Active energy ray-curable composition and laminate

Abstract

To provide a rosin-modified compound-containing active energy ray-curable composition and a laminate that have good adhesion to a wide range of substrates and have excellent cured coated film chemical resistance.SOLUTION: Provided are an active energy ray-curable composition, which is an active energy ray-curable composition that contains a (meth)acrylate compound (excluding cases where it is a silicon compound), a polymerization initiator, a rosin-modified compound, and a silicon compound, and in which, characterized, the ratio of a rosin-derived structural unit in the rosin-modified compound is 20 to 80 mass% based on the total structural units constituting the rosin-modified compound, and a laminate using the composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable composition containing a rosin-modified compound, which exhibits good adhesion to a wide range of substrates and provides a cured coating film with excellent chemical resistance, and to a laminate. [Background technology]

[0002] In recent years, active energy ray-curable compositions can be cured by irradiation with active energy rays such as ultraviolet rays, visible light, and electron beams for a very short time, and are therefore highly productive and capable of providing high coating film resistance, and therefore have been widely used in fields where durability is required.

[0003] However, when the substrate to be printed is plastic, the active energy ray-curable composition has a problem that good adhesion cannot be obtained depending on the type of plastic, particularly to olefin-based substrates such as polyethylene and polypropylene, which have low polarity, and to polystyrene substrates, and various studies have been conducted to address this problem.

[0004] Furthermore, in recent years, as part of efforts to reduce environmental impact, the Japan Organics Resources Association has established a new biomass mark system, which calls for replacing raw materials contained in compositions with biomass-derived raw materials and increasing their proportion.

[0005] However, when the ratio of biomass-derived raw materials is increased in an active energy ray-curable composition, there is a problem that sufficient adhesion to the substrate and coating film resistance cannot be obtained, and various investigations have been carried out to address this problem.

[0006] For example, Patent Document 1 discloses an active energy ray-curable resin composition containing 10 to 50% by weight of a styrene-acrylic acid ester copolymer having a nitrogen-containing (meth)acrylic monomer with a weight-average molecular weight of 3,000 to 50,000, and 50 to 90% by weight of a reactive diluent. However, although the composition improves adhesion to acrylic and polyester substrates to some extent, it is not sufficient, and there is a problem in that good adhesion cannot be obtained to olefin substrates such as polyethylene and polypropylene, which have low polarity, or polystyrene substrates.

[0007] For example, Patent Document 2 discloses an active energy ray-curable resin composition containing 5 to 95 wt% of rosin epoxy acrylate, 5 to 95 wt% of a polyurethane resin having a carbon-carbon unsaturated bond group and a number-average molecular weight of 1,000 to 50,000, and 0 to 70 wt% of a reactive diluent. However, although the use of rosin epoxy acrylate increases the biomass ratio, there is a problem in that sufficient adhesion cannot be obtained. Furthermore, because both the rosin epoxy acrylate and the polyurethane resin are monofunctional, there is a problem in terms of coating film resistance.

[0008] For example, Patent Documents 3 and 4 disclose active energy ray-curable resin compositions that improve adhesion. However, although the adhesion is improved, there is a problem that the coating film becomes flexible and sufficient coating film resistance cannot be obtained. Furthermore, since biomass-derived raw materials are not used, it can be said that the environmental friendliness is insufficient.

[0009] For example, Patent Documents 5 and 6 disclose printing ink compositions using rosin-modified resins. However, although biomass-derived raw materials are used, there are problems in that the chemical resistance, which is the resistance of the coating film, is not sufficiently obtained, and in particular, adhesion to plastic substrates such as polyethylene, polypropylene, and polystyrene is not obtained. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 3-215543 [Patent Document 2] Japanese Patent Application Publication No. 8-143635 [Patent Document 3] Japanese Patent Application Laid-Open No. 2004-339487 [Patent Document 4] Japanese Patent Application Laid-Open No. 2011-225751 [Patent Document 5] International Publication No. 2017 / 164246 [Patent Document 6] Japanese Patent Application Publication No. 2019-116579 Summary of the Invention [Problem to be solved by the invention]

[0011] The problem to be solved by the present invention is to provide an active energy ray-curable composition and laminate containing a rosin-modified compound, which have good adhesion to a wide range of substrates and provide a cured coating film with excellent chemical resistance. [Means for solving the problem]

[0012] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the active energy ray-curable composition shown below, and have thus completed the present invention.

[0013] That is, the present invention provides an active energy ray-curable composition containing a (meth)acrylate compound (except when it is a silicon compound), a polymerization initiator, a rosin-modified compound, and a silicon compound, The present invention relates to an active energy ray-curable composition, wherein the proportion of structural units derived from rosin in the rosin-modified compound is 20 to 80 mass % based on the total structural units constituting the rosin-modified compound.

[0014] The present invention also relates to the above-mentioned active energy ray-curable composition, wherein the content of the rosin-modified compound is 5 to 30% by mass based on the total mass of the active energy ray-curable composition.

[0015] The present invention also relates to the active energy ray-curable composition, wherein the content of the silicon compound is 0.1 to 10% by mass relative to the total mass of the active energy ray-curable composition.

[0016] The present invention also relates to the above-mentioned active energy ray-curable composition, wherein the silicon compound contains silicon (meth)acrylate.

[0017] The present invention also relates to an active energy ray-curable varnish containing the above active energy ray-curable composition.

[0018] The present invention also relates to an actinic ray-curable ink containing the actinic ray-curable composition and a colorant.

[0019] The present invention also relates to a laminate having, on a substrate, a layer formed by curing the above-mentioned active energy ray-curable ink with active energy rays.

[0020] The present invention also relates to a laminate having a layer of the above-mentioned active energy ray-curable varnish cured by active energy rays on a substrate or on the printed surface of a substrate on which ink has been printed.

