Active energy ray curing overprint varnish, and printed materials using it

Abstract

The objective is to provide an active energy ray curable overprint varnish that offers excellent misting properties and can provide a coating layer with higher gloss. [Solution] The reaction components include at least an acid-modified rosin, a monobasic acid having a cyclic structure, and a polyol having three or more hydroxyl groups in one molecule, and a polyester with an acid value of more than 10 mg KOH / g, A photopolymerization initiator, a (meth)acrylic monomer, An active energy ray curing overprint varnish and printed material characterized by containing 3 to 15% by mass of at least one extender pigment selected from the group consisting of calcium carbonate, silica, and magnesium carbonate, relative to the non-volatile components of the varnish.

Description

[Technical Field]

[0001] This invention relates to an active energy ray curable overprint varnish and a printed material using the same. [Background technology]

[0002] Overprint varnish (sometimes called overcoat varnish or OP varnish) is used after printing to improve the gloss of printed materials and protect the surface. Specifically, a colorless, transparent overprint varnish is printed after each color of printing ink has been applied. Overprint varnishes include solvent-type varnishes that contain organic solvents and form a varnish film upon drying, as well as active energy ray-curable overprint varnishes. (See, for example, Patent Documents 1 and 2.)

[0003] Active energy ray curable overprint varnishes harden instantly, forming a highly glossy film, and are widely used for printed materials such as magazine covers, picture books, posters, and calendars, as well as paper containers such as cosmetic cases. In recent years, even higher gloss levels have been required than before. Patent documents 1 and 2 disclose overprint varnishes that use rosin-modified resins and have high gloss. However, the overprint varnishes described in patent documents 1 and 2 sometimes experience misting, where ink is scattered in a mist-like manner from the printing press during printing, which can adversely affect gloss.

[0004] On the other hand, as a binder resin for active energy ray curable inks for lithographic offset printing with excellent misting properties, polyesters are known that contain at least acid-modified rosin, a monobasic acid having a cyclic structure, and a polyol having three or more hydroxyl groups in one molecule as reactants, and have an acid value of more than 10 mgKOH / g. (See, for example, Patent Document 3). [Prior art documents] [Patent Documents]

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] The problem to be solved by the present invention is to provide an active energy ray-curable overprint varnish that is excellent in mixing properties and can provide a coating layer having higher glossiness.

Means for Solving the Problems

[0007] As a result of intensive studies, the present inventors have found that an active energy ray-curable overprint varnish containing at least an acid-modified rosin, a monobasic acid having a cyclic structure, and a polyol having three or more hydroxyl groups in one molecule as reaction components, a polyester having an acid value of more than 10 mgKOH / g, and at least one extender pigment selected from the group consisting of calcium carbonate, silica, and magnesium carbonate solves the above problems.

[0008] That is, the present invention provides an active energy ray-curable overprint varnish containing at least an acid-modified rosin, a monobasic acid having a cyclic structure, and a polyol having three or more hydroxyl groups in one molecule as reaction components, a polyester having an acid value of more than 10 mgKOH / g, a photoinitiator, a (meth)acrylic monomer, and at least one extender pigment selected from the group consisting of calcium carbonate, silica, and magnesium carbonate in an amount of 3% to 15% by mass based on the non-volatile components of the varnish.

[0009] The present invention also provides the active energy ray curable overprint varnish described above, wherein the monobasic acid having a cyclic structure in the polyester is one or more selected from benzoic acid, phenylacetic acid, cinnamic acid, mandelic acid, salicylic acid, atrolactinic acid, anisic acid, toluic acid, ethylbenzoic acid, isopropylbenzoic acid, naphthoic acid, methylnaphthoic acid, anthronic acid, adamantic acid, hexahydrobenzoic acid, tetrahydrobenzoic acid, gum rosin, wood rosin, tall oil rosin, and hydrogenated rosin, and the reaction component does not contain any dibasic acids other than the acid-modified rosin.

[0010] The present invention also provides the overprint varnish described above, which contains the polyester in an amount of 6% to 30% by mass relative to the non-volatile components of the varnish, and the content of the resin containing the polyester is 35% by mass or less.

[0011] The present invention also provides the active energy ray curable overprint varnish described above, which contains a hydroxyacetophenone compound and / or an acylphosphine oxide compound as the photopolymerization initiator.

[0012] The present invention also provides the active energy ray curable overprint varnish described above, which contains the (meth)acrylic monomer in an amount of 20% to 50% by mass relative to the non-volatile components of the varnish.

[0013] The present invention also provides the above-described active energy ray curable overprint varnish containing an olefin-based wax and / or a silicone-based additive.

[0014] Furthermore, the present invention provides printed materials using the active energy ray curable overprint varnish described above. [Effects of the Invention]

[0015] The present invention provides an active energy ray curable overprint varnish that offers excellent misting properties and a coating layer with higher gloss. [Modes for carrying out the invention]

[0016] The following describes one embodiment of the present invention. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications without impairing the effects of the present invention. The compounds described herein may be derived from fossil resources or from biological resources (biomass).

[0017] (Definition of terms) In this specification, "~" means a value greater than or equal to the value before the "~" notation, and a value less than or equal to the value after the "~" notation.

[0018] [Binder resin] The binder resin used in this invention must be a polyester in which at least one of the reactants is an acid-modified rosin, a monobasic acid having a cyclic structure, and a polyol having three or more hydroxyl groups in one molecule. The binder resin used in this invention has a short-chain, highly branched structure to ensure the elasticity of the resin itself, and also incorporates a rosin skeleton and has an acid value of over 10 mg KOH / g to achieve excellent fluidity.

