JP2003055582A - Curable coating composition, curable printing ink, curable varnish and print thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable coating composition reducing fouling and improving printability such as emulsification suitability during printing, especially in offset printing using dampening water and having excellent adhesion to oily inks and plastic films even when used as an overcoat varnish in an active energy ray-curable printing ink. SOLUTION: This curable coating composition is characterized by compatibilizing an acrylic monomer or oligomer with an acrylic resin having 50-180 deg.C softening point and high lipophilicity. The acrylic resin contains an acrylic or a methacrylic esterified substance of a 5-60C cyclic alcohol as a constituent component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention comprises an acrylic monomer or oligomer and an acrylic resin having a softening point of 50 to 180.degree. The present invention relates to a curable coating composition such as a composition, a curable printing ink, a curable overcoat varnish, and a printed matter thereof.

[0002]

2. Description of the Related Art Conventionally, active energy ray-curable coating compositions have been extensively researched, and among them, practical application is progressing in the fields of printing inks, clear varnishes, paints and the like. Particularly, the active energy ray-curable printing ink is a non-reactive resin (inert resin) having a melting point of 50 ° C. or higher, represented by a diallyl phthalate resin, a radical polymerizable oligomer, a radical polymerizable monomer, and a radical polymerization initiator if necessary. It consists of a photosensitizer, a pigment, and various additives. As non-reactive resin (inert resin),
Ortho or isotype diallyl phthalate resins are widely used. Alkyd acrylates, polyester acrylates, epoxy acrylates, urethane-modified acrylates and the like are used as radically polymerizable oligomers. Bisphenol A alkylene oxide adduct diacrylate as a radically polymerizable monomer,
Ethylene glycol diacrylate, propylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane (tri or) tetraacrylate, dipentaerythritol (penta or) hexaacrylate, etc. are used. ing. As the radical polymerization initiator and photosensitizer, benzoin-based, (dialkyldiamino) arylketone-based, and xanthone-based compounds are used.

In recent years, there has been a trend toward higher printing speed in the printing industry, and in order to cope with this trend, active energy ray-curable printing inks having even better printability are required. The lipophilicity of the innerto resin and the reactive oligomer is insufficient, and in offset printing using a fountain solution, these active energy ray-curable printing ink compositions have stains during printing, printability such as emulsification suitability, and the like. Had insufficient adhesion to the plastic film. Further, the conventional active energy ray overcoat varnish also has insufficient adhesion to a plastic film or oil-based ink.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides an active energy ray-curable printing ink having improved printing suitability such as stains and emulsification suitability during printing particularly in offset printing using a fountain solution. A curable coating composition having excellent adhesion to oil-based inks and plastic films even when used.

[0005]

The present invention relates to a curable coating composition comprising an acrylic monomer or oligomer and a highly lipophilic acrylic resin having a softening point of 50 to 180 ° C. which are compatible with each other. .

Further, in the present invention, the acrylic resin is C5.
The present invention relates to the above curable coating composition containing a (meth) acrylic acid esterified product of a C60 cyclic alcohol as a constituent component.

The present invention further relates to the above curable coating composition wherein the C5 to C60 cyclic alcohol is a terpene alcohol.

The present invention further relates to the above curable coating composition further containing a radically polymerizable initiator.

The present invention further relates to the above curable coating composition containing a colorant.

The present invention further relates to a printing ink comprising the above curable coating composition.

The present invention further relates to a curable overcoat varnish comprising the above curable coating composition.

The present invention further relates to a printed matter obtained by printing or coating the above printing ink or curable overcoat varnish on a substrate.

[0013]

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

In the present invention, the acrylic resin having a softening point of 50 to 180 ° C. is a resin obtained by polymerizing an alkyl ester of (meth) acrylic acid or an aromatic vinyl compound such as styrene in combination. The acrylic resin of the present invention preferably has high lipophilicity in order to improve adhesion to a plastic film in offset printing. Also in the curable overcoat varnish, a resin system having high lipophilicity is desired to improve the adhesion to oil-based inks and plastic films.

The acrylic resin of the present invention uses an acrylic ester of an alcohol having a C1 or more, preferably a (meth) acrylic ester of an alcohol having a C4 or more in order to improve lipophilicity. However, among these alcohols, chain-structured alcohols often plasticize and have a softening point of 50 ° C. or lower, and when used for curable printing inks or curable overcoat varnishes, the general printing speed is 80 to 1
At a printing speed of 50 m / min, curability becomes insufficient.

In order to obtain an acrylic resin having a softening point of 50 to 180 ° C., a C5 to C60 cyclic compound in which the alcohol component of the (meth) acrylic ester of a monohydric alcohol has a ring composed of at least 5 or more carbon atoms. Alcohol is preferred.

In the present invention, the C5 to C60 cyclic alcohol (meth) acrylic ester is 0.1% in the acrylic resin.
The amount of the C5 to C60 cyclic alcohol (meth) acrylic ester is 50% by weight or more, and the acrylic resin has insufficient solubility with the (meth) acrylic monomer or oligomer.