[0021] The present invention also relates to the above laminate, wherein the substrate is a paper container or a plastic container. [Effects of the Invention]

[0022] The present invention has made it possible to provide an active energy ray-curable composition and laminate containing a rosin-modified compound that have good adhesion to a wide range of substrates and produce a cured coating film with excellent chemical resistance. DETAILED DESCRIPTION OF THE INVENTION

[0023] Hereinafter, embodiments of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

[0024] The terms used in this specification are explained below. "(Meth)acrylate" means acrylate and / or methacrylate. "Active energy rays" means energy rays, such as ultraviolet rays and electron beams, that have the property of causing chemical changes, such as chemical reactions, in the irradiated object.

[0025] <Active energy ray-curable composition> One embodiment of the present invention relates to an active energy ray-curable composition, which contains a (meth)acrylate compound (except when it is a silicon compound), a polymerization initiator, a rosin-modified compound, and a silicon compound, wherein the proportion of rosin-derived structural units in the rosin-modified compound is 20 to 80 mass% of all structural units constituting the rosin-modified compound. Components that are or can be contained in the active energy ray-curable composition of this embodiment (hereinafter also simply referred to as "composition") will be described below.

[0026] [(Meth)acrylate compounds] The active energy ray-curable composition of the present invention contains a (meth)acrylate compound. There are no particular limitations on the (meth)acrylate compound, and known compounds can be used. Furthermore, "PO" stands for "propylene oxide" and "EO" stands for "ethylene oxide." Furthermore, X in EO-modified (X) and PO-modified (X) represents the number of moles of EO and PO modified, and Y in polyethylene glycol (Y) di(meth)acrylate represents the approximate molecular weight of the polyethylene glycol portion. Among the rosin-modified compounds described below, there are some that have a (meth)acryloyl group, but in the present invention, these rosin-modified compounds that have a (meth)acryloyl group are treated as rosin-modified compounds and are not included in (meth)acrylate compounds.

[0027] In the present invention, the content of the (meth)acrylate compound is preferably 20 to 60% by mass, more preferably 25 to 55% by mass, relative to the total mass of the composition.

[0028] Specific examples of the (meth)acrylate compound include 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, β-carboxyethyl (meth)acrylate, 4-tert-butylcyclohexanol (meth)acrylate, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, caprolactone (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isoamyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isodecyl (meth)acrylate, 3,3,5-trimethylsilyl (meth)acrylate, methyl ... monofunctional (meth)acrylate compounds such as trimethylcyclohexanol (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (oxyethyl) (meth)acrylate, 1,4-cyclohexanedimethanol (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, benzyl (meth)acrylate, EO-modified (2) nonylphenol acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, and acryloylmorpholine; 1,3-Butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol (200) di(meth)acrylate, polyethylene glycol (300) di(meth)acrylate, polyethylene glycol (400) di(meth)acrylate, polyethylene glycol (600) di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dipropylene Difunctional (meth)acrylate compounds such as glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, EO-modified (2) 1,6-hexanediol di(meth)acrylate, PO-modified (2) neopentyl glycol di(meth)acrylate, (neopentyl glycol-modified) trimethylolpropane di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, EO-modified (4) bisphenol A di(meth)acrylate, PO-modified (4) bisphenol A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tris(2-hydroxyethyl)isocyanurate di(meth)acrylate; trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, EO-modified (3) trimethylolpropane tri(meth)acrylate, PO-modified (3) trimethylolpropane tri(meth)acrylate, ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate, ethoxylated isocyanuric acid tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; tetrafunctional (meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; pentafunctional (meth)acrylate compounds such as dipentaerythritol penta(meth)acrylate; hexafunctional (meth)acrylate compounds such as dipentaerythritol hexa(meth)acrylate, Examples include: The term "n-functional (meth)acrylate compound" refers to a (meth)acrylate compound having n (meth)acryloyl groups.

[0029] Furthermore, as the (meth)acrylate compound, urethane acrylate, polyester acrylate, epoxy acrylate, etc. can also be used.

[0030] Urethane acrylates include, for example, those obtained by reacting a diisocyanate with a (meth)acrylate having a hydroxyl group, and those obtained by reacting an isocyanate group-containing urethane prepolymer obtained by reacting a polyol with a polyisocyanate under conditions of an excess of isocyanate groups with a (meth)acrylate having a hydroxyl group. Alternatively, they can also be obtained by reacting a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol with a polyisocyanate under conditions of an excess of hydroxyl groups with a (meth)acrylate having an isocyanate group.

[0031] The polyester acrylate can be obtained, for example, by reacting a polyester polycarboxylic acid obtained by polycondensing a polybasic acid and a polyhydric alcohol with a hydroxyl group-containing (meth)acrylate or the like.

[0032] Examples of epoxy acrylates include those obtained by esterifying the glycidyl group of an epoxy resin with (meth)acrylic acid to change the functional group to a (meth)acrylate group, such as a (meth)acrylic acid adduct of a bisphenol A type epoxy resin and a (meth)acrylic acid adduct of a novolac type epoxy resin.

[0033] In the present invention, the (meth)acrylate compounds may be used alone or in combination of two or more.

[0034] Among these, it is preferable to contain a di- to hexa-functional (meth)acrylate compound from the viewpoint of adhesion and chemical resistance.

[0035] Furthermore, when a monofunctional (meth)acrylate compound is contained, its content is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the composition, from the viewpoint of chemical resistance.

[0036] [Polymerization initiator] The active energy ray-curable composition of the present invention contains a polymerization initiator. The polymerization initiator preferably contains a polymerizable initiator for radical polymerization, and more preferably contains a photopolymerization initiator. The polymerization initiator of the present invention is a compound that undergoes a chemical change to generate radicals through the action of light or through interaction with the electronically excited state of the sensitizing dye, and among these, a photoradical polymerization initiator is preferred from the viewpoint that polymerization can be initiated by means of exposure to light.