[0019] In this invention, "reactive components" refers to the components that make up polyester, and does not include solvents, catalysts, etc., that do not constitute polyester. The reactive components of the binder resin used in this invention will be described below.

[0020] Rosin is a naturally derived ingredient containing monocarboxylic acids having carbon-carbon unsaturated double bonds and fused rings, such as abietic acid, neoabietic acid, parastric acid, levopimal acid, pima acid, and isopimal acid. The acid-modified rosin, which is a reactive component, is obtained by reacting one or more of the aforementioned monocarboxylic acids, or rosin itself, with an α,β-unsaturated carboxylic acid (Diels-Alder addition reaction).

[0021] Rosin includes natural rosin such as gum rosin, wood rosin, and tall oil rosin; and stabilized rosin such as hydrogenated rosin and disproportionated rosin; however, natural rosin such as gum rosin, wood rosin, and tall oil rosin is preferred. Furthermore, the rosin used may be a single type or two or more types may be used in combination.

[0022] Acid-modified rosin improves the stability of the binder resin by reducing the number of carbon-carbon unsaturated double bonds in the rosin through reaction with α,β-unsaturated carboxylic acids. In addition, the polybasicization of monobasic rosin by α,β-unsaturated carboxylic acids improves the crosslinking density of the binder resin, thereby increasing its elastic modulus.

[0023] Examples of α,β-unsaturated carboxylic acids that denature rosin include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, isocrotonic acid, cinnamic acid, and 2,4-hexadienonic acid. The α,β-unsaturated carboxylic acid may be a derivative such as an acid anhydride. Furthermore, the α,β-unsaturated carboxylic acid used may be a single type or two or more types may be used in combination.

[0024] When reacting rosin with an α,β-unsaturated carboxylic acid to produce acid-modified rosin, it is advisable to react 0.5 to 2.0 moles of α,β-unsaturated carboxylic acid with 1 mole of rosin.

[0025] Acid-modified rosin preferably contains maleopimar acid. This maleopimar acid is an acid produced by the reaction of levopimar acid and maleic acid contained in rosin, and may be included as a main component (50% by mass or more) in maleic acid-modified rosin, for example, obtained by reacting natural rosin with maleic acid. In the case of stabilized rosins such as hydrogenated rosin and disproportionated rosin, the amount of levopimar acid, which has a carbon-carbon unsaturated double bond, is reduced, and even when reacted with maleic acid, maleopimar acid does not become the main component.

[0026] The proportion of acid-modified rosin in the reaction components is, for example, in the range of 5% to 90% by mass, preferably in the range of 10% to 80% by mass, more preferably in the range of 20% to 70% by mass, and even more preferably in the range of 30% to 60% by mass, relative to the total amount of reaction components.

[0027] The "cyclic structure" in a monobasic acid having a cyclic structure may be either an aromatic ring or an aliphatic ring, and may also be a heterocycle further containing heteroatoms (boron, nitrogen, sulfur, oxygen, or phosphorus) in its structure.

[0028] Specific examples of monobasic acids having a cyclic structure include benzoic acid, phenylacetic acid, cinnamic acid, mandelic acid, salicylic acid, atrolactinic acid, anisic acid, toluic acid, ethylbenzoic acid, isopropylbenzoic acid, naphthoic acid, methylnaphthoic acid, anthronic acid, adamantic acid, hexahydrobenzoic acid, tetrahydrobenzoic acid, gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, and disproportionated rosin. The monobasic acid having the cyclic structure may be a derivative such as an ester. Furthermore, the monobasic acid having the cyclic structure may be used alone or in combination of two or more types.

[0029] The proportion of monobasic acids having a cyclic structure in the reaction components is, for example, in the range of 5% to 60% by mass, preferably in the range of 5% to 50% by mass, more preferably in the range of 10% to 45% by mass, and even more preferably in the range of 15% to 40% by mass, relative to the total amount of reaction components.

[0030] Specific examples of polyols having three or more hydroxyl groups in a single molecule (hereinafter sometimes simply referred to as "polyols") include trihydric alcohols such as glycerin, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2,3,4-pentanetriol, and 1,2,5-hexanetriol; tetrahydric alcohols such as pentaerythritol; and pentahydric or higher alcohols such as dipentaerythritol, glucose, sucrose, and sorbitol. The polyol may be a derivative such as an ester. Furthermore, the polyol used may be a single type or two or more types may be used in combination.

[0031] The proportion of polyol in the reaction components is, for example, in the range of 5% to 50% by mass, preferably in the range of 5% to 40% by mass, more preferably in the range of 5% to 30% by mass, and even more preferably in the range of 5% to 25% by mass, relative to the total amount of reaction components.

[0032] The reactive components of the binder resin used in the present invention may further contain a dialkylene glycol having 2 to 6 carbon atoms. Dialkylene glycols, which are the reactive components and have 2 to 6 carbon atoms, are diols having a structure in which two alkylene chains are linked by an ether bond (-O-). Specific examples include diethylene glycol and dipropylene glycol. The aforementioned dialkylene glycol may be a derivative such as an ester. Furthermore, the dialkylene glycol used may be a single type or two or more types may be used in combination.

[0033] When using a dialkylene glycol having 2 to 6 carbon atoms as a reaction component, the proportion of the dialkylene glycol having 2 to 6 carbon atoms is, for example, in the range of 5% to 30% by mass, preferably in the range of 10% to 20% by mass, relative to the total amount of reaction components.

[0034] The binder resin used in the present invention may be any polyester comprising at least acid-modified rosin, a monobasic acid having a cyclic structure, a polyol, and any dialkylene glycol as reaction components, wherein the total proportion of acid-modified rosin, a monobasic acid having a cyclic structure, a polyol, and any dialkylene glycol in the reaction components is, for example, 90% by mass or more, 95% by mass or more, or 100% by mass.

[0035] The binder resin used in the present invention is preferably a polyester in which acid-modified rosin, a monobasic acid having a cyclic structure, and a polyol are reactants, or a polyester in which acid-modified rosin, a monobasic acid having a cyclic structure, a polyol, and a dialkylene glycol having 2 to 6 carbon atoms are reactants.

[0036] The reactive components of the binder resin used in the present invention may include other components besides acid-modified rosin, monobasic acids having a cyclic structure, polyols, and dialkylene glycols having 2 to 6 carbon atoms, as long as they do not impair the effects of the present invention. Examples of such other components include aliphatic diols other than dialkylene glycols having 2 to 6 carbon atoms, dibasic acids containing α,β-unsaturated carboxylic acids, hydroxyl (meth)acrylate compounds (such as HEMA), monobasic acids other than monobasic acids having a cyclic structure, and can be used in a range of 0% to 10% by mass of the total amount of reactive components.

[0037] In order to obtain a short-chain, multi-branched structure, the binder resin used in this invention preferably does not contain dibasic acids other than acid-modified rosin as a reaction component, and more preferably does not contain aliphatic dicarboxylic acids as a reaction component.

[0038] The binder resin used in this invention has an acid value greater than 10 mgKOH / g. By having an acid value greater than 10 mgKOH / g, the binder resin does not gel during manufacturing, and the fluidity of the resulting ink can be ensured. More preferably, it is greater than 25 mgKOH / g, and more preferably 26 mgKOH / g or more. There is no particular upper limit to the acid value of the binder resin used in this invention, but for example, it is 60 mgKOH / g. The acid value of the binder resin used in this invention is determined by the method described in the examples.

[0039] The hydroxyl value of the polyester binder resin used in the present invention is preferably in the range of 1 mg KOH / g to 200 mg KOH / g, more preferably in the range of 20 mg KOH / g to 160 mg KOH / g, and even more preferably in the range of 40 mg KOH / g to 130 mg KOH / g. The hydroxyl value of the aforementioned polyester is determined by the method described in the examples.

[0040] The weight-average molecular weight of the polyester binder resin used in the present invention is preferably in the range of 3,000 to 400,000, more preferably in the range of 5,000 to 350,000, and even more preferably in the range of 8,000 to 300,000. The weight-average molecular weight is a value converted to polystyrene based on gel permeation chromatography (GPC) measurement, and is measured by the method described in the examples.

[0041] The properties of the polyester binder resin used in this invention vary depending on its molecular weight and composition, but it is usually a solid at room temperature.

[0042] The binder resin used in the present invention may be any polyester having at least acid-modified rosin, a monobasic acid having a cyclic structure, and a polyol as reactants, and for example, two or more polyesters with different structures may be used.

[0043] The polyester binder resin used in this invention can be produced by reacting, for example, acid-modified rosin, a monobasic acid having a cyclic structure, a polyol, and any dialkylene glycol having 2 to 6 carbon atoms all at once, with the amounts of hydroxyl groups and carboxyl groups in the reactants being equal, or with the amount of hydroxyl groups slightly in excess of the carboxyl groups.

[0044] In the production of polyester, the reaction of the reaction components may be carried out in the presence of an esterification catalyst as needed, for example, in a temperature range of 170°C to 250°C for 10 to 25 hours. Furthermore, the temperature, time, and other conditions for the esterification reaction are not particularly limited and may be set as appropriate.

[0045] Examples of the esterification catalysts include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; zinc-based catalysts such as zinc acetate; tin-based catalysts such as tin octoate and dibutyltin oxide; and organic sulfonic acid-based catalysts such as p-toluenesulfonic acid.

[0046] The amount of esterification catalyst used can be set as appropriate, but it is usually used in the range of 0.0001 parts by mass to 0.1 parts by mass per 100 parts by mass of the total amount of reaction components.

[0047] The polyester is preferably present in an amount of 6.0% to 30.0% by mass relative to the non-volatile component of the overprint varnish of the present invention, and more preferably in an amount of 7.5% to 27.0% by mass. Within this range, gloss is particularly excellent. Furthermore, the content of the resin containing the polyester is preferably 35% by mass or less relative to the non-volatile components of the overprint varnish of the present invention, more preferably 8.0% to 35.0% by mass, and even more preferably 8.4% to 30.0% by mass. Within this range, gloss is particularly excellent.

[0048] In the overprint varnish of the present invention, in addition to the polyester, known binder resins may be used in combination, to the extent that they do not impair the effects of the present invention. Examples include diallyl phthalate resin, epoxy resin, epoxy ester resin, polyurethane resin, polyester resin, petroleum resin, rosin ester resin, poly(meth)acrylic acid ester, cellulose derivative, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, butadiene-acrylonitrile copolymer, and the like. These binder resins may be used alone or in combination of one or more. The resin used in combination is preferably a diallyl phthalate resin. These binder resins other than polyester are preferably used in combination in an amount ranging from 2% to 30% by mass relative to the non-volatile components of the overprint varnish of the present invention.

[0049] (Extender pigments) The present invention is characterized by the use of at least one extender pigment (hereinafter sometimes referred to as extender pigment A) selected from the group consisting of calcium carbonate, silica, and magnesium carbonate. By using the polyester with calcium carbonate, silica, or magnesium carbonate, an overprint varnish with an excellent balance of gloss and misting properties can be obtained. In the present invention, extender pigment A is preferably present in an amount of 3% to 15% by mass relative to the non-volatile components of the overprint varnish of the present invention, and more preferably in an amount of 4% to 12% by mass. Within this range, the misting properties are particularly excellent.

[0050] The active energy ray-curable overprint varnish of the present invention contains a photopolymerization initiator and an active energy ray-curable monomer. Known monomers can be used for both of these.

[0051] (Activated energy ray curable monomer)

[0052] The ink composition of the present invention contains an active energy ray curable monomer. Active energy ray curable monomers function as diluents and are, for example, monomers and / or oligomers having carbon-carbon unsaturated double bonds, and known monomers and / or oligomers can be used in active energy ray curable inks.

[0053] The active energy ray curable monomer is preferably a monofunctional (meth)acrylate and / or a polyfunctional (meth)acrylate.

[0054] Specific examples of monofunctional (meth)acrylates include ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, isoamyl (meth)acrylate, isodecyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol ( Examples include meth)acrylate, nonylphenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, nonylphenoxyethyl tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate.

[0055] Among polyfunctional (meth)acrylates, specific examples of difunctional (meth)acrylates include alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; polyalkylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate; 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dicyclopentadiene di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, and dicyclo Examples include clopentanyl di(meth)acrylate; pentaerythritol di(meth)acrylate, bisphenol A ethylene oxide (EO)-added diacrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate or alkylene oxide-modified derivatives thereof, divinylbenzene, butanediol-1,4-divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether, triethylene glycol divinyl ether, phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer, phenylglycidyl ether acrylate toluene diisocyanate urethane prepolymer, and the like.

[0056] Among polyfunctional (meth)acrylates, specific examples of (meth)acrylates with three or more functions include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(acryloxyethyl) isocyanurate, or their alkylene oxide modified forms, tri(meth)acrylates of isocyanuric acid alkylene oxide modified forms, etc.; ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate or Examples include tetrafunctional (meth)acrylates such as these alkylene oxide modified products; pentafunctional (meth)acrylates such as dipentaerythritol penta(meth)acrylate or alkylene oxide modified products thereof; dipentaerythritol hexa(meth)acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, caprolactone-modified dipentaerythritol hexa(meth)acrylate or alkylene oxide modified products thereof, and other hexafunctional (meth)acrylates.

[0057] The activated energy ray-curable monomer may be used alone or in combination of two or more types.

[0058] Examples of oligomers having carbon-carbon unsaturated double bonds include epoxy (meth)acrylate compounds, urethane (meth)acrylate compounds, and polyester (meth)acrylate compounds.

[0059] Among active energy ray curable monomers, trifunctional or more (meth)acrylate monomers having three or more (meth)acrylate groups, such as trimethylolpropane tri(meth)acrylate, alkylene oxide modified trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, are preferred because they can greatly contribute to improving curability and strength in printing applications on paper substrates such as fine paper, coated paper, art paper, imitation paper, thin paper, and cardboard.

[0060] Polyfunctional (meth)acrylate monomers having three or more (meth)acrylate groups are highly reactive and therefore exhibit excellent curability, but tend to have poor fluidity. The binder resin used in the present invention incorporates a rosin skeleton and has an acid value exceeding 10 mg KOH / g, thereby improving its affinity with pigments. This ensures that the fluidity of the ink composition of the present invention can be maintained even when using the aforementioned polyfunctional (meth)acrylate monomers.

[0061] The active energy ray-curable monomer is preferably contained in an amount of 20% to 50% by mass relative to the non-volatile components of the overprint varnish of the present invention, and more preferably 25% to 50% by mass. Within this range, the curability is particularly excellent.

[0062] Furthermore, when using a trifunctional or higher (meth)acrylate as the active energy ray curable monomer, the content of the trifunctional or higher (meth)acrylate is preferably in the range of 15% to 75% by mass relative to the nonvolatile components of the overprint varnish of the present invention, more preferably in the range of 20% to 70% by mass, and even more preferably in the range of 25% to 65% by mass. Furthermore, if the substrate is plastic, the content of trifunctional or higher (meth)acrylate should be in the range of 0% to 50% by mass relative to the non-volatile components of the overprint varnish of the present invention.

[0063] (Photopolymerization initiator) As a photopolymerization initiator, any known photopolymerization initiator can be used, such as α-aminoalkylphenone compounds, acylphosphine oxide compounds, benzophenone compounds, thioxanthone compounds, ketocoumarin compounds, hydroxyacetophenone compounds, benzyldimethylketal compounds, etc.

[0064] Specific examples of α-aminoalkylphenone compounds that act as photopolymerization initiators include 2-(dimethylamino)-2-methyl-1-[4-(4-morpholinyl)phenyl]-3-phenyl-1-propanone, 1-butanone, 2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-2-(phenylmethyl)-,(2S)-, 2-(dimethylamino)-2-methyl-3-(4-methylphenyl)-1-[4-(4-morpholinyl)phenyl]-1-propanone, 2-(dimethylamino)-1-[4 -(4-morpholinyl)phenyl]-2-(phenylmethyl)-1-pentanone, 2-(dimethylamino)-2-[(4-ethylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-hydroxyphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-[(4-butylphenyl)methyl]-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 1-butanone,2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-2-[(4-propylphenyl)methyl]-, 2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-2-phenyl-1-butanone, 3-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-3-(phenylmethyl)-2-pentanone, 2-(dimethylamino)-2-ethyl-1-[4-(4-morpholinyl)phenyl]-4-phenyl-1-butanone, 3-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-3-phenyl-2-butanone, 1-(4-mercaptophenyl)-2-methyl-2-(4-morpholinyl)-1-propanone, 1-[4-(ethylthio)phenyl]-2-methyl-2-(4-morpholinyl)-1-propanone, dimethyl[4-[2-methyl-2-(4-morpholinyl)-1-oxopropyl]phenyl]sulfonium, 2-methyl-1-[4-[(1-methylethyl) Thio]phenyl]-2-(4-morpholinyl)-1-propanone, ethylmethyl[4-[2-methyl-2-(4-morpholinyl)-1-oxopropyl]phenyl]sulfonium, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morph Examples include olinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-piperidinylphenyl)-1-butanone, 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, 1-(4-methoxyphenyl)-2-methyl-2-morpholin-4-ylpropan-1-one, polyethylene glycol (200) di(β-4[4-(2-dimethylamino-2-benzyl)butanonylphenyl]piperazine propionate, etc.

[0065] Examples of acylphosphine oxide compounds that act as photopolymerization initiators include compounds represented by the following general formula (1).

[0066] [ka] (In the general formula (1), R 1 ~R 4 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Y 1 is an alkyl group having 1 to 6 carbon atoms or a group represented by the following general formula (2), Y 2 is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a (poly) alkoxyalkyl group (the alkoxyalkyl group part is an alkoxyalkyl group having 2 to 12 carbon atoms), a phenyl group, or a group represented by the following general formula (3), Y 3 is a phenyl group or a group represented by the following general formula (2).)

[0067]

Chemical formula

[0068] R 1 ~R 13 Examples of the alkyl group having 1 to 6 carbon atoms for R

[0069] R 14and R 15 Examples of alkylene groups having 1 to 6 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, or hexylene groups.

[0070] Among the acylphosphine oxide compounds represented by the general formula (1) above, R 1 , R 2 and R 4 is a methyl group, R 3 and Y 1 Y is a hydrogen atom, 2 The group is an ethyl group, Y 3 Ethylphenyl (2,4,6-trimethylbenzoyl) phosphinate, in which the group is a phenyl group, is preferred. Ethylphenyl (2,4,6-trimethylbenzoyl) phosphonate is commercially available as TPO-L (#CAS 84434-11-7, manufactured by SARTOMER).

[0071] Among the acylphosphine oxide compounds represented by the general formula (1) above, R 1 , R 2 and R 4 is a methyl group, R 3 Y is a hydrogen atom. 2 This is a polyalkoxymethyl group with 2 carbon atoms, Y 3 This is represented by the structural part shown by general formula (2), R 6 , R 7 and R 9 is a methyl group, R 5 and R 8 Compounds in which the atom is a hydrogen atom are preferred. The compound in question is available commercially as Omnirad 820 (manufactured by IGM Resins BV).

[0072] Among the acylphosphine oxide compounds represented by the general formula (1) above, R 1 , R 2 and R 4 is a methyl group, R 3 Y is a hydrogen atom, 1This is represented by the structural part shown by general formula (2), R 5 ~R 9 Y is a hydrogen atom, 2 The group is an ethyl group, Y 3 Ethyl (3-benzoyl-2,4,6-trimethylbenzoyl)(phenyl) phosphate, in which the group is a phenyl group, is preferred. Ethyl (3-benzoyl-2,4,6-trimethylbenzoyl)(phenyl) phosphinate is commercially available as SpeedCure XKm (#CAS 1539267-56-5, manufactured by SARTOMER).

[0073] Among the acylphosphine oxide compounds represented by the general formula (1) above, R 1 , R 2 and R 4 is a methyl group, R 3 and Y 1 Y is a hydrogen atom, 3 is a phenyl group, Y 2 The group is represented by the general formula (3), and R 10 , R 11 and R 13 is a methyl group, R 12 and Y 11 Y is a hydrogen atom, 33 is a phenyl group, R 14 and R 15 A compound in which the group is a (poly)oxyalkylene group having 2 carbon atoms is preferred. This compound is commercially available as Omnipol TP (#CAS 1834525-17-5, manufactured by IGM Resins BV).

[0074] Examples of benzophenone compounds that act as photopolymerization initiators include 4,4'-dialkylaminobenzophenones (e.g., 4,4'-bis-(dimethylamino)benzophenone, 4,4'-bis-(diethylamino)benzophenone), 4-benzoyl-4'-methyldiphenyl sulfide, and 4-methylbenzophenone, with 4,4'-bis-(diethylamino)benzophenone being preferred.

[0075] Examples of thioxanthone compounds used as photopolymerization initiators include 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-hydroxy-3-(3,4-dimethyl-9-oxo-9Hthioxanthone-2-yloxy-N,N,N-trimethyl-1-propanamine hydrochloride. Of these, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone are preferred.

[0076] Examples of ketocoumarin compounds that act as photopolymerization initiators include 3-benzoylcoumarin, 3-(4-methoxybenzoyl)coumarin, 3-benzoyl-7-methoxycoumarin, 3-(4-methoxybenzoyl)7-methoxy-3-coumarin, 3-acetyl-7-dimethylaminocoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3,3'-coumarinoketone, and 3,3'-bis(7-diethylaminocoumarino)ketone.

[0077] Examples of hydroxyacetophenone compounds that act as photopolymerization initiators include ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, 1-hydroxycyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

[0078] An example of a benzyldimethyl ketal compound used as a photopolymerization initiator is 2,2-dimethoxy-2-phenylacetophenone.

[0079] Among the photopolymerization initiators, it is preferable that they contain hydroxyacetophenone compounds and / or acylphosphine oxide compounds.

[0080] The content of the photopolymerization initiator can be appropriately set according to the intended use. For example, it is often in the range of 1% to 20% by mass relative to the non-volatile component of the overprint varnish of the present invention, and preferably in the range of 5% to 15% by mass.

[0081] Specific examples of photosensitizers include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, and sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothironium-p-toluenesulfonate.

[0082] The content of the photosensitizer can be appropriately set according to the intended use, for example, it may be in the range of 1% to 20% by mass relative to the nonvolatile component of the overprint varnish of the present invention, and preferably in the range of 1% to 10% by mass.

[0083] (Other ingredients) The overprint varnish of the present invention may also contain known additives such as antioxidants, polymerization inhibitors, photosensitizers, silicone-based additives, waxes, metal complexes (chelating agents), photoinitiators, curing accelerators (such as cobalt naphthenate), fillers, thickeners, foaming agents, antioxidants (such as tocopherol, butylhydroxyanisole, and dibutylhydroxytoluene), flame retardants, ultraviolet absorbers, and antibacterial agents.

[0084] (Antioxidant) Specific examples of antioxidants include hindered phenol antioxidants, hindered amine antioxidants, organosulfur antioxidants, and phosphate ester antioxidants.

[0085] The content of the antioxidant can be appropriately set according to the intended use, for example, it may be in the range of 0.1% to 5% by mass relative to the non-volatile component of the overprint varnish of the present invention.

[0086] Specific examples of polymerization inhibitors include (alkyl)phenol, hydroquinone, methoquinone, catechol, resorcinol, 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, capferone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N-(3-oxyanilino-1,3-dimethylbutylidene)aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime, cyclohexanone oxime, copper dimethyldithiocarbamate, and copper dibutyldithiocarbamate.

[0087] The content of the polymerization inhibitor can be appropriately set according to the intended use, for example, it may be in the range of 0.1% to 5% by mass relative to the non-volatile components of the overprint varnish of the present invention.

[0088] Specific examples of silicone-based additives include, for example, polyorganosiloxanes having alkyl or phenyl groups such as dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethylpolysiloxane copolymer, and amino-modified dimethylpolysiloxane copolymer; polydimethylsiloxane having polyether-modified acrylic groups; and polydimethylsiloxane having polyester-modified acrylic groups.

[0089] Silicone-based additives are added to printed materials to impart slipperiness, and their content can be appropriately set according to the intended application. For example, a range of 0.01% to 1% by mass relative to the non-volatile component of the overprint varnish of the present invention is preferable.

[0090] Specific examples of waxes include olefin waxes such as polyethylene wax and polyethylene oxide wax, paraffin wax, carnauba wax, beeswax, microcrystalline wax, polytetrafluoroethylene wax, amide wax, and fatty acids with approximately 8 to 18 carbon atoms, such as coconut oil fatty acids and soybean oil fatty acids.

[0091] The wax is added to improve curing properties, and its content can be appropriately set depending on the intended use. For example, it is preferable to set it in the range of 0.1% to 5% by mass relative to the non-volatile components of the overprint varnish of the present invention.

[0092] The active energy ray-curable overprint varnish of the present invention can be used without solvents, or a suitable solvent can be used as needed. The solvent is not particularly limited as long as it does not react with the aforementioned components, and can be used alone or in combination of two or more.

[0093] The production of the active energy ray curable overprint varnish of the present invention can be carried out by the same method as in the conventional method. For example, raw materials such as the resin, acrylic monomer or oligomer, polymerization inhibitor, initiator, sensitizer such as an amine compound, photocatalyst and other additives used in the present invention are produced at a temperature between room temperature and 100°C using a kneading, mixing, and processing machine such as a kneader, three-roll machine, attritor, sand mill, or gate mixer.

[0094] (Printed material) The printed material of the present invention is obtained by applying the active energy ray-curable overprint varnish of the present invention to a printed material either directly on a substrate or on a printed material printed using a lithographic offset printing press with a printing ink composition. The varnish may be applied to the entire surface of the printed material or to only a part of it. The amount of varnish applied can be adjusted as appropriate depending on the purpose of application, but as an example, it is adjusted so that the film thickness of the active energy ray-curable overprint varnish after drying is about 0.5 μm to 1.5 μm.

[0095] The coating method may be an in-line method, in which a coating device is incorporated into a lithographic offset printing press and the active energy ray curable overprint varnish of the present invention is applied immediately after printing with a printing ink composition, or it may be an offline method, in which the varnish is applied after printing with a lithographic offset printing press using a coater machine equipped with a gravure or flexographic coating device.

[0096] (Paper base material) There are no particular restrictions on the substrate material, and conventionally known materials can be used, but it is particularly suitable for printing on paper substrates such as coated paper, matte coated paper, and fine paper. Backing paper, impregnated paper, cardboard, and paperboard can also be used.

[0097] (Plastic base material) Furthermore, it may be applied to a plastic substrate. The plastic substrate can be any substrate used for plastic materials, molded products, film substrates, packaging materials, etc. Specifically, examples include films and laminates made of thermoplastic resins such as polyamide resins like nylon 6, nylon 66, nylon 46, etc., polyester resins such as polyethylene terephthalate (hereinafter sometimes referred to as PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, etc., biodegradable resins such as polyhydroxycarboxylic acids such as polylactic acid, aliphatic polyester resins such as poly(ethylene succinate), poly(butylene succinate), etc., polyolefin resins such as polypropylene, polyethylene, etc., polyimide resins, polyarylate resins, or mixtures thereof. Among these, films made of polyethylene terephthalate (PET), polyester, polyamide, polyethylene, and polypropylene can be preferably used. These substrate films may be unstretched or stretched films, and their manufacturing method is not limited. Furthermore, the thickness of the base film is not particularly limited, but is usually in the range of 1 μm to 500 μm. It is also preferable that the base film be subjected to corona discharge treatment, and aluminum, silica, alumina, etc. may be deposited on it. The base material may also be a laminate (sometimes referred to as a laminated film) having a laminated structure obtained by laminating the aforementioned paper base material or film base material by dry lamination, solvent-free lamination, or extrusion lamination.

[0098] The aforementioned paper or plastic substrate may further have a printing ink layer. There are no particular limitations on the printing ink used in the printing ink layer, and it is possible to coat the printing layer with offset lithographic inks, gravure printing inks, flexographic printing inks, inkjet printing inks, etc. In particular, as mentioned above, a method of coating a printed material printed by a lithographic offset printing press using an offset printing ink composition is industrially preferred.

[0099] (containers, packaging materials) The single-layer paper substrate or film substrate, or laminate having a laminated structure, can be expressed in various ways depending on the industry and method of use, such as functional films, flexible packaging films, shrink films, films for packaging household goods, pharmaceutical packaging films, food packaging films, cartons, posters, flyers, CD jackets, direct mail, brochures, and packaging for cosmetics, beverages, pharmaceuticals, toys, equipment, etc., using high-quality paper, coated paper, art paper, imitation paper, thin paper, thick paper, and various synthetic papers. However, the active energy ray curable overprint varnish of the present invention can be used without any particular limitations. Furthermore, these substrates, after being coated with the active energy ray curable overprint varnish of the present invention, are molded into containers and packaging materials. In this case, it is preferable that the active energy ray curable overprint varnish of the present invention be applied to the surface that becomes the outermost layer when these are used as containers or packaging materials. [Examples]

[0100] The present invention will be specifically described below with reference to examples and comparative examples. Furthermore, the present invention is not limited to the following embodiments. Also, hereafter, "parts" and "%" are based on mass.

[0101] In the embodiments of this application, the acid value and hydroxyl value are values ​​evaluated by the following method. [Method for measuring acid value] Measurements were taken according to the method specified in JIS K0070-1992. [Method for measuring hydroxyl value] Measurements were taken according to the method specified in JIS K0070-1992.

[0102] In the embodiments of this invention, the number-average molecular weight and weight-average molecular weight of polyester are values ​​converted to polystyrene based on GPC measurement, and the measurement conditions are as follows. [GPC measurement conditions] Measurement device: Tosoh Corporation high-speed GPC system "HLC-8420GPC" Column: Two "TSKgel SuperMultiporeHZ-H" columns manufactured by Tosoh Corporation. Detector: RI (Differential Refractometer) Data processing: EcoSEC Data Analysis version 1.07 manufactured by Tosoh Corporation. Column temperature: 40℃ Developing solvent: tetrahydrofuran Flow rate: 0.35mL / min Measurement sample: 7.5 mg of the sample was dissolved in 10 ml of tetrahydrofuran, and the resulting solution was filtered through a microfilter to be used as the measurement sample. Sample injection volume: 20 μl Standard material: "PStQuick MP-H" manufactured by Tosoh Corporation

[0103] In the embodiments of this application, the content of acid-modified rosin (main component maleopimal acid) is: 13 Evaluation was performed by 13C-NMR measurement. The measurement conditions were as follows: [ 13 C-NMR measurement conditions] Measurement equipment: JEOL AL400 / ECA500 nuclear magnetic resonance spectrometer Total: 400 times Measurement temperature: room temperature NNE mode Sample concentration: 30 wt% deuterated chloroform solution Relaxation agent: Tris(2,4-pentanedionato)chromium(III)

[0104] (Synthesis Example 1: Preparation of Polyester Resin A1) 279.2 g of gum rosin and 85.0 g of maleic anhydride were placed in a 1-liter four-necked flask equipped with a thermometer, stirrer, and reflux condenser, and the temperature was gradually raised to 180°C while stirring under a nitrogen atmosphere. The mixture was then heated at 180°C for 1 hour to obtain maleic acid-modified rosin containing 50% or more by mass of maleopimar acid. Heating was stopped, and 137.7 g of benzoic acid, 127.0 g of diethylene glycol, 70.8 g of pentaerythritol, and 0.35 g of tetraisopropyl titanate as an esterification catalyst were charged into the flask. The mixture was then gradually heated to 250°C while stirring under a nitrogen atmosphere. Heating was then continued at 250°C, and the generated water was continuously removed to obtain polyester resin A1 (acid value 27.3, hydroxyl value 56.6, weight-average molecular weight 164,340).

[0105] (Examples 1-10 and Comparative Examples 1-5: Preparation and Evaluation of Active Energy Ray Curable Inks) Active energy ray-curable inks were prepared with the compositions (parts) shown in Tables 1 and 2. The raw materials used are as follows: NeoLight GP-20: (Calcium Carbonate) (Manufactured by Takehara Chemical Industry Co., Ltd.) Magnesium Carbonate TT (Naikai): (Magnesium Carbonate) (Manufactured by Naikai Salt Industry Co., Ltd.) AEROJIL 200: (Silicon Dioxide) (Manufactured by Nippon Aerosil Co., Ltd.) AEROJIL 972R: (Silicon Dioxide) (Manufactured by Nippon Aerosil Co., Ltd.) Rheoroseal MT-10: (Silicon Dioxide) (Manufactured by Tokuyama Corporation) High Filler 5000pj: (Talc) (Manufactured by Matsumura Sangyo Co., Ltd.) TEGO WET 270: (Polyether-modified siloxane copolymer) (Evonik Japan Co., Ltd.) S-381-N1: (Polyethylene Wax) (Manufactured by Shamrock Technologies Inc.) Polyester resin A1: (Manufactured by DIC Graphics Co., Ltd.) DAP-A: (Diallyl phthalate resin) (Manufactured by Osaka Soda Co., Ltd.) Miramer M600:(DPHA)(manufactured by Miwon Specialty Chemical Co., Ltd.) Miramer M240: (Bisphenol A EO-modified diacrylate) (Manufactured by Miwon Specialty Chemical Co., Ltd.) Miramer M3130: (Trimethylolpropane EO-modified triacrylate) (Manufactured by Miwon Specialty Chemical Co., Ltd.) EPICLON UE-8410: (Epoxy acrylate) (Manufactured by DIC Corporation) Aronics M-7300K: (Polyester acrylate) (Manufactured by Toagosei Co., Ltd.) (1) TPO: (2,4,6-trimethylbenzoyldiphenylphosphine oxide) (manufactured by TIANJIN JIURI NEW MATERIALS CO., LTD.) (1) Omnirad 819: (Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide) (manufactured by IGM Japan LLC) (2) TR-184: (1-Hydroxycyclohexylphenyl ketone) (Manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) (3) Omnirad 379: (2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one) (manufactured by IGM Japan LLC) (3) RUNTECURE 1607: (1-(4-methoxyphenyl)-2-methyl-2-morpholin-4-ylpropan-1-one) (manufactured by TIANJIN JIURI NEW MATERIALS CO., LTD.) (4) RUNTECURE DETX: (2,4-Diethylthioxanthone) (Manufactured by TIANJIN JIURI NEW MATERIALS CO., LTD.) 64X0008-2: (Acrylate mixture containing polymerization inhibitor) (Manufactured by DIC Corporation)

[0106] (Evaluation method) (How to create evaluation samples) (curable) A UV irradiation device (manufactured by iGraphics Co., Ltd., output 80-160 W / cm) equipped with a water-cooled metal halide lamp and a belt conveyor was used to form an ink-cured layer for evaluation. The material to be colored with black ink was placed on the conveyor and passed through at a conveyor speed of 100 m / min. Next, the colored material, after applying the photocurable overprint varnishes of Examples 1-10 and Comparative Examples 1-5 onto the ink-cured layer obtained by the above method, was irradiated with ultraviolet light to cure and dry the overprint varnish.

[0107] (Evaluation item 1: Curability evaluation of active energy ray curing ink) The hardening properties of the cured film were evaluated by rubbing the cured ink layer with a fingernail immediately after curing. The evaluation criteria were as follows: ◎: It does not get scratched even when rubbed with strong force, and its UV curing properties are excellent. ○: It may get slightly scratched if rubbed with strong force. △: Rubbing with strong force will clearly cause scratches. ×: Even light rubbing causes clear scratches, indicating poor UV curing properties.

[0108] (Evaluation Item 2: Mistakes) After attaching a piece of white paper to the cover of a digital incomometer (Toyo Seiki), the degree of misting was determined by rotating a roller coated with light-curing overprint varnish at 1200 rpm for 3 minutes. The evaluation criteria were as follows: ○: Mist is scattered across a portion of the blank paper. △: Mist is scattered across a blank sheet of paper. ×: Mist is scattered over a wide area of ​​the blank paper.

[0109] (Evaluation item 3: Storage stability) The active energy ray-curable inks for lithographic offset printing obtained in the examples and comparative examples were left at 70°C, and their storage stability was evaluated by visual inspection and tactile examination with a metal spatula after 2 weeks and 4 weeks. The evaluation criteria were as follows: ○: 4 weeks later, no abnormalities, good condition. △: No abnormalities after 2 weeks. Gel formed after 4 weeks. Practical range. ×: The ink gelled after two weeks. Unusable.

[0110] (Evaluation item 4: Gloss) The 60° gloss value of the test samples was measured using a gloss meter. The obtained gloss values ​​were evaluated using the following four-point scale. The evaluation criteria were as follows: ◎: Gloss value is 80 or higher. ○: The gloss value is 60 or higher. △: Gloss value is 40 or higher. ×: Gloss value is 39 or less.

[0111] The results are shown in Tables 1 and 2. Blank spaces indicate that the ingredient was not included.

[0112] [Table 1]

[0113] [Table 2]

Claims

1. Acid-modified rosin, a monobasic acid having a cyclic structure, and a polyol having three or more hydroxyl groups in one molecule are at least the reactants, and a polyester with an acid value of more than 10 mg KOH / g is used. A photopolymerization initiator, a (meth)acrylic monomer, An active energy ray curing type overprint varnish characterized by containing at least one extender pigment selected from the group consisting of calcium carbonate, silica, and magnesium carbonate in an amount of 3% to 15% by mass relative to the non-volatile components of the varnish.

2. The active energy ray curable overprint varnish according to claim 1, wherein the polyester is one or more monobasic acids having a cyclic structure selected from benzoic acid, phenylacetic acid, cinnamic acid, mandelic acid, salicylic acid, atrolactinic acid, anisic acid, toluic acid, ethylbenzoic acid, isopropylbenzoic acid, naphthoic acid, methylnaphthoic acid, anthronic acid, adamantic acid, hexahydrobenzoic acid, tetrahydrobenzoic acid, gum rosin, wood rosin, tall oil rosin, and hydrogenated rosin, and the reaction component does not contain any dibasic acids other than the acid-modified rosin.

3. The overprint varnish according to claim 1, wherein the polyester is contained in an amount of 6.0% to 30.0% by mass relative to the non-volatile components of the varnish, and the content of the resin containing the polyester is 35.0% by mass or less.

4. The active energy ray curable overprint varnish according to claim 1, comprising a hydroxyacetophenone compound and / or an acylphosphine oxide compound as the photopolymerization initiator.

5. The active energy ray curable overprint varnish according to claim 1, wherein the (meth)acrylic monomer is contained in an amount of 20% to 50% by mass relative to the non-volatile components of the varnish.

6. The active energy ray curable overprint varnish according to claim 1, comprising an olefin-based wax and / or a silicone-based additive.

7. A printed material using the active energy ray curable overprint varnish described in any one of claims 1 to 6.

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