Examples of the (meth) acrylic ester of a C5 to C60 cyclic alcohol include benzyl alcohol,
Ethylene oxide or propylene oxide of carboxylic acid,
Cresol ethylene oxide or propylene oxide, butylphenol ethylene oxide or propylene oxide, octylphenol ethylene oxide or propylene oxide, nonylphenol ethylene oxide or propylene oxide, dodecylphenol ethylene oxide or propylene oxide, alicyclic alcohols such as rosin alcohol (Avitol manufactured by Hercules). Examples thereof include (meth) acrylic acid esters such as tricyclodecane monomethylol. Further, (meth) acrylic esters such as ethylene glycol monorosin ester, trimethylolpropane or glycerin dirosin ester, and pentaerythritol trirosin ester are exemplified. Furthermore, borneol (bornyl alcohol), isoborneol (isobornyl alcohol), citronellol, pinocampheol, geraniol, fentyl alcohol, nerol, linalool, menthol, terpineol, carpeol, twill alcohol, farnesol, patchoulial (meta).
Acrylic ester call, nerolidol, carotol,
Examples thereof include (meth) acrylic acid esters of terpene alcohols such as casino lan lanseol, eudesmol, cedrol, guayol, quessoglycol, phytol, sclareol, manol, hinokiol, ferguinol and totarol.

Further, the acrylic resin of the present invention preferably contains 50 to 99% by weight of a (meth) acrylic ester of a monohydric alcohol such as methanol or ethanol in the acrylic resin, and further contains a C3 to C20 aliphatic monoester. A (meth) acrylic ester of a polyhydric alcohol may be used in combination with 0 to 50% by weight.

Examples of the (meth) acrylic ester of a C3 to C20 linear or branched aliphatic monohydric alcohol include propanol, (normal, iso, tertiary) butanol, (normal, iso, tertiary) hexanol,
Examples are (meth) acrylic acid esters such as (normal, iso, tertiary) octanol, 2-ethylhexyl alcohol, (normal, iso, tertiary) nonanol, decanol, dodecanol, hexadecanol, octadecanol, icosanol, allyl alcohol. It

Further, the acrylic resin of the present invention is C1 ~
A (meth) acrylic acid ester, which is a residual hydroxyl compound in the esterification reaction of a C20 fatty acid and a divalent or higher valent polyol, may be used in an amount of 0 to 50% by weight in the acrylic resin.

Examples of the (meth) acrylic acid ester of the residual hydroxyl group compound in the esterification reaction of a C1 to C20 fatty acid and a divalent or higher valent polyol include ethylene glycol monobutyl ester, propylene glycol monohexyl ester, glycerin and trimethylolpropane. Examples include (meth) acrylic esters of dioctylic acid.

The esterification reaction of the above alcohol with (meth) acrylic acid is a conventional method and is generally carried out as follows. A four-necked flask equipped with a stirrer, a thermometer, and a cooling separation tube was charged with the above alcohol compound, (meth) acrylic acid, and a polymerization inhibitor, and then blown with air, or a mixture of air and nitrogen or nitrogen was blown to obtain toluene, MIBK. , A solvent such as cyclohexane, and reacted at a temperature range of 80 to 120 ° C. for 5 to 20 hours to give an acid value of 20 or less, preferably 15
The reaction is continued until it becomes 10 or less,
Remove solvent under reduced pressure.

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

Examples of the polymerization inhibitor include alkylphenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p.
-Benzoquinone, nitrosobenzene, 2,5-di-tert
-Butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino-1,3-dimethylbutylidene) aniline oxide, Dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methylethylketoxime, cyclohexanone oxime and the like are used.

The acrylic resin of the present invention may be a polymer of the above (meth) acrylic acid ester and an aromatic vinyl compound.

As the aromatic vinyl compound, styrene,
Divinylbenzene, vinyltoluene, 1-vinylnaphthalene, 2-vinylnaphthalene, 9-vinylanthracene, 2-vinylphenanthrene, 3-vinylphenanthrene, acenaphthylene, phenyl vinyl ether, o-
Examples include cresyl vinyl ether, p-cresyl vinyl ether, α-naphthyl vinyl ether, β-naphthyl vinyl ether and the like. The reaction ratio of the (meth) acrylic acid ester and the aromatic vinyl compound is 50 to 100% by weight of the (meth) acrylic acid ester and the aromatic vinyl compound 0 to the total amount of the (meth) acrylic acid ester and the aromatic vinyl compound. It is 50% by weight.

The acrylic resin of the present invention can be obtained by thermally polymerizing the above monomer at 60 to 120 ° C., preferably 80 to 100 ° C. in the presence of a catalyst.

As the catalyst, benzoyl peroxide,
Cumene hydroperoxide, t-butyl hydroperoxide, isopropyl peroxycarbonate, di-t-
Tertiary butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate and other peroxide compounds, azobisisobityronitrile, azobis2,4
Azobis compounds such as dimethylvaleronitrile, tetramethylthiuram disulfide, alkali metals and oxygen or oxygen compounds, triethylboron or tributylboron and oxygen, diethylzinc and oxygen, Cr (CO) 6, Mo (CO)
There are metal carbonyls such as 6, W (CO) 6, Mn (CO) 6 and Ni (CO) 6.

The reaction solvent is solvent-free or, if necessary, n-hexane, cyclohexane, ethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethyl acetate, butyl acetate, MEK, MIBK, diisobutyl ketone, cyclohexanone, ethanol, isopropanol, butanol, etc. Is exemplified. The solvent is removed under reduced pressure after the reaction is completed.

The acrylic resin of the present invention has a weight average molecular weight (in terms of polystyrene) of 1,000 to 500,000, preferably 1 to 50,000 and a softening point of 50 to 180 ° C., particularly 80 to 120.
C is preferred.

The acrylic monomer of the present invention is 1
Alkyl as a functional monomer (carbon number is 1-18)
There are (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, Further, (meth) acrylates of alkylphenol ethylene oxide adducts such as benzyl (meth) acrylate, butylphenol, octylphenol or nonylphenol or dodecylphenol, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecane monomethylol (meth) acrylate. Etc. are illustrated. Further, as bifunctional monomers, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di ( Meta)
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 hydroxypivale Todi (meth) acrylate (commonly called Manda), hydroxypivalyl hydroxypivalate dicaprolactonate di (meth) acrylate,
1,6 hexanediol di (meth) acryle, 1,2-
Hexanediol di (meth) acrylate, 1,5-hexanediol di (meth) acrylate, 2,5-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol Di (meth) acrylate, 1,2-octanediol di (meth) acrylate di (meth) acrylate, 1,9-nonanediol di (meth) acrylate,
1,2-decanediol di (meth) acrylate, 1,
10-decanediol di (meth) acrylate, 1,2
-Decanediol di (meth) acrylate, 1,12-
Dodecanediol di (meth) acrylate, 1,2-dodecanediol di (meth) acrylate, 1,14-tetradecanediol di (meth) acrylate, 1,2-
Tetradecanediol di (meth) acrylate, 1,1
6-hexadecanediol di (meth) acrylate,
1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate
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-pentane Diol di (meth) acrylate, dimethylol octane di (meth) acrylate,
2-ethyl-1,3-hexanediol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2
-Ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, 1,2-hexanediol di (meth) acrylate, 1,5-hexane Diol di (meth) acrylate, 2,5-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,2-octanediol di (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,2-decanediol di (meth)
Acrylate, 1,10-decanediol di (meth) acrylate, 1,2-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 1,2-dodecanediol di (meth) acrylate, 1,14-tetradecanediol di (meth) acrylate, 1,2-tetradecanediol di (meth) acrylate, 1,16-hexadecanediol di (meth) acrylate, 1,2-hexadecanediol di (meth) acrylate, 2- Methyl-2,4-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, dimethyloloctanedi (meth) acrylate (manufactured by Mitsubishi Chemical Corporation), 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, tricyclode Candimethylol dicaprolactonate di (meth) acrylate, bisphenol A tetraethylene oxide adduct 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-added bisphenol F tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol A di (meth) acrylate, water-added bisphenol F di (meth) acrylate, bisphenol A tetraethylene oxide adduct dicaprolactonate di (meth) Examples thereof include acrylates and bisphenol F tetraethylene oxide adduct dicaprolactonate di (meth) acrylate. Glycerine tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolhexane tri (meth) acrylate as a trifunctional monomer , Trimethylol octane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and the like. Pentaerythritol tetra (meth) as a tetra- or higher functional monomer
Acrylate, pentaerythritol tetracaprolactonate tetra (meth) acrylate, diglycerin tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane tetracaprolactonate, tetra (meth) acrylate, ditrimethylolethane Tetra (meth) acrylate, ditrimethylolbutane tetra (meth) acrylate, ditrimethylolhexane tetra (meth) acrylate, ditrimethylol octane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth)
Examples thereof include acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol polyalkylene oxide hepta (meth) acrylate and the like.

Further, as the acrylic monomer of the present invention, there is an alkylene oxide adduct (meth) acrylate of an aliphatic alcohol compound. Alkylene oxide adduct of aliphatic alcohol compound (meth) acrylate Mono- or poly (1-20) alkylene (C2 to C20) oxide adduct of aliphatic alcohol compound as a monomer (e.g., ethylene oxide, propylene oxide, butylene as an alkylene oxide) Oxide, pentylene oxide, hexylene oxide, etc.) mono- or poly (1-10) (meth) acrylate. Alkylene oxide adduct (meth) acrylate having 2 to 20 carbon atoms as a monofunctional monomer, for example, methanol mono or poly (1 to 20) alkylene (C2 to C20)
Oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, ethanol mono- or poly (1-20) alkylene (C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, Propylene oxide, butylene oxide) (meth) acrylate, butanol mono- or poly (1-20) alkylene (C2 -C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, hexanol Mono or poly (1-
20) Alkylene (C2 to C20) oxide adducts (for example, as alkylene oxides, ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, octanol mono or poly (1 to 20)
Alkylene (C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, dodecanol mono or poly (1-20) alkylene (C2 to C20) oxide adduct (alkylene As the oxide, for example, ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate,
Stearyl mono or poly (1-20) alkylene (C
2 to C20) Oxide adduct (Alkylene oxide includes, for example, ethylene oxide and propylene oxide. Furthermore, poly (1 to 20) alkylene (C2 to C20) oxide adduct (alkylene oxide) of butylphenol, octylphenol, nonylphenol or dodecylphenol. Examples thereof include ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, etc. Further, as the bifunctional monomer, ethylene glycol mono or poly (1-2).
0) Alkylene (C2-C20) oxide adducts (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, diethylene glycol mono or poly (2
To 20) alkylene (C2 to C20) oxide adduct (eg alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, triethylene glycol poly (2 to 20) alkylene (C2 to C20) oxide addition (Eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, polyethylene glycol poly (2 to 20) alkylene (C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide and propylene oxide) , Butylene oxide) di (meth) acrylate, propylene glycol poly (2
To 20) alkylene (C2 to C20) oxide adduct (eg alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, dipropylene glycol poly (2 to 20) alkylene (C2 to C20) oxide addition Body (for example, as alkylene oxide, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, tripropylene glycol poly (2-20) alkylene (C2 to C20) oxide adduct (for example, as alkylene oxide, ethylene oxide, propylene) Oxide, butylene oxide) di (meth) acrylate, polypropylene glycol poly (2-20) alkylene (C2 -C20) oxide adduct (for example, alkylene oxide is Tylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, butylene glycol poly (2-
20) Alkylene (C2-C20) oxide adducts (as alkylene oxides, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth)
Acrylate, pentyl glycol poly (2-20) alkylene (C2-C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (methaneopentyl glycol poly (2-20) (for example, ethylene oxide , Propylene oxide, butylene oxide, etc.)
Adduct di (meth) acrylate, hydroxypivalyl hydroxypivalate poly (2-20) alkylene (C2
To C20) oxide adduct (for example, as alkylene oxide, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate (commonly called Manda), hydroxypivalyl hydroxypivalate dicaprolactonate poly (2-20) alkylene (C2) ~ C2
0) Oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,6 hexanediol poly (2-20) alkylene (C2-C20)
Oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) di (meth) acrylate, 1,6 hexanediol poly (2-20) alkylene oxide adduct (for example, ethylene oxide, propylene oxide,
Butylene oxide, etc.) di (meth) acrylate, 1,
2-hexanediol di (meth) acrylate, 1,5
-Hexanediol poly (2-20) alkylene (C2
To C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,5-
Hexanediol Poly (2-20) alkylene (C2-
C20) Oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,7-heptanediol poly (2-20) alkylene (C2-C2)
0) Oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,8-octanediol poly (2-20) alkylene (C2-C2)
0) Oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-octanediol poly (2-20) alkylene (C2-C2)
0) Oxide adduct (for example, as alkylene oxide, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate di (meth) acrylate, 1,9-nonanediol poly (2-20) alkylene (C2-C20) oxide Adducts (as alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-decanediol poly (2-20) alkylene (C2 to C20) oxide adducts (as alkylene oxides, for example Ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,10-decanediol poly (2-20) alkylene (C2 -C20) oxide adduct (for example, ethylene oxide as ethylene oxide Cide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-decanediol poly (2-20) alkylene (C2 -C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) Di (meth) acrylate,
1,12-dodecanediol poly (2-20) alkylene (C2-C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate,
1,2-dodecanediol mono or poly (1-20)
Alkylene (C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,14-tetradecanediol poly (2-2)
0) alkylene (C2 to C20) oxide adducts (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-tetradecanediol poly (2-
20) Alkylene (C2-C20) oxide adducts (as alkylene oxides, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth)
Acrylate, 1,16-hexadecanediol mono- or poly (2-20) alkylene (C2 -C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2- Hexadecanediol poly (2-20) alkylene (C2-C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2-methyl-2,4-
Pentanediol Poly (2-20) alkylene (C2-
C20) Oxide adduct (for example, as alkylene oxide, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 3-methyl-1,5-pentanediol poly (2-20) alkylene (C2-C20) oxide addition Body (for example, as alkylene oxide, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate,
2-Methyl-2-propyl-1,3-propanediol poly (2-20) alkylene (C2-C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide)
Di (meth) acrylate, 2,4-dimethyl-2,4-
Pentanediol Poly (2-20) alkylene (C2-
C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) di (meth) acrylate, 2,2-diethyl-1,3-propanediol mono or poly (2
To 20) alkylene (C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,2,4-trimethyl-1,
3-Pentanediol mono- or poly (2-20) alkylene (C2-C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, dimethylol octane poly (2-20) ) Alkylene (C2-C20) oxide adducts (as alkylene oxides, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2
-Ethyl-1,3-hexanediol poly (2-20)
Alkylene (C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol poly (2-20) alkylene ( C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide)
Di (meth) acrylate, 2-methyl-1,8-octanediol poly (2-20) alkylene (C2-C20)
Oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2-butyl-2-
Ethyl-1,3-propanediol poly (2-20) alkylene (C2 -C20) oxide adduct (eg alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,4-diethyl- 1,5-Pentanediol poly (2-20) alkylene (C2 -C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate is exemplified. Glycerin poly (2-20) alkylene (C2-C2) as trifunctional monomer
0) Oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolpropane poly (2-20) alkylene (C2-C2)
0) Oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolethane poly (2-20) alkylene (C2 to C20)
Oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolhexane poly (2-20) alkylene (C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide) , Propylene oxide, butylene oxide) tri (meth) acrylate, trimethylol octane poly (2-20) alkylene (C2 to C20) oxide adduct (for example, as alkylene oxide, ethylene oxide, propylene oxide, butylene oxide) tri (meth) Acrylate, trimethylol octane poly (3-20) alkylene (C2 -C20) oxide adduct (for example, ethylene oxide, propylene as alkylene oxide) Kisaido, butylene oxide) tri (meth) acrylate, pentaerythritol poly (2-20) alkylene (C2 to C20) oxide adduct (e.g. ethylene oxide as alkylene oxide-de, propylene oxide, butylene oxide)
Tri (meth) acrylate etc. are illustrated. Pentaerythritol poly (2-2
0) Alkylene (C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, diglycerin poly (2 to 20) alkylene (C2 to C20) oxide adduct ( As the alkylene oxide, for example, 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, Ditrimethylol propane poly (2-2
0) Alkylene (C2-C20) oxide adducts (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, ditrimethylolpropane poly (2
To 20) alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.)
Tetra (meth) acrylate, ditrimethylol propane tetracaprolactonate, tetra (meth) acrylate, ditrimethylol ethane poly (2-20) alkylene (C2-C20) oxide adduct (for example, ethylene oxide, propylene oxide as alkylene oxide) , Butylene oxide) tetra (meth) acrylate, ditrimethylolethane poly (2-20) alkylene oxide (eg ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth)
Acrylate, ditrimethylol butane poly (2-2
0) alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylolhexane poly (2-20) alkylene (C2 to C20) oxide adduct (for example, as alkylene oxide, ethylene oxide, propylene) Oxide, butylene oxide)
Tetra (meth) acrylate, ditrimethylol hexane poly (2-20) alkylene oxide (eg ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylol octane (2-20) alkylene (C2-C20) oxide Adducts (for example, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) tetra (meth) acrylate, ditrimethylol octane poly (4-200) alkylene oxide (for example, ethylene oxide, propylene oxide,
Butylene oxide, etc.) tetra (meth) acrylate,
Dipentaerythritol poly (5-20) alkylene (C2-C20) oxide adduct (eg alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) penta (meth) acrylate, dipentaerythritol poly (2-20) alkylene ( C2 to C20) Oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) hexa (meth) acrylate, propylene oxide, butylene oxide) hexa (meth) acrylate, dipentaerythritol hexacaprolactonate poly (2-20) Alkylene (C2-C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) hexyl (Meth) acrylate, tripentaerythritol poly (2-20) alkylene (C2 -C20) oxide adduct (eg alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) hepta (meth) acrylate, tripentaerythritol poly (2) To 20) alkylene (C2 to C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) octa (meth) acrylate, tripentaerythritol poly (2 to 20) alkylene (C2 to C20) oxide addition Body (for example, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) hexa (meth) acrylate, tripentaerythritol polyalkylene oxide Saidoheputa (meth) acrylate, tripentaerythritol poly (2-20) alkylene (C2 -C20)
Oxide adducts (for example, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) octa (meth) acrylate and the like are exemplified.

The acrylic oligomer of the present invention includes
Examples thereof include polyols, polybasic acids and esterified products of (meth) acrylic acid, and epoxy acrylate. As the above-mentioned polyol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc. are used, and as the polybasic acid, phthalic anhydride, isophthalic acid, (anhydrous) succinic acid, (anhydrous) maleic acid, adipic acid, sebacic acid, etc. are used. It The ester reaction of the polyol, polybasic acid and (meth) acrylic acid is carried out by a conventional method.

As the gelling agent used for gelling the varnish containing an acrylic resin in the present invention, an aluminum complex compound may be mentioned. Cyclic aluminum compounds such as cyclic aluminum oxide octate (Kawaken Fine Chemical Co., Ltd.). Algoma 800),
Cyclic aluminum oxide stearate (Algomer 1000S manufactured by Kawaken Fine Chemicals Co., Ltd.), aluminum ethylate as aluminum alcoholate, aluminum isopropylate (AIPD manufactured by Kawaken Fine Chemicals Co., Ltd.), aluminum-sec-butyrate (ASPD manufactured by Kawaken Fine Chemicals Co., Ltd.), Aluminum isopropylate-mono-sec-butyrate (AMD manufactured by Kawaken Fine Chemicals Co., Ltd.), aluminum alkyl acetates such as aluminum-di-n-butoxide-ethylacetoacetate (Chelope- manufactured by Hope Pharmaceutical Co., Ltd.
Al-EB2), aluminum-di-iso-butoxide-methylacetoacetate (Chem, manufactured by Hope Pharmaceutical Co., Ltd.
ope-Al-MB12), aluminum-di-iso
-Butoxide-ethylacetoacetate (Chelope-Al-EB102 manufactured by Hope Pharmaceuticals), aluminum-di-iso-butoxide-ethylacetoacetate (Chelope-Al-EB2 manufactured by Hope Pharmaceuticals), aluminum-di-iso-propoxide-ethylacetoacetate. (Chope-Al-E manufactured by Hope Pharmaceutical Co., Ltd.
P12, ALken manufactured by Kawaken Fine Chemicals Co., Ltd., aluminum-Tris (acetylacetonate) (ALCH-TR manufactured by Kawaken Fine Chemicals Co., Ltd.), aluminum-Tris (acetyl acetoacetate) (aluminum chelate-A manufactured by Kawaken Fine Chemicals Co., Ltd.), Aluminum-bis (ethylacetylacetonate) -monoacetylacetonate (Aluminum chelate D manufactured by Kawaken Fine Chemicals Co., Ltd.), aluminum chelate M (manufactured by Kawaken Fine Chemicals Co., Ltd.), aluminum chelate NB-15 (manufactured by Hope Pharmaceuticals Co., Ltd.), Kerop S (Hope Pharmaceuticals Co., Ltd.) Kelope ACS-2 (Hope Pharmaceuticals,
Examples of the liquid OILEP AOO (made by Hope Pharmaceutical Co., Ltd.) and liquid OILEP AOS (manufactured by Hope Pharmaceutical Co., Ltd.) Aluminum stearate as an aluminum soap (NOF CORPORATION)
And aluminum oleate, aluminum naphthonate, aluminum urate, aluminum acetylacetonate and the like. These gelling agents are used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of varnish. Other gelling agents include cyclic dipeptides, bisamides such as ethylene bis (12-hydroxyoctadecanoic acid) amide having the property of gelling an organic liquid, Al-Mg-hydroxycaprylate, Al
Examples thereof include powdery aluminum-magnesium compounds such as -Mg-hydroxymyristate, Al-Mg-hydroxypalmitate, and Al-Mg-hydroxybehenate. Furthermore, AIP, ASB, AIE-M, ASE-
M, OAO, OAO-EF, OAO-HT, Cyco-G
el, Ketalin, Ketalin-II, Ketalin-III, TRI
-HLP-49, P-95, KHD, ATC-30, O
ASMS, OAS / 607, ALAC, AO-L47
(Above, Chattem Chemicals, Inc). Further, organic titanates such as tetraisopropyl titanate, tetra n-butyl titanate, tetreoctyl titanate, titanium acetylacetonate, titanium octylene glycolate, titanium lactate and titanium lactate ethyl ester are exemplified. Furthermore, organic zirconium such as zirconium-tetrabutoxide, zirconium acetylacetone, zirconium acetylacetone, zirconium acetylacetone, acetylacetone zirconium butoxide, ethyl acetoacetate zirconium butoxide and the like are exemplified.

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

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

Next, the form of use as the printing ink composition in the present invention will be explained. The printing ink composition of the present invention is usually used in the form of a lithographic printing ink. Generally, pigment 10 to 30% by weight resin varnish or resin gel varnish 20 to 50% by weight monomer having a radical polymerizable double bond 20 to 70% by weight radical polymerization inhibitor 0.01 to 1% by weight radical polymerization initiation Used in a composition consisting of 0 to 15% by weight of an agent and / or a sensitizer and 0 to 10% by weight of other additives. Since the acrylic resin is solid at room temperature, it is used as a resin varnish prepared by dissolving it in an acrylic monomer or oligomer and adding a radical polymerization inhibitor. The viscosity of the resin varnish is such that it is easy to prepare a printing ink composition (100 to 300 Pa.s /
25 ° C.), the composition ratio is resin / acrylic monomer and oligomer / radical polymerization inhibitor = 20 to
50 parts by weight / 80 to 50 parts by weight / 0.01 to 1 part by weight are charged and dissolved at 80 to 120 ° C. in an air stream for 30 minutes to 1 hour. Further, to prepare a resin gel varnish, 0.1 to 3 parts by weight of a gelling agent is added to the above-mentioned dissolved resin varnish 1
It is obtained by reacting at 00 to 120 ° C. for 30 to 1 hour. At that time, if 0.1 to 5% by weight of a C2 to C50 chain polybasic acid having an acid residue obtained by esterification reaction of succinic acid, adipic acid, sebacic acid or chain polyol and chain polybasic acid is added. The gel ability increases.

Generally, lithographic printing inks can be used at room temperature to 10
A printing ink composition component such as a pigment, a resin varnish and / or a gel varnish thereof, an acrylic monomer or oligomer, a radical polymerization inhibitor, a radical polymerization initiator and / or a sensitizer, and other additives is added at 0 ° C. It is manufactured using a kneading machine such as a kneader, a triple roll, an attritor, a sand mill, and a gate mixer, a mixing and adjusting machine.

The pigment may be an inorganic pigment or an organic pigment. Inorganic pigments include yellow lead, zinc yellow, navy blue, barium sulfate, cadmium red, titanium oxide, zinc white, rouge, alumina white, calcium carbonate, ultramarine blue, carbon black, graphite, aluminum powder, red iron oxide, etc. Is a β-naphthol-based, β-oxynaphthoic acid-based, β-oxynaphthoic acid anilide-based, acetoacetic anilide-based, pyrazolone-based soluble azo pigments, β-naphthol-based, β-oxynaphthoic acid-based anilide-based, Acetoacetic acid anilide monoazo,
Insoluble azo pigments such as acetoacetic acid anilide disazo and pyrazolone, copper phthalocyanine blue, halogenated (chlorine or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, phthalocyanine pigments such as metal-free phthalocyanine, quinacridone, dioxazine , Polycyclic pigments such as slene (pyrantron, anthanthrone, indanthrone, anthrapyrimidine, flavantron, thioindigo, anthraquinone, perinone, perylene), isoindolinone, metal complex, quinophthalone, etc. Various publicly known pigments such as heterocyclic pigments can be used.

Further, as a polymerization inhibitor, (alkyl) phenol, hydroquinone, catechol, resorcin, p
-Methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1 picrylhydrazyl, phenothiazine, p-benzoquinone, nitrosobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyl disulfide , Picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3
Examples include -oxyanilino-1,3-dimethylbutylidene) aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methylethylketoxime, cyclohexanone oxime.

Further, other additives can be used in the printing ink, if necessary. For example,
Carnauba wax, wood wax, lanolin, as anti-friction agents, anti-blocking agents, slip agents, and anti-scratch agents
Examples thereof include natural waxes such as montan wax, paraffin wax, and microcrystalline wax, Fischer-Tropse wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, polyamide wax, and synthetic waxes such as silicone compounds.

The active energy ray-curable printing ink is usually applied to offset printing using dampening water, but also to waterless printing not using dampening water. In addition to color printing, it is also applied to yellow, red, indigo, black, and other color printing, as well as transparent overprint varnish (commonly called OP varnish) that is printed by a printing machine after printing them. Active energy ray curable printed materials include foam printed materials, various printed materials for books, various printed materials for packaging such as carton paper, various plastic printed materials, stickers, label printed materials, art printed materials, metal printed materials (art printed materials, beverage can printed materials, canned foods, etc.). Food print). Furthermore, the curable coating composition of the present invention is also applied to an active energy ray curable overcoat varnish which is coated with a roll coater.

Examples and comparative examples of the present invention will be described below. The invention is expressed in parts by weight. Example of polymer compound (polymer P1) Isoborneol (isobornyl alcohol) 15 in a four-necked flask equipped with a stirrer, water separation tube, and thermometer.
4 parts, 0.2 parts of hydroquinone, 20 parts of toluene, 86 parts of methacrylic acid, and 2 parts of P-toluenesulfonic acid are charged and reacted under air blowing at 90 to 115 ° C. until the acid value becomes 15 or less. Then, 12 parts of a 20% aqueous sodium hydroxide solution was charged and neutralized, then washed three times with 200 ml of water 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 80 parts was added under a nitrogen stream.
The temperature was raised to 0 ° C., and a solution in which 30 parts of the above-mentioned isoborneol methacrylic ester (isobornyl methacrylate), 70 parts of methyl methacrylate, and 3 parts of benzoyl peroxide were previously dissolved was added dropwise over 3 hours. Two hours after the completion of the dropping, 0.5 part of benzoyl peroxide was added and the reaction was continued for another two hours, and then the solvent was removed to obtain a polymer having a softening point of 100 ° C. and a weight average molecular weight of 12,000.
(Example polymer P1) The same procedure as shown in Table 1 is performed below. Incidentally, borneol acrylic ester (bornyl acrylate) is an equimolar reaction of borneol and acrylic acid, terpineol methacrylic ester is an equimolar reaction of terpineol and methacrylic acid, butyl methacrylate is butanol and methacrylic acid are equimolar, and butyl acrylate is butanol. Obtained by an equimolar reaction of acrylic acid and a reaction operation method similar to that of isoborneol methacrylic ester. Commercially available methyl methacrylate and methyl acrylate were used.

[0045]

[Table 1]

Production Example (Preparation of Resin Varnish)

[0047]

Varnish Example 1 To prepare a resin varnish for printing ink, a four-necked flask equipped with a stirrer, equipped with a water separation cooling tube, and equipped with a thermometer was used, and 30 parts of resin (Example Polymer P1) and ditrimethylolpropane tetraacrylate 69 were used. .9 parts, hydroquinone 0.1 parts were charged, dissolved in an air stream at 100 ° C. for 30 minutes to 1 hour, sampled, and the viscosity was measured with a B-type viscometer to find that it was 148 Pa · s / 25 ° C. It was (Example varnish V1). Example varnishes were similarly prepared in Tables 2 and 3 below.

[0048]

[Table 2]

[0049]

[Table 3]

In Table 3, Example V10 of Example Varnish.
Is a four-necked flask equipped with a stirrer, a water separation cooling tube, and a thermometer, 35 parts of resin (Example Polymer P1), 62.4 parts of trimethylolpropane tripropylene oxide adduct triacrylate, 0.1 part of hydroquinone, ALC
H (Kawaken Fine Chemicals Co., Ltd. gelling agent) 0.5
And adipic acid (2 parts) were heated and dissolved in an air stream at 110 ° C. for 1 hour, the viscosity was measured with a B-type viscometer, and a gel varnish of 148 Pa · s / 25 ° C. was obtained. . (Example varnish V10).

[0051]

[Comparative Example 1 of varnish] To prepare a resin varnish for printing ink, 30 parts of Dap Tote DT170 (Dialuruphthalate resin manufactured by Tohto Kasei Co., Ltd.) in a four-necked flask with a stirrer, a water separation cooling tube and a thermometer, 69.9 parts of ditrimethylolpropane tetraacrylate and 0.1 part of hydroquinone were charged, and the mixture was heated at 100 ° C. for 30 minutes to 1 under an air stream.
It was found to be 152 Pa · s / 25 ° C. when it was dissolved in time, sampled and the viscosity was measured with a B-type viscometer.
(Comparative example varnish V1). Comparative example varnishes were similarly prepared in Table 4 below.

[0052]

[Table 4]

In Table 4, Comparative Example V6 of Comparative Varnish is a four-necked flask equipped with a stirrer, a water separation cooling tube, and a thermometer, and Daptoto DT170 (Dialuruphthalate resin manufactured by Tohto Kasei Co., Ltd.) 27. 4 parts, ditrimethylolpropane tetraacrylate 70 parts, hydroquinone 0.
1 part, ALCH (Kawaken Fine Chemicals Co., Ltd. gelling agent) 0.5 part, and adipic acid 2 parts were charged, heated and dissolved at 110 ° C for 1 hour under air flow, sampled, and viscosity was measured with a B-type viscometer. Was measured to be 150 Pa · s / 25
A gel varnish at ℃ was obtained. (Comparative example varnish V6).

Production example of printing ink

[0055]

Example Red 1 Carmine 6B as a red pigment (Red pigment manufactured by Toyo Ink Mfg. Co., Ltd.) 18 parts Example Varnish V125
Part, ditrimethylolpropane tetraacrylate 3
1.9 parts, dipentaerythritol hexaacrylate 20 parts, EAB (4,4'-bis (diethylamino) benzophenone 2.5 parts, Irgacure 907 (Ciba Specialty Chemicals Initiator) 2.5 parts, hydroquinone 0. 1 part was prepared and prepared by a conventional method using a triple roll mill (Example Beni 1).
Prepared at 8/25 ° C.

An ink was prepared in the same manner below. Table 5, Table 6 and Table 7 show Example Inks and Comparative Inks of printing ink formulations and properties.

[0057]

[Table 5]

[0058]

[Table 6]

[0059]

[Table 7]

Next, the active energy ray overcoat varnish will be described.

15 parts of resin (Example Polymer P1) was placed in a four-necked flask equipped with a stirrer, a water separation cooling tube, and a thermometer.
Hydroquinone (0.1 part) and trimethylolpropane triacrylate (24 parts) are charged and heated and dissolved at 100 ° C. in an air stream. Then, at 60 ° C., 30 parts of bisphenol A tetraethylene oxide adduct diacrylate, 23.9 parts of tripropylene glycol diacrylate and 0.1 part of hydroquinone were charged, and 3 parts of Irgacure 184 (initiator manufactured by Ciba Special Chemicals), O − Benzoylbenzoic acid methyl ester 2 parts, triethanolamine 2
When 30 parts to 1 hour were charged at 60 ° C. under an air stream charged and sampled and the viscosity was measured with a B-type viscometer, it was 380 mPa · s / 25 ° C. (Example varnish NV1).

Similarly, as shown in Table 8, the varnishes of the examples NV2 to NV2
NV4 was produced.

[0063]

[Table 8]

Ink test method * Tack value: Incometer 400 RPM, room temperature 25
℃, roll temperature 30 ℃, value after 1 minute with standard ink amount.

* Flow value: 25 ° C. with a standard parallel plate viscometer,
Flow radius value of ink after 1 minute (millimeters) * Water width: Lithrone 226 (offset printing machine manufactured by Komori Corporation) to Mitsubishi special art paper manufactured by Mitsubishi Paper Mills (weight of 90 kg / ream) 1000 per hour
By printing at the printing speed of 0 sheets and changing the water dial that adjusts the water source roller, the water width lower limit value causing scumming and the water mark generation point caused by excessive emulsification of ink are set to the water width upper limit. The value is set, and the wider the width, the better. There are 0 to 10 water dials on the water roller,
0 is a dial that does not emit water at all, 10 is an excessive dial, and normally 4 is a normal dial. First, print with the normal dial 4, and after the print density stabilizes, gradually lower the water dial and check the background stain dial, then immediately change to the normal dial 4 and gradually raise the water dial.

* Stain recovery: In the above water width test, immediately after the occurrence of background stain, the water dial is set to 4, and the number of sheets where the background stain disappears is made smaller.

* Curability test: After printing with Lithrone 226, for irradiation with ultraviolet rays, an irradiation device UVC-2535 manufactured by USHIO Co., Ltd. (3 lamps of 120 W / cm ultra-high pressure meta-hala lamp, conveyor speed 100 m / min) was used. When the printed materials of the ink compositions shown in Tables 5 to 7 were cured, the printed materials of the ink compositions of Examples and Comparative Examples were similarly cured. Regarding electron beam irradiation, the above printed matter of the ink composition of Comparative Example 6 in Table 6 Example 10 and Table 7 was taken out after printing, and a low energy electron beam irradiation device (pressurization voltage 175 KV, oxygen Concentration 500ppm
When exposed to 30 KGy of nitrogen, the printed matter of the ink compositions of Comparative Examples and Examples was similarly cured. Further, the active energy ray varnishes in Table 8 were also coated with a varnish-dedicated coating machine installed on the rear body of the printing machine, and were cured by irradiation with the ultraviolet rays and electron beams.

* Adhesion: Directly on the PP film or RI
0.3CC with a tester (simple printer manufactured by Akira Seisakusho Co., Ltd.)
After printing the inks of Example 1, Comparative Example 1, Example 10, and Comparative Example 5 or CK Win Echo Indigo (Toyo Ink Mfg. Co., Ltd. oil-making carton ink) on the above ink swell, the varnish in Table 8 was wetted. Coated NV1 (base: no ink or Example 1 ink or CK win echo indigo), NV3
(Substrate: no ink or Comparative Example 1 ink or CK wincho indigo) is UV irradiation (UV illumination), NV2 (Substrate: no ink or Example 10 ink or CK wincho indigo), NV4 (Substrate: no ink or comparison) The ink of Example 5 or CK winchoindigo) was irradiated with an electron beam (EB irradiation), and after 24 hours, a cellophane tape peeling test was performed.

[0069]

INDUSTRIAL APPLICABILITY The present invention uses a printing ink containing a highly lipophilic acrylic resin having a softening point of 50 to 180 ° C. or a curable overcoat varnish, and particularly in offset printing using a fountain solution. Staining during printing, printability such as emulsification suitability, adhesion to plastic film, curable overcoat varnish on oil-based ink, curable coating composition aiming to improve adhesion to plastic film, and printed matter thereof Is.

Continued front page    F-term (reference) 4J038 CG142 CH032 CH042 CH052                       CH062 CH072 CH082 CJ022                       FA111 FA231 FA251 JA29                       JA32 JA55 JB14 JC02 JC18                       JC38 KA03 KA08 MA13 NA07                       NA12 NA17 PA17 PB14 PC08                       PC10                 4J039 AD09 AD21 BA02 BA06 BA13                       BA16 BA18 BA23 BC03 BC16                       BC39 BC59 BC60 BE01 BE12                       BE23 BE26 CA02 EA04 EA43                       FA02 GA01 GA02 GA25

Claims (8)

[Claims] 1. A curable coating composition comprising an acrylic monomer or oligomer and an acrylic resin having a softening point of 50 to 180 ° C. which are compatible with each other. 2. The curable coating composition according to claim 1, wherein the acrylic resin contains a (meth) acrylic acid ester of a C5 to C60 cyclic alcohol as a constituent component. 3. The curable coating composition according to claim 2, wherein the C5 to C60 cyclic alcohol is a terpene alcohol. 4. The curable coating composition according to claim 1, which contains a radically polymerizable initiator. 5. The curable coating composition according to claim 1, which contains a colorant. 6. A curable printing ink comprising the curable coating composition according to claim 5. 7. A curable overcoat varnish comprising the curable coating composition according to claim 1. 8. A printed matter obtained by printing or coating the curable printing ink or curable overcoat varnish according to claim 6 or 7 on a substrate.