[0037] In the present invention, the photoradical polymerization initiator is not particularly limited, and known ones can be used, specific examples of which include benzophenone compounds, dialkoxyacetophenone compounds, α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, acylphosphine oxide compounds, and thioxanthone compounds.

[0038] Examples of the benzophenone compounds include benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, and [4-(methylphenylthio)phenyl]-phenylmethanone.

[0039] Examples of the dialkoxyacetophenone compounds include 2,2-dimethoxy-2-phenylacetophenone, dimethoxyacetophenone, and diethoxyacetophenone.

[0040] Examples of the α-hydroxyalkylphenone compounds include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxymethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl]-2-methyl-propan-1-one.

[0041] Examples of the α-aminoalkylphenone compounds include 2-methyl-1-[4-(methoxythio)-phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl-1-butanone.

[0042] Examples of the acylphosphine oxide compounds include diphenylacylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0043] Examples of the thioxanthone compounds include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone.

[0044] In the present invention, the above polymerization initiators may be used alone or in combination of two or more.

[0045] Among these, from the viewpoint of adhesion and chemical resistance, it is preferable to include an α-aminoalkylphenone compound and an acylphosphine oxide compound.

[0046] In the present invention, the content of the polymerization initiator is preferably 0.5 to 20% by mass, more preferably 5 to 15% by mass, based on the total mass of the composition.

[0047] [Rosin modified compound] The rosin-modified compound contained in the active energy ray-curable composition of the present invention is characterized in that the proportion of structural units derived from rosin in the rosin-modified compound (hereinafter also referred to as "rosin content") is 20 to 80 mass % of the total structural units constituting the rosin-modified compound.

[0048] In the present invention, the rosin-modified compound is not particularly limited as long as the proportion of rosin-derived structural units is 20 to 80 mass % of the total structural units constituting the rosin-modified compound, and known compounds can be used. For example, the following rosin-modified resins can be mentioned. A compound obtained by subjecting a conjugated rosin acid to a Diels-Alder addition reaction with an ethylenically unsaturated double bond-containing compound having a carboxy group, followed by an esterification reaction between the carboxy group of the reaction compound and the hydroxyl group of a polyol. A compound obtained by subjecting a conjugated rosin acid to a Diels-Alder addition reaction with an ethylenically unsaturated double bond-containing compound having a carboxy group, and then reacting the carboxy group of the reaction compound, the carboxy group of the ethylenically unsaturated double bond-containing compound having a carboxy group, and the hydroxyl group of a polyol (see JP 2018-150469 A). A compound obtained by subjecting a conjugated rosin acid to a Diels-Alder addition reaction with an ethylenically unsaturated double bond-containing compound having a carboxy group, and then reacting the carboxy group of the reaction compound with the hydroxyl group of a polyol, followed by an addition reaction of the epoxy group of an ethylenically unsaturated double bond-containing compound having an epoxy group with the remaining hydroxyl group and / or carboxy group. A compound obtained by subjecting a conjugated rosin acid to a Diels-Alder addition reaction with an ethylenically unsaturated double bond-containing compound having a carboxy group, and then reacting the carboxy group of the reaction compound with a hydroxyl group of a polyol, followed by an addition reaction of the remaining hydroxyl group with a carboxy group of the ethylenically unsaturated double bond-containing compound having a carboxy group and / or an isocyanate group of an ethylenically unsaturated double bond-containing compound having an isocyanate group. A compound obtained by subjecting a conjugated rosin acid to a Diels-Alder addition reaction with an ethylenically unsaturated double bond-containing compound having a carboxy group, followed by an esterification reaction between the carboxy group of the reaction compound and the hydroxyl group of an ethylenically unsaturated double bond-containing compound having a hydroxyl group (see JP 2007-56185 A). A compound obtained by subjecting a conjugated rosin acid to an esterification reaction with a polyol, followed by an addition reaction of a hydroxyl group of the reaction compound with one or more members selected from the group consisting of a carboxy group of an ethylenically unsaturated double bond-containing compound having a carboxy group, an epoxy group of an ethylenically unsaturated double bond-containing compound having an epoxy group, and an isocyanate group of an ethylenically unsaturated double bond-containing compound having an isocyanate group. A compound obtained by the Diels-Alder addition reaction of a conjugated rosin acid with a compound containing an ethylenically unsaturated double bond. A compound obtained by subjecting a conjugated rosin acid to a Diels-Alder addition reaction with an ethylenically unsaturated double bond-containing compound (excluding those having a carboxy group), followed by an esterification reaction between the carboxy group of the reaction compound and the hydroxyl group of a polyol (see JP 2000-080326 A). A compound obtained by subjecting a conjugated rosin acid to a Diels-Alder addition reaction with an ethylenically unsaturated double bond-containing compound (excluding those having a carboxy group), followed by an esterification reaction between the carboxy group of the reactant compound and the hydroxyl group of a polyol, followed by an addition reaction of the epoxy group of an ethylenically unsaturated double bond-containing compound having an epoxy group to the remaining hydroxyl group and / or carboxy group. A compound obtained by subjecting a conjugated rosin acid to a Diels-Alder addition reaction with an ethylenically unsaturated double bond-containing compound (excluding those having a carboxy group), followed by an esterification reaction between the carboxy group of the reaction compound and the hydroxyl group of a polyol, followed by an addition reaction of the carboxy group of an ethylenically unsaturated double bond-containing compound having a carboxy group and / or the isocyanate group of an ethylenically unsaturated double bond-containing compound having an isocyanate group to the remaining hydroxyl group.

[0049] The conjugated rosin acid used to obtain the rosin-modified compound of the present invention is a rosin acid having a conjugated double bond. In this specification, "rosin acids" refers to organic monobasic acids having a cyclic diterpene skeleton and their derivatives. Examples of rosin acids include rosin acid, disproportionated rosin acid, hydrogenated rosin acid, and alkali metal salts of these compounds. Furthermore, the term "conjugated double bond" refers to a bond in which multiple double bonds are alternately connected with a single bond sandwiched between them. However, this does not include the π-electron conjugated double bonds contained in aromatic compounds. In other words, the term "conjugated rosin acid" used in this specification refers to the above rosin acids, excluding hydrogenated rosin acid and the like, which do not have conjugated double bonds.

[0050] Specific examples of conjugated rosin acids include abietic acid and its conjugated compounds, such as neoabietic acid, palustric acid, and levopimaric acid. Natural resins containing these conjugated rosin acids include gum rosin, wood rosin, and tall oil rosin. Generally, the natural resins contain rosin acids without conjugated double bonds in addition to the conjugated rosin acid (A1). These natural resins may be used in the production of the rosin-modified resin (A), and the rosin acids without conjugated double bonds in the natural resins function as monobasic acids and are incorporated into the resin.

[0051] The polyol that can be used to obtain the rosin-modified compound of the present invention is not particularly limited, and any known polyol can be used. Specific examples of the linear alkylene dihydric alcohol include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,16-hexadecanediol, and 1,2-hexadecanediol. Branched alkylene dihydric alcohols such as 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, dimethylol octane, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,4-diethyl-1,5-pentanediol are also included. Cyclic alkylene dihydric alcohols such as 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cycloheptanediol, tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, hydrogenated catechol, hydrogenated resorcinol, and hydrogenated hydroquinone, Further, dihydric alcohols such as polyether polyols, polyester polyols, etc., such as polyethylene glycol (n=2 to 20), polypropylene glycol (n=2 to 20), polytetramethylene glycol (n=2 to 20), etc. Examples of the alcohol include trivalent or higher alcohols such as linear, branched, and cyclic polyhydric alcohols, such as glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, 3-methylpentane-1,3,5-triol, hydroxymethylhexanediol, trimethylol octane, diglycerin, ditrimethylolpropane, dipentaerythritol, sorbitol, inositol, and tripentaerythritol. The above polyols may be used alone or in combination of two or more.

[0052] The ethylenically unsaturated double bond-containing compound that can be used to obtain the rosin-modified compound of the present invention is not particularly limited, and known compounds can be used. Specific examples of ethylenically unsaturated double bond-containing compounds having a carboxy group include acrylic acid, methacrylic acid, β-carboxyethyl (meth)acrylate, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, isocrotonic acid, cinnamic acid, 2,4-hexadienoic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 2-ethyl-3-butenoic acid, 4-methyl-4-pentenoic acid, 5-methyl-5-hexenoic acid, 6-methyl-6-heptenoic acid, 3-propyl-3-butenoic acid, 3-(2-propenyl)benzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, and acid anhydrides thereof.

[0053] Examples of the ethylenically unsaturated double bond-containing compound having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, pentaerythritol (meth)triacrylate, dipentaerythritol penta(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, ethyl-α-hydroxymethyl acrylate, N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 2-hydroxyethyl allyl ether, 3-hydroxypropyl allyl ether, and 4-hydroxybutyl allyl ether. Furthermore, an ethylenically unsaturated double bond-containing compound obtained by adding an alkylene oxide and / or a lactone to the above-mentioned ethylenically unsaturated double bond-containing compound having a hydroxyl group can also be used as the ethylenically unsaturated double bond-containing compound having a hydroxyl group in the method of the present invention. Among these, from the viewpoint of flexibility of the coating film, a resin structure with less branching is preferred, and therefore, an ethylenically unsaturated double bond-containing compound having two or less hydroxyl groups is preferred, and a (meth)acrylate compound having two or less hydroxyl groups is more preferred.

[0054] Examples of the ethylenically unsaturated double bond-containing compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl(meth)acrylate glycidyl ether, glycidyl allyl ether, 2,3-epoxy-2-methylpropyl(meth)acrylate, 3,4-epoxycyclohexyl(meth)acrylate, 4-vinyl-1-cyclohexene-1,2-epoxide, glycidyl cinnamate, 1,3-butadiene monoepoxide, and Celloxide 2000 (manufactured by Daicel Chemical Industries, Ltd.).

[0055] Examples of the ethylenically unsaturated double bond-containing compound having an isocyanate group include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-(2-acryloyloxyethyloxy)ethyl isocyanate, and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate. Furthermore, compounds in which part of the isocyanate groups of a polyisocyanate has reacted with hydroxyl groups of a (meth)acrylate compound having a hydroxyl group can also be used as the ethylenically unsaturated double bond-containing compound having an isocyanate group.

[0056] As the ethylenically unsaturated double bond-containing compound other than those mentioned above, ethylenically unsaturated double bond-containing compounds other than the above-mentioned ethylenically unsaturated double bond-containing compound having a carboxy group, the ethylenically unsaturated double bond-containing compound having a hydroxyl group, the ethylenically unsaturated double bond-containing compound having an epoxy group, and the ethylenically unsaturated double bond-containing compound having an isocyanate group can be used. Specifically, 2-ethylhexyl (meth)acrylate, 4-tert-butylcyclohexanol (meth)acrylate, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isoamyl (meth)acrylate, ) acrylate, 2-phenoxyethyl (meth)acrylate, isodecyl (meth)acrylate, 3,3,5-trimethylcyclohexanol (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (oxyethyl) (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, benzyl (meth)acrylate, EO-modified (2) nonylphenol acrylate, 2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, monofunctional (meth)acrylate compounds such as acryloylmorpholine, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol (200) di(meth)acrylate, polyethylene glycol (300) di(meth)acrylate, polyethylene glycol (400) di(meth)acrylate, polyethylene glycol (60 Bifunctional (meth)acrylate compounds such as 0) di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, EO-modified (2) 1,6-hexanediol di(meth)acrylate, PO-modified (2) neopentyl glycol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, EO-modified (4) bisphenol A di(meth)acrylate, PO-modified (4) bisphenol A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, and dicyclopentanyl di(meth)acrylate; trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, EO-modified (3) trimethylolpropane tri(meth)acrylate, PO-modified (3) trimethylolpropane tri(meth)acrylate, ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate, and ethoxylated isocyanuric acid tri(meth)acrylate; tetrafunctional (meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; hexafunctional (meth)acrylate compounds such as dipentaerythritol hexa(meth)acrylate, Examples include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, butyl vinyl ether, ethyl vinyl ether, 1-hexene, allyl acetate, allyl cyanide, vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, acetylene, and ethynyltoluene. Among these, compounds having 2 to 4 ethylenically unsaturated double bonds are preferred, and di- to tetrafunctional (meth)acrylates are more preferred, since a resin structure with fewer branches is preferred from the viewpoint of flexibility of the coating film.

[0057] The above ethylenically unsaturated double bond-containing compounds may be used alone or in combination of two or more.

[0058] The rosin content of the rosin-modified compound is more preferably 25 to 60% by mass from the viewpoint of coating film strength.

[0059] The weight average molecular weight (hereinafter also referred to as Mw) of the rosin-modified compound is preferably 1,000 to 50,000, and more preferably 2,000 to 8,000.

[0060] In the present invention, Mw was measured by gel permeation chromatography (hereinafter referred to as "GPC"). The specific measurement method for GPC is as follows. An HLC-8020 manufactured by Tosoh Corporation was used, and a calibration curve was prepared using a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M columns (manufactured by Tosoh Corporation) were used. Measurements were performed at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40°C.

[0061] From the viewpoint of chemical resistance of the coating film, the content of the rosin-modified compound is preferably 5 to 40 mass %, more preferably 10 to 35 mass %, and particularly preferably 15 to 30 mass %, relative to the total mass of the active energy ray-curable composition.

[0062] [Silicon compounds] The active energy ray-curable composition of the present invention contains a silicon compound to develop adhesion and coating film resistance. As the silicon compound, a non-reactive silicon compound or a silicon (meth)acrylate is used. Note that the term "non-reactive" in the non-reactive silicon compound means that the structure does not contain reactive groups such as (meth)acryloyl groups, allyl groups, vinyl groups, or vinyl ether groups. (Non-reactive silicon-based compounds) The non-reactive silicon-based compound preferably has a polyorganosiloxane skeleton, more preferably a polydimethylsiloxane structure (I).

[0063] General formula (I) Polydimethylsiloxane [ka]

[0064] Suitable examples of the polydimethylsiloxane include amino-modified polydimethylsiloxane resins, polyether-modified polydimethylsiloxane resins, alkyl-modified polydimethylsiloxane resins, aralkyl-modified polydimethylsiloxane resins, epoxy-modified polydimethylsiloxane resins, carboxyl-modified polydimethylsiloxane resins, carbinol-modified polydimethylsiloxane resins, mercapto-modified polydimethylsiloxane resins, phenol-modified polydimethylsiloxane resins, heterofunctional group-modified polydimethylsiloxane resins, methylstyryl-modified polydimethylsiloxane resins, higher fatty acid ester-modified polydimethylsiloxane resins, higher alkoxy-modified polydimethylsiloxane resins, higher fatty acid-containing modified polydimethylsiloxane resins, fluorine-modified polydimethylsiloxane resins, and polyether-modified polydimethylsiloxanes. The non-reactive silicone compounds may be used alone or in combination of two or more. Among them, polyether-modified polydimethylsiloxane resins are preferred because their compatibility with (meth)acrylate compounds can be controlled by adjusting the type and number of alkylene oxides added to the polyether chain. Preferred alkylene oxides include polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol copolymers.

[0065] (Silicone (meth)acrylate) In the active energy ray-curable composition of the present invention, the silicon compound preferably contains a (meth)acryloyl group in the molecule. Silicon (meth)acrylate is a compound having a polyorganosiloxane skeleton and containing (meth)acryloyl groups in its structure. The polyorganosiloxane skeleton preferably has the polydimethylsiloxane structure (general formula (I)). Since the silicon (meth)acrylate contains (meth)acryloyl groups in its structure, it can react with the (meth)acrylate compound in the composition by irradiation with active energy rays. From the viewpoint of reactivity, the number of (meth)acryloyl groups in one molecule is preferably 1 to 10, more preferably 2 to 6.

[0066] The content of the silicon compound is preferably 0.1 to 10 mass %, more preferably 2 to 7 mass %, based on the total mass of the active energy ray-curable composition, from the viewpoint of adhesion and coating strength.

[0067] [Other ingredients] The active energy ray-curable composition of the present invention may contain, in addition to the above-mentioned components, a resin other than the rosin-modified compound, a colorant, an extender pigment, a pigment dispersant, a sensitizer, a wax, a polymerization inhibitor, a surface tension adjuster, an antifoaming agent, an ultraviolet absorber, an antioxidant, and the like, as needed, within a range that does not impair the effects of the present invention.

[0068] [Coloring agent] The colorant used in the active energy ray-curable composition of the present invention may be at least one of a pigment and a dye. From the viewpoint of light resistance, a pigment is preferred. The pigment that can be used in the present invention is not particularly limited, and any known pigment can be used. Both inorganic and organic pigments can be used.

[0069] Examples of the inorganic pigment include carbon blacks such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide.

[0070] Examples of the organic pigments include soluble azo pigments such as β-naphthol-based, β-hydroxynaphthoic acid-based, β-hydroxynaphthoic acid anilide-based, acetoacetic acid anilide-based, and pyrazolone-based pigments; Examples of suitable pigments include insoluble azo pigments such as β-naphthols, β-oxynaphthoic acid anilides, monoazo acetoacetate anilides, disazo acetoacetate anilides, and pyrazolones; phthalocyanine pigments such as copper phthalocyanine blue, halogenated (e.g., chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, and metal-free phthalocyanine; and polycyclic and heterocyclic pigments such as quinacridones, dioxazines, threnes (pyranthrones, anthanthrones, indanthrones, anthrapyrimidines, flavanthrones, thioindigo, anthraquinones, perinones, and perylenes), isoindolinones, metal complexes, quinophthalones, and diketopyrrolopyrroles.

[0071] More specifically, in terms of the CI color index, examples of black pigments include CI Pigment Black 1, 6, 7, 9, 10, 11, 28, 26, 31, and the like.

[0072] Examples of white pigments include CI Pigment White 5, 6, 7, 12, and 28.

[0073] Examples of yellow pigments include CI Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 18, 24, 73, 74, 75, 83, 93, 95, 97, 98, 100, 108, 109, 110, 114, 120, 128, 129, 138, 139, 174, 150, 151, 154, 155, 167, 180, 185, and 213.

[0074] Blue or cyan pigments include CI Pigment Blue 1, 2, 14, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and the like.

[0075] Red or crimson pigments include CIPigment RED 1, 3, 5, 19, 21, 22, 31, 38, 42, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 50, 52, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 83, 90, 104, 108, 11 2, 114, 122, 144, 146, 148, 149, 150, 166, 168, 169, 170, 172, 173, 176, 177, 178, 184, 185, 187, 193, 202, 209, 214, 242, 254, 255, 264, 266, 269, CI Pigment Violet 19, etc.

[0076] Green pigments include CI Pigment Green 1, 2, 3, 4, 7, 8, 10, 15, 17, 26, 36, 45, 50, and the like.

[0077] Purple pigments include CI Pigment Violet 1, 2, 3, 4, 5:1, 12, 13, 15, 16, 17, 19, 23, 25, 29, 31, 32, 36, 37, 39, and 42. Orange pigments include CI Pigment Orange 13, 16, 20, 34, 36, 38, 39, 43, 51, 61, 63, 64, and 74.

[0078] In the present invention, the above pigments may be used alone or in combination of two or more.

[0079] In the present invention, the pigment can be used in any content as long as the desired concentration can be reproduced, and the content is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, relative to the total mass of the composition.

[0080] [resin] The active energy ray-curable composition of the present invention may further contain a resin (other than the above-mentioned rosin-modified compound).

[0081] The content of the resin is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 5 to 20% by mass, relative to the total mass of the composition.

[0082] From the viewpoint of adhesion and coating film resistance, the Mw of the resin is preferably from 5,000 to 30,000, and more preferably from 10,000 to 20,000.

[0083] The resin is not particularly limited, and known resins can be used. Specific examples include polyvinyl chloride, poly(meth)acrylic resin, polystyrene resin, styrene(meth)acrylic resin, epoxy resin, polyester resin, polyurethane resin, cellulose derivatives (e.g., ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride-vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, diallyl phthalate resin, alkyd resin, rosin-modified alkyd resin, petroleum resin, urea resin, and synthetic rubber such as butadiene-acrylonitrile copolymer.

[0084] (pigment dispersant) In the present invention, the composition preferably contains a pigment dispersant to improve pigment dispersibility. There are no particular limitations on the pigment dispersant, and known pigment dispersants can be used. Among these, resin-type pigment dispersants having a basic functional group are preferred, and examples of the basic functional group include primary, secondary, or tertiary amino groups, and nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine. Furthermore, as the skeleton constituting the resin-type pigment dispersant, a fatty acid amine skeleton and / or a urethane skeleton are more preferred since good pigment dispersibility can be easily obtained.

[0085] The pigment dispersant can be obtained from the Ajisper series (Ajisper PB821, PB822, PB824, etc.) manufactured by Ajinomoto Fine-Techno Co., Ltd., the Solsperse series (Solsperse 24000, Solsperse 32000, Solsperse 38500, etc.) manufactured by The Lubrizol Corporation, or the Disperbyk series (BYK-162, BYK-168, BYK-183, etc.) manufactured by BYK-Chemie.

[0086] The content of the pigment dispersant is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass, relative to the total mass of the composition.

[0087] [Sensitizer] In the present invention, the composition may contain a sensitizer to improve curability. There are no particular limitations on the sensitizer, and known sensitizers can be used. Specific examples include triethanolamine, methyldiethanolamine, triisopropanolamine, aliphatic amines, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and dibutylethanolamine.

[0088] The content of the sensitizer is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, relative to the total mass of the composition.

[0089] [wax] In the present invention, the composition preferably contains a wax to improve abrasion resistance, anti-blocking properties, smoothness, and scratch resistance. There are no particular limitations on the wax, and known waxes can be used. For example, natural waxes and synthetic waxes can be used. Examples of natural waxes include carnauba wax, Japan wax, lanolin, montan wax, paraffin wax, and microcrystalline wax. Examples of synthetic waxes include Fischer-Tropsch wax, polyethylene wax, polypropylene wax, and polytetrafluoroethylene wax.

[0090] The content of the wax is preferably 0.1 to 5% by mass relative to the total mass of the composition.

[0091] [Polymerization inhibitor] In the present invention, a polymerization inhibitor can be used in the composition to improve storage stability. As the polymerization inhibitor, a hindered phenol compound, a phenothiazine compound, a hindered amine compound, or a phosphorus compound is particularly preferably used. Specific examples include 4-methoxyphenol, hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, and aluminum salts of N-nitrosophenylhydroxylamine. Among these, it is preferable to contain a hindered phenol compound and / or a phenothiazine compound, and it is more preferable to contain 2,6-di-t-butyl-4-methylphenol and phenothiazine.

[0092] The content of the polymerization inhibitor is preferably 0.01 to 2% by mass relative to the total mass of the composition, from the viewpoint of maintaining curability and improving storage stability.

[0093] In the present invention, from the viewpoint of reducing the environmental load, the composition preferably contains substantially no organic solvent, which means that the organic solvent content is less than 3% by mass, more preferably less than 1% by mass, relative to the total mass of the composition.

[0094] (Biomass ratio) The Japan Organic Resources Association defines the biomass ratio as follows: Biomass ratio = ("dry weight of biomass used" ÷ "dry weight of product") x 100 Biomass mark certification requires a biomass content of 10% or more. In the present invention, the biomass degree is preferably 10% or more. The means for achieving a biomass degree of 10% or more is not particularly limited except for the inclusion of a rosin-modified compound, and known methods can be used.

[0095] <Laminate> When the active energy ray-curable composition is an active energy ray-curable ink, the laminate of the present invention can be obtained by printing the active energy ray-curable ink on a substrate and curing it with active energy rays. When the active energy ray-curable composition is an active energy ray-curable varnish, the laminate can be obtained by printing the active energy ray-curable varnish on a substrate, or by printing the active energy ray-curable varnish on a printed material in which ink is printed on a substrate, and curing it with active energy rays. The substrate is not particularly limited, and known substrates can be used. Specific examples include coated paper such as art paper, coated paper, and cast paper, uncoated paper such as fine paper, medium-quality paper, and newsprint, synthetic paper such as Yupo paper, and plastic films such as PET (polyethylene terephthalate), PP (polypropylene), and OPP (biaxially oriented polypropylene). Among these, good adhesion can be obtained to polyethylene, polypropylene, and polystyrene films.

[0096] As a specific application of the laminate of the present invention, it is preferably used for containers in which the substrate is a paper container or a plastic container, and particularly preferably for containers in which the substrate is a plastic container. By applying the laminate of the present invention to container applications, containers having sufficient coating resistance and being environmentally friendly can be obtained.

[0097] In the present invention, the method for printing the active energy ray-curable composition is not particularly limited, and known methods can be used, such as offset printing, flexographic printing, gravure printing, and screen printing.

[0098] In the present invention, the method for curing the active energy ray-curable composition is not particularly limited, and any known method for curing an active energy ray source can be used. Specific examples include mercury lamps, xenon lamps, metal hydride lamps, LEDs (light-emitting diodes) such as ultraviolet light-emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs), electron beams, and gas / solid-state lasers. [Example]

[0099] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0100] Details of the various measurements carried out in the following examples are as follows. (Weight average molecular weight) The weight-average molecular weight was measured using a gel permeation chromatography (HLC-8320) manufactured by Tosoh Corporation. A calibration curve was prepared using standard polystyrene samples. Tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M columns (manufactured by Tosoh Corporation) were used. Measurements were performed at a flow rate of 0.6 mL / min, an injection volume of 10 μL, and a column temperature of 40°C. (Rosin content) The rosin content was determined by the following formula: Rosin content = ("Dry mass of rosin acids used" ÷ "Dry mass of rosin-modifying compound") x 100

[0101] [Rosin-modified compound A] A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 48.1 parts of abietic acid and 15.6 parts of maleic anhydride, and heated at 180°C for 1 hour while blowing in nitrogen gas to obtain a reaction mixture. Then, as described above, gas chromatography-mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was complete. Next, 7.3 parts of bisphenol A, 4.7 parts of octanediol, 13.3 parts of 2,2-dimethyl-1,3-propanediol, 11.1 parts of 2-hydroxyethyl acrylate, and 0.1 parts of p-toluenesulfonic acid monohydrate as a catalyst were added to the reaction mixture, and a dehydration condensation reaction was carried out at 230°C for 12 hours to obtain a rosin-modified polyester compound A with a rosin content of 48.1% and three (meth)acroyl groups. The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 4500.

[0102] [Rosin modified compound B] A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 47.0 parts of abietic acid and 15.2 parts of maleic anhydride, and heated at 180°C for 1 hour while blowing in nitrogen gas to obtain a reaction mixture. Then, as described above, gas chromatography-mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was complete. Next, 7.1 parts of bisphenol A, 4.5 parts of octanediol, 12.9 parts of 2,2-dimethyl-1,3-propanediol, 13.2 parts of 2-acryloyloxyethyl isocyanate, and 0.1 parts of p-toluenesulfonic acid monohydrate as a catalyst were added to the reaction mixture, and a dehydration condensation reaction was carried out at 230°C for 12 hours to obtain a rosin-modified polyester compound B with a rosin content of 47.0% and three (meth)acryloyl groups. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 3,500.

[0103] [Rosin modified compound C] A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 50.2 parts of abietic acid and 18.2 parts of ditrimethylolpropane tetraacrylate, and the mixture was heated at 180°C for 1 hour while blowing in nitrogen gas to obtain a reaction mixture. Then, as described above, gas chromatography-mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was complete. Next, 9.5 parts of bisphenol A, 6.0 parts of 1,4-cyclohexanedimethanol, 4.3 parts of 2,2-dimethyl-1,3-propanediol, 11.8 parts of glycidyl acrylate, and 0.1 parts of p-toluenesulfonic acid monohydrate as a catalyst were added to the reaction mixture, and a dehydration condensation reaction was carried out at 230°C for 12 hours to obtain a rosin-modified polyester compound C with a rosin content of 50.2% and two (meth)acroyl groups. The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 7,600.

[0104] [Rosin-modified compound D] A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 50.3 parts of abietic acid and 18.2 parts of ditrimethylolpropane tetraacrylate, and the mixture was heated at 180°C for 1 hour while blowing in nitrogen gas to obtain a reaction mixture. Then, as described above, gas chromatography-mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was complete. Next, 9.5 parts of bisphenol A, 6.0 parts of 1,4-cyclohexanedimethanol, 4.3 parts of 2,2-dimethyl-1,3-propanediol, 11.7 parts of 2-acryloyloxyethyl isocyanate, and 0.1 parts of p-toluenesulfonic acid monohydrate as a catalyst were added to the reaction mixture, and a dehydration condensation reaction was carried out at 230°C for 12 hours to obtain a rosin-modified polyester compound D with a rosin content of 50.3% and two (meth)acryloyl groups. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 2100.

[0105] [Rosin-modified compound E] A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 26 parts of abietic acid and 13 parts of maleic anhydride, and heated to 180°C while blowing in nitrogen gas. Subsequently, 38 parts of benzoic acid, 23 parts of pentaerythritol, and 0.1 parts of p-toluenesulfonic acid monohydrate as a catalyst were added, and a dehydration condensation reaction was carried out at 230°C for 18 hours, yielding a rosin-modified compound E with a rosin content of 26%. The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 30,000.

[0106] [Rosin modified compound F] A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 50 parts of abietic acid and 15 parts of maleic anhydride, and heated to 180°C while blowing in nitrogen gas. Then, 35 parts of 3,3-dimethylolheptane and 0.1 parts of p-toluenesulfonic acid monohydrate as a catalyst were added, and a dehydration condensation reaction was carried out at 230°C for 18 hours, yielding rosin-modified compound F with a rosin content of 50.0%. The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 3,000.

[0107] [Rosin modified compound G] A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 10.8 parts of abietic acid, 21.0 parts of maleic anhydride, and 15.5 parts of 1,4-cyclohexanedicarboxylic acid, and the mixture was heated at 180°C for 1 hour while blowing in nitrogen gas to obtain a reaction mixture. Then, as described above, gas chromatography-mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was complete. Next, 18.9 parts of bisphenol A, 15.7 parts of 2,2-dimethyl-1,3-propanediol, 18.1 parts of 2-hydroxyethyl acrylate, and 0.1 parts of p-toluenesulfonic acid monohydrate as a catalyst were added to the reaction mixture, and a dehydration condensation reaction was carried out at 230°C for 12 hours to obtain a rosin-modified polyester compound G with a rosin content of 10.8% and two (meth)acroyl groups. The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 4000.

[0108] [Rosin modified compound H] A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 83.1 parts of abietic acid, 6.2 parts of pentaerythritol, 10.6 parts of 2-hydroxyethyl acrylate, and 0.1 parts of p-toluenesulfonic acid monohydrate as a catalyst, and a dehydration condensation reaction was carried out at 230°C for 12 hours to obtain a rosin-modified polyester compound H with a rosin content of 83.1% and two (meth)acroyl groups. The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 2100.

[0109] [Rosin Varnish A] A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 29.9 parts of Miramar M3130 and 0.1 parts of hydroquinone, and the temperature was raised to 110°C in the atmosphere. 70.0 parts of rosin-modified polyester compound A was gradually added and dissolved, yielding rosin varnish A.

[0110] Rosin varnishes B to H and varnish I were obtained in the same manner as rosin varnish A, except that the raw materials and amounts shown in Table 1 were used. The diallyl phthalate resin used in varnish I was Daiso DAP A manufactured by Osaka Soda Co., Ltd.

[0111] [Table 1]

[0112] Examples 1 to 31, Comparative Examples 1 to 8 [Method of producing active energy ray-curable composition 1] 20.0 parts of LIONOL BLUE FG-7330 as a colorant, 1.0 part of AJISPER PB821, 26.9 parts of ARONIX M-315 as a (meth)acrylate compound, 40.0 parts of rosin varnish A, 20.0 parts of varnish I as a (meth)acrylate compound, 3.0 parts of Omnirad379EG, 3.0 parts of KAYACURE DETX-S, and 0.1 parts of hydroquinone as a polymerization initiator were added, and the mixture was stirred and mixed using a butterfly mixer, and dispersed using a three-roll mill so that the maximum particle size was 15 μm or less, to prepare active energy ray-curable composition 1 with a biomass content of 13.5%.

[0113] [Method of producing active energy ray-curable compositions 2 to 35] Active energy ray-curable compositions 2 to 35 were obtained in the same manner as active energy ray-curable composition 1, except that the raw materials and amounts shown in Table 2 were changed. Note that the numerical values ​​in the table represent "parts by mass" unless otherwise specified, and blank spaces indicate that no ingredient was added. The active energy ray-curable compositions 1 to 23 and 25 to 35 are active energy ray-curable inks, and the active energy ray-curable composition 24 is an active energy ray-curable varnish.

[0114] [Table 2]

[0115] [Table 2]

[0116] [Table 2]

[0117] The abbreviations in Table 2 are as follows: [Pigment] LIONOL BLUE FG-7330: Toyo Color Co., Ltd., CI Pigment Blue 15:3 [Pigment dispersant] AJISPER PB821: Ajinomoto Fine-Techno Co., Ltd., comb-shaped dispersant containing basic functional groups [(Meth)acrylate compounds] Aronix M-315: Tris(2-hydroxyethyl) isocyanurate triacrylate, manufactured by Toagosei Co., Ltd. Ebecryl 1142: Ditrimethylolpropane tetraacrylate, manufactured by Daicel-Orkunex Corporation MIