly (2-20) alkylene (C2 to C20) oxide adduct (as alkylene oxide, for example, ethylene oxide , Propylene oxide, butylene oxide) di (meth) acrylate, 1,2-decanediol poly (2-20) alkylene (C2 -C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (Meth) acrylate, 1,10-decanediol poly (2-20) alkylene (C2 to C20) oxide adduct (alkylene oxide such as ethylene oxide, propylene oxide, butylene) Oxide) di (meth) acrylate, 1,2-decanediol poly (2-20) alkylene (C2 to C20) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, as alkylene oxide. 1,12-dodecanediol poly (2-20) alkylene (C2 to C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate as alkylene oxide, glycerin poly (2 as trifunctional monomer) -20) alkylene (C2 to C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolpropane poly (2-2 0) 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 as alkylene oxide (Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate. 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 (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, etc. Illustrated.
When the (meth) acrylic monomer (E) of the present invention is used in an active energy ray-curable composition, it is preferably 0 to 90% by weight, more preferably 0 to 70% by weight. For printing ink applications using active energy ray-curable compositions, (meth) acrylic monomers may not be used, but varnishes may be used supplementarily to adjust varnish viscosity and prevent ruled line cracking after curing. Therefore, the above range of use is desirable.

Resin (F) having a softening point of 50 to 180 ° C. of the present invention is a dibasic acid diallyl ester polymer (diallyl phthalate resin, etc.), alkyd resin, ketone resin, styrene acrylic resin, epoxy resin, epoxy ester resin, rosin phenol resin, Examples include melamine resin, terpene resin, coumarone indene resin, and the like.
When the resin (F) having a softening point of 50 to 180 ° C. of the present invention is used in an ink using the active energy ray-curable composition, the ink viscosity is too low when it is less than 1%, and the ink viscosity is high when it is large. Therefore, it is not preferable because the viscosity is not suitable (20 to 100 P · S / 25 ° C., preferably 30 to 60 P · S / 25 ° C.) and normal printing cannot be performed with a printing press.

The dibasic acid diallyl ester polymer contained in the active energy ray-curable composition of the present invention is not particularly limited, and the dibasic acid diallyl ester monomer is radically polymerized or ionically polymerized by a conventional method. Is obtained. Other monomers such as (meth) acrylic ester, styrene and vinyl compounds may be copolymerized. The weight average molecular weight of the polymer is preferably 3000 to 100,000, more preferably 10,000 to 50,000. If the weight average molecular weight is less than 3000, the physical properties such as the coating film hardness of the cured product are likely to deteriorate, and if it exceeds 100,000, the viscosity of the active energy ray-curable composition containing the dibasic acid diallyl ester polymer tends to increase. It is not preferable. The dibasic acid diallyl ester monomer used for polymerization is not particularly limited, and examples thereof include orthophthalic acid diallyl ester, isophthalic acid diallyl ester, terephthalic acid diallyl ester, methylated tetrahydrophthalic acid diallyl ester, Examples include tetrahydrophthalic acid diallyl ester, tetrahydroisophthalic acid diallyl ester, succinic acid diallyl ester, maleic acid diallyl ester, itaconic acid diallyl ester, and the like, and mixtures thereof. In view of printability and film properties after curing, orthophthalic acid diallyl ester or isophthalic acid diallyl ester is preferred.

The alkyd resin is obtained by an esterification reaction of a monobasic acid, a polyol and a polybasic acid. The monobasic acid of the present invention is preferably 0 to 50% by weight of an aliphatic monobasic acid and / or 50 to 100% by weight of an aromatic or alicyclic cyclic monobasic acid. Examples of the aliphatic monobasic acid include C2 to C20 fatty acids, fatty acids of vegetable oils represented by coconut, linseed oil, soybean oil and the like. The aromatic monobasic acid is a compound in which a carboxylic acid group is directly bonded to an aromatic compound such as benzene or naphthalene, and other substituents such as an alkyl group may be bonded to the aromatic ring. Specific examples of the aromatic monobasic acid include benzoic acid, methyl benzoic acid, tertiary butyl benzoic acid, naphthoic acid, orthobenzoyl benzoic acid and the like. Examples of the alicyclic monobasic acid include rosins (gum rosin, tall oil rosin, wood rosin, disproportionated rosin, hydrogenated rosin), cyclohexane monocarboxylic acid, tricyclodecane monocarboxylic acid, and the like.

As polyols for alkyd resins, divalent polyols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, nepentyl glycol, branched alkyl diols such as butyl, ethyl, propanediol, tricyclodecane dimethylol, dicyclopentadiene diallyl. Alcohol copolymer, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, hydrogenated catechol, hydrogenated resorcin, hydrogenated hydroquinone, hydrogenated trivalent polyol, glycerin, trimethylolethane, trimethylolpropane, trimethylol Trimethylol alkanes such as hexane and trimethylol octane, pentaerythritol, diglycerin, ditrimethylol group as tetravalent or higher polyols Bread, sorbitan, sorbitol, dipentaerythritol, inositol, tripentaerythritol, and the like. Glycerin, trimethylolpropane, trimethylolethane and pentaerythritol are preferred for economic reasons.

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

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

The alicyclic polybasic acid for alkyd includes a cyclic polybasic acid which is a reaction product of petroleum resin and / or rosins and α, β-ethylenically unsaturated carboxylic acid or its anhydride.
The petroleum resin of the present invention can be obtained by subjecting the C5 fraction or C9 fraction obtained by naphtha decomposition to cation, anion or radical polymerization. Petroleum resin containing a C5 fraction is a cyclopentadiene, methylcyclopentadiene, a dimer or pentamer thereof, a cyclopentadiene monomer such as a co-multimer, or a cyclopentadiene monomer. It is obtained by thermally polymerizing a mixture with a polymerizable comonomer in the presence of a catalyst or without a catalyst. As the catalyst, a Friedel-Craft type Lewis acid catalyst, for example, boron trifluoride and its complex with phenol, ether, acetic acid and the like are usually used.

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

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

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

The Diels-Alder reaction of petroleum resin or rosin and α, β-ethylenically unsaturated carboxylic acid or its anhydride can be performed by a known method. For example, the reaction temperature is 120 to 300 ° C, preferably 180 to 260 ° C, and the reaction time is 1 to 4 hours.

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

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

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

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

Furthermore, styrene acrylic resin is a copolymer of styrene and (meth) acrylic ester, and (meth) acrylic ester is methyl (meth) acrylate, ethyl (meth) acrylate, 2 ethylhexyl (meth) acrylate, isobornyl (meth) acrylate. Is illustrated

Further, examples of the epoxy resin include Epicoat 828, Epicoat 1001, Epicoat 1004, Epicoat 1007, Epicoat 1009 (manufactured by Yuka Shell Co., Ltd.), which are glycidyl ethers of bisphenol A or F. Further, the epoxy ester resin is composed of the above epoxy resin and the above C2-20 aliphatic monobasic acid (for example, fatty acid of vegetable oil such as soybean oil and linseed oil), cyclic monobasic acid (for example, benzoic acid, t-butylbenzoic acid, rosin, Examples are esterified products with disproportionated rosin, hydrogenated rosin and the like.

As rosin-modified phenolic resins, phenols such as carboxylic acid, hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, (tertiary) butylphenol, (tertiary) octylphenol, nonylphenol, dodecylphenol, hexadecylphenol, and mixtures thereof and alkali Alternatively, a resole or novolak phenol resin condensed with an acidic catalyst and a rosin (gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, etc.) are subjected to a chromanization reaction, and glycerin and pentaerythritol. Such as p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, etc., magnesium oxide, calcium oxide catalyst A resin having a weight average molecular weight of 1 to 1,000,000, preferably 3 to 150,000 is used, and the reaction method is a conventional method. To increase the molecular weight of the resin, phenols are especially used for synthesizing resole. It is desirable to increase the formaldehyde ratio relative to the ratio. (For example, 1.5 mol to 4 mol, preferably 2 to 3 mol of formaldehyde with respect to 1 mol of phenol is desirable.) Furthermore, when reacting resoles and rosins, resoles / rosins = 20 to 60/80 to 40, preferably resoles / rosins = 40-60 / 60-40 are desirable. Furthermore, (alpha) and (beta) unsaturated carboxylic acid, such as maleic acid and a fumaric acid, may be used together 0.1 to 10weight%.
In order to increase the cohesive strength of the dry lithographic ink composition and improve the suitability of the dry lithographic ink, it is necessary to increase the weight average molecular weight of the rosin modified phenolic resin.

Next, the vegetable oil or fatty acid ester thereof used in the present invention will be described. First, vegetable oil is triglyceride in which at least one fatty acid is a fatty acid having at least one carbon-carbon unsaturated bond in triglyceride of glycerin and fatty acid. Real oil, linseed oil, eno oil, oil deer oil, olive oil, cacao oil, kapok oil, kayak oil, mustard oil, kyounin oil, kiri oil, kukui oil, walnut oil, poppy oil, sesame oil, safflower oil, radish seed oil , Soybean oil, Daifucho oil, Camellia oil, Corn oil, Rapeseed oil, Niger oil, Nuka oil, Palm oil, Castor oil, Sunflower oil, Grape seed oil, Gentia oil, Pine seed oil, Cottonseed oil, Palm oil, Peanut oil And dehydrated castor oil. Further preferred vegetable oils are vegetable oils having an iodine value of at least 100 or more (in parentheses indicate the oil and fat chemical product manual: the iodine value quoted from the Nikkan Kogyo Shimbun), Asa oil (149 or more), Linseed oil (over 170), Eno oil (over 192), deer oil (over 140), Kapok oil (85-102), kaya oil (over 130), mustard oil (over 101), Kyonin oil (97-109) , Kiri oil (145 or higher), kukui oil (136 or higher), walnut oil (143 or higher), poppy oil (131 or higher), sesame oil (104 or higher), safflower oil (130 or higher), radish seed oil (98 to 112) ), Soybean oil (117 or more), large fusose oil (101), corn oil (109 or more), rapeseed oil (97 to 107), niger oil (126 or more), nuka oil (92 to 1) 5), sunflower oil (125 or more), grape seed oil (124 or more), gentian oil (93 to 105), pine seed oil (146 or more), cottonseed oil (99 to 113), peanut oil (84 to 102), dehydrated Castor oil (147 or more) is preferably used, and 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 ester, ethyl oleate, propyl oleate, butyl oleate, allyl oleate, isoamyl oleate, heptyl oleate, 2-ethylhexyl oleate, methyl elaidate, ethyl elaidate, propyl elaidate, Allyl elaidate, butyl elaidate, isobutyl elaidate, tert-butyl elaidate, isoamyl elaidate, 2-ethylhexyl elaidate, methyl linoleate, ethyl linoleate, allyl linoleate, propyl linoleate, isopropyl linoleate , Butyl linoleate, isobutyl linoleate, tert-butyl linoleate, pentyl linoleate, hexyl linoleate, heptyl linoleate, 2-ethylhexyl linoleate, linolenic acid Cyl, ethyl linolenate, allyl linolenate, propyl linolenate, isopropyl linolenate, butyl linolenate, isobutyl linolenate, tert-butyl linolenate, pentyl linolenate, hexyl linolenate, heptyl linolenate, linolenic acid-2- Ethylhexyl, methyl arachidonic acid, ethyl arachidonic acid, allyl arachidonic acid, propyl arachidonic acid, isopropyl arachidonic acid, butyl arachidonic acid, isobutyl arachidonic acid, arachidonic acid-tert-butyl, pentyl arachidonic acid, hexyl arachidonic acid, heptyl arachidonic acid, arachidone 2-ethylhexyl acid, methyl eicosenoate, ethyl eicosenoate, allyl eicosenoate, propyl eicosenoate, isopropyl eicosenoate, butyl eicosenoate, Isobutyl senate, eicenoic acid-tert-butyl, eicosenic acid pentyl, eicosenoic acid hexyl, eicosenoic acid heptyl, eicosenoic acid-2-ethylhexyl, eicosapentaenoic acid methyl, eicosapentaenoic acid ethyl, eicosapentaenoic acid allyl, eicosapentaenoic acid propyl, 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 , Docosahexaenoic acid-tert-butyl, docosahexaenoate pentyl, docosahexaenoate hexyl, docosahexaenoate heptyl, docosahexaenoate-2-ethylhexyl, methyl ricinoleate, ethyl ricinoleate, allyl ricinoleate, propyl ricinoleate, isopropyl ricinoleate, butyl ricinoleate , Isobutyl ricinoleate, tert-butyl ricinoleate, pentyl ricinoleate, Lumpur hexyl, heptyl ricinoleate, and the like can be exemplified ricinoleic acid 2-ethylhexyl.

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

  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. These are used in soybean oil inks.

  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.

  Further, esterification reaction products 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 soybean 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, pentaerythritol, or residual hydroxyl groups of esterification products of soybean oil fatty acids and polyols such as glycerin, trimethylolpropane, pentaerythritol and trimethylolpropane 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 vegetable oil or fatty acid ester thereof is particularly used for the hybrid ink and the like.

Further, the varnish can be made into a gel varnish using a gelling agent. As the gelling agent, usually an aluminum complex compound can be mentioned. Cyclic aluminum compounds such as cyclic aluminum oxide octate (Algomer 800 manufactured by Kawaken Fine Chemical Co., Ltd.), etc., aluminum alcoholates such as aluminum ethylate, aluminum isopropylate (AIKEN manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum-sec-butylate (river ASPD manufactured by Ken Fine Chemical Co., Ltd.), aluminum isopropylate-mono-sec-butyrate (AMD manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum alkyl acetates such as aluminum di-iso-butoxide-methyl acetoacetate (Chelope-Al- manufactured by Hope Pharmaceutical Co., Ltd.) MB12), aluminum-di-iso-butoxide-ethyl acetoacetate (Chelope-Al-EB102 manufactured by Hope Pharmaceutical), aluminum Um-Tris (acetylacetonate) (ALCH-TR manufactured by Kawaken Fine Chemical Co., Ltd.), Aluminum-Tris (Atylacetoacetate) (Aluminum Chelate manufactured by Kawaken Fine Chemical Co., Ltd.), Liquid Olymp AOS (manufactured by Hope Pharmaceutical Co., Ltd.) Illustrated. 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. Further examples include organic titanates such as tetraisopropyl titanate, tetra n-butyl titanate, tetreoctyl titanate, titanium acetylacetonate, titanium octylene glycolate, titanium lactate, and titanium lactate ethyl ester. Furthermore, organic zirconium such as zirconium-tetrabutoxide, zirconium acetylacetone, zirconium acetylacetone, zirconium acetylacetone, acetylacetone zirconium butoxide, ethyl acetoacetate butoxide, and the like are exemplified. The preparation of the gel varnish is usually obtained by adding 0.1 to 3 parts by weight of a gelling agent and reacting in a temperature range of 100 to 200 ° C. for 30 minutes to 2 hours.

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

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

The printing ink of the present invention comprises a pigment, a resin varnish and / or its gel varnish, a fatty acid-modified monomer, a monomer having a radical polymerizable double bond, a radical polymerization inhibitor, a radical polymerizable initiator, Alternatively, the printing ink composition components such as a sensitizer and other additives are produced by using a kneader, a kneader such as a kneader, three rolls, an attritor, a sand mill, and a gate mixer, a mixing machine, and an adjusting machine.

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

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

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

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

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples. Parts indicate parts by weight.
Synthesis Example 1 of Fatty Acid-Modified Monomer
A separable four-necked flask is equipped with a temperature control regulator, a condenser, and a stirrer, charged with 144 parts of octylic acid, 813 parts of acrylic acid, 45 parts of paratoluenesulfonic acid, and 4.5 parts of hydroquinone, and heated in an air stream. The mixture was reacted at 120 ° C. for 5 hours to obtain a compound having an acid value of 507 (k = 0.51, n = 0.5). After cooling the reaction compound to 80 ° C., 272 parts of pentaerythritol (molecular weight 136) and 300 parts of toluene were added and reacted for 16 hours while refluxing and dehydrating at 100 to 115 ° C. Further, after completion of the reaction, the mixture was cooled to 40 ° C., 306 parts of a 20% aqueous sodium hydroxide solution was added, vigorously stirred for 30 minutes, and allowed to stand to remove the aqueous layer. Further, 300 parts of water was added, and the static water layer removal by stirring vigorously for 30 minutes was repeated twice. The solvent was removed at about 90 ° C. under a reduced pressure of 20 mmHg to obtain a fatty acid-modified monomer 1.

Synthesis example 2 of fatty acid-modified monomer
A separable four-necked flask is equipped with a temperature control regulator, a condenser, and a stirrer and charged with 200 parts of coconut oil fatty acid, 1033 parts of acrylic acid, 45 parts of paratoluenesulfonic acid, and 4.5 parts of hydroquinone, and the temperature is raised under an air stream. The mixture was reacted at 120 ° C. for 9.5 hours to obtain a compound having an acid value of 399 (k = 0.94, n = 0.8). After cooling the reaction compound, 272 parts of pentaerythritol (molecular weight 136) and 400 parts of toluene were added and reacted for 16 hours while refluxing and dehydrating at 100 to 115 ° C. After completion of the reaction, the reaction mixture was cooled to 40 ° C., 302 parts of 20% aqueous sodium hydroxide solution was added and stirred vigorously for 30 minutes, and allowed to stand to remove the aqueous layer. Further, 300 parts of water was added, and the static water layer removal by stirring vigorously for 30 minutes was repeated twice. The solvent was removed at about 90 ° C. under a reduced pressure of 20 mmHg to obtain fatty acid-modified monomer 2.

Fatty acid-modified monomer Example 3
A separable four-necked flask was equipped with a temperature control regulator, a condenser, and a stirrer, charged with 88 parts of butyric acid, 490 parts of acrylic acid, 24 parts of paratoluenesulfonic acid, and 3.3 parts of hydroquinone, and heated up under an air stream. Reaction was performed at 120 ° C. for 5 hours to obtain a compound having an acid value of 507 (k = 0.51, n = 0.5). After cooling the reaction compound to 40 ° C., 268 parts of trimethylolpropane (molecular weight 134) and 200 parts of toluene were charged and reacted for 16 hours while refluxing and dehydrating at 100 to 115 ° C. After completion of the reaction, the mixture was cooled to 40 ° C., 223 parts of a 20% aqueous sodium hydroxide solution was added, and the mixture was vigorously stirred for 30 minutes. After standing for 2 hours, the aqueous layer was removed. Further, 223 parts of water was added, and the mixture was vigorously stirred for 30 minutes, allowed to stand for 2 hours, and the aqueous layer was removed twice. The solvent was removed at about 90 ° C. under a reduced pressure of 20 mmHg to obtain fatty acid-modified monomer 3.

(Synthesis example of alkyd resin)
Example resin R1
A four-necked flask equipped with a stirrer, equipped with a water separation tube and equipped with a thermometer was charged with 68 parts of benzoic acid, 340 parts of disproportionated rosin, 278 parts of trimethylolpropane, and 50 parts of xylene. When the acid value was reduced to 5 or less by reacting at 4 ° C., cooled to 180 ° C., charged with 315 parts of phthalic anhydride, then gradually heated up and reacted at 230 ° C. for 10 hours, resulting in an acid value of 20. After removing the solvent under reduced pressure at the same temperature, the solution was pumped out. Resin R1 (weight average molecular weight 57,000 in terms of polystyrene by gel permeation chromatography measurement, softening point 95 ° C.) was obtained.

(Production example of resin varnish)
Example varnish V1
To make a resin varnish for printing ink, a stirrer, a water separation condenser tube, a thermometer four-necked flask, DOTTOTE DT170 (diallyl phthalate resin manufactured by Tohto Kasei Co., Ltd.), 30 parts of the fatty acid-modified monomer 1 69.9 parts and 0.1 part of hydroquinone were charged, dissolved in air at 100 ° C. for 30 minutes to 1 hour, sampled and measured for viscosity with a B-type viscometer at 150 Pa · s / 25 ° C. there were.
In the same manner, Table 1 shows Example varnishes V2 to V3.

Comparative Example Production Example of Varnish (V4) (Active Energy Ray Curing Varnish)
A four-necked flask with a stirrer, a water separation condenser, and a thermometer, 30 parts of Dap Tote DT170 (Dialylphthalate resin manufactured by Tohto Kasei Co., Ltd.), 69.9 parts of ditrimethylolpropane tetraacrylate, 0.1 part of hydroquinone Was dissolved in an air stream at 100 ° C. for 30 minutes to 1 hour. When the viscosity was measured with a cone plate viscometer, it was 152 Pa · s / 25 ° C. Similarly, Comparative Example Varnish V5 was prepared with the formulation shown in Table 1.

Production Example of Curable Ink (Ink 1) 18 parts of Lionol Blue FG7330 (Indigo Pigment manufactured by Toyo Ink Co., Ltd.) as an indigo pigment, 50 parts of Example Varnish V1, 23.9 parts of Example Fatty Acid Modified Monomer 1 , 4,4′-bis (diethylamino) benzophenone (EAB), 2.5 parts Irgacure 907 (initiator manufactured by Ciba Specialty Co., Ltd.), 0.1 part hydroquinone, -Manufactured in a conventional manner with Lumil.
Inks 2 to 3 were produced according to the formulation shown in Table 2 below. Inks 1 and 2 are examples of ultraviolet curable ink, and ink 3 is an example of electron beam curable ink. Furthermore, ink 2 is a hybrid type ink.

Comparative example UV curable ink (ink 4)
18 parts of Lionol Blue FG7330 (Indigo Pigment manufactured by Toyo Ink Co., Ltd.), 30 parts of varnish V4, 23.9 parts of ditrimethylolpropane tetraacrylate, 2.5 parts of EAB, 2.5 parts of Irgacure 907, hydroquinone 0.1 part was charged and prepared by a conventional method using a three-roll mill.

  In the same manner, Comparative UV curable ink 5 (hybrid type ink) was produced according to the formulation shown in Table 2.

Comparative Example Electron curable ink (ink 6)
18 parts of Lionol Blue FG7330 (Toyo Ink Manufacturing Co., Ltd. indigo pigment), 50 parts of varnish V5, 28.9 parts by weight of ditrimethylolpropane tetraacrylate, 3 parts of trimethylolpropane triacrylate and 0.1 part of hydroquinone are charged. It was prepared by a conventional method using a three-roll mill.

  Furthermore, Table 3 shows active energy ray-curable varnish formulations. Each raw material was charged and stirred at 60 ° C. for 30 minutes to adjust the viscosity to 2 to 4 mPa · S / 25 ° C.

The effects of the present invention will be described in terms of curability, friction resistance, and cost. (Examples 1-3, Comparative Examples 4-6)
-In case of UV irradiation-
Use an RI tester (simple printing machine manufactured by Akira Seisakusho Co., Ltd.) for maricoat paper (coated cardboard manufactured by Hokuetsu Paper Industries Co., Ltd.), color-print each ink with 0.3 cc of ink, and then irradiate with ultraviolet rays. After that, the curability and rub resistance were tested. For UV irradiation, an irradiation device UVC-2535 (three 120 W / cm meta-hara lamps) manufactured by USHIO was used.
-In the case of electron beam irradiation-
After applying the electron beam curable varnish under the same conditions as in the case of ultraviolet irradiation, the electron beam irradiation curability and friction resistance were immediately tested. For the electron beam irradiation, Iwasaki Electric Co., Ltd. ultra-low voltage electron beam irradiation apparatus EZ-V {acceleration voltage 50-70 KV, processing capacity 3000 KGy · m / min (at 70 KV) nitrogen-substituted atmosphere with oxygen concentration 500 ppm} was used. .
-In case of UV irradiation-
Immediately apply a wire bar # 3K-lock sprue (RKPRINT-COAT INSTRUMENTS Ltd) to Malicoat paper (Hokuetsu Paper Co., Ltd. coated cardboard), and then irradiate it with ultraviolet rays, and then irradiate it with ultraviolet rays to cure and resist friction. Was tested. For UV irradiation, an irradiation device UVC-2535 (3 lamps of 120 W / cm super high pressure mercury ozone uncut lamp) manufactured by USHIO Co., Ltd. was used.
-In the case of electron beam irradiation-
After applying the electron beam curable varnish under the same conditions as in the case of ultraviolet irradiation, the electron beam irradiation curability and friction resistance were immediately tested. For the electron beam irradiation, Iwasaki Electric Co., Ltd. ultra-low voltage electron beam irradiation apparatus EZ-V {acceleration voltage 50-70 KV, processing capacity 3000 KGy · m / min (at 70 KV) nitrogen-substituted atmosphere with oxygen concentration 500 ppm} was used. .

The above results are summarized in Table 4.
Curability: Displayed at a tack-free conveyor speed (m / m) in a dry touch test when the printed material was cured under the above conditions.
* Water width: Using Lithron 226 (offset printing machine manufactured by Comorie Corporation), printing on Mitsubishi special paper (Mitsubishi Paper Co., Ltd.) (article weight 90Kg / ream) at a printing speed of 10,000 sheets per hour. By changing the water dial that adjusts the original roller, the water width lower limit value that causes soiling and the water mark occurrence point that occurs when the ink is excessively emulsified is set as the water width upper limit value, and the wide width is good. . There are 0 to 10 water dials on the water source roller, 0 is a dial that does not emit water at all, 10 is an excessive dial, and usually 4 is a normal dial. First, the normal dial 4 is used for printing, and after the print density is stabilized, the water dial is gradually lowered, and after confirming the soiled dial, it is immediately changed to the normal dial 4 and then the water dial is gradually raised. A wider water width is judged to be better.

Table 5 below shows the costs of the example monomer and the comparative example monomer.
The cost indicates the cost in the general market at the time of filing this patent.

Claims (5)

By reaction of a fatty acid _{(C m H 2m ± 1 -COOH} ) and acrylic acid _{(CH 2 = CH-COOH)} , and (a1 + a2) molar multimeric mixtures of the following formula 1, 2 (A), Fatty acid-modified acrylic monomer (C) obtained by esterification reaction with b mol of polyol (B).
The multimeric mixture (A) is represented by the formula 1: (a1) CH ₂ ═CH—COO (CH ₂ CH ₂ COO) _k —H
{Wherein k represents 0 or an integer, and the average value k is 0.1 to 3. }
Formula _{2: (a2) C m H} 2m ± 1 -COO (CH 2 CH 2 COO) 2n -H
{In the formula, m represents an integer of 1 to 20, n represents 0 or an integer, and the average value n is 0.1 to 3. } And a mixture with
0.05 ≦ a2 / a1 ≦ 0.5
0.9 ≦ (a1 + a2) /bx≦1.5 Note: x satisfies the number of functional groups of the hydroxyl group of the polyol (B). The fatty acid-modified acrylic monomer (D) according to claim 1, wherein the polyol (B) is selected from pentaerythritol, trimethylolpropane, trimethylolethane, and glycerin. 1 to 90% by weight of the fatty acid-modified acrylic monomer (D) according to claim 1; 1 to 90% by weight of a (meth) acrylic monomer (E); 1 to 50% by weight of a softening point of 50 to 180 ° C. An active energy ray-curable composition comprising (F). The active energy ray-curable composition according to any one of claims 1 to 3, comprising 1 to 20% by weight of vegetable oil or a fatty acid ester thereof. A printed matter obtained by printing the active energy ray-curable composition according to claim 3 or 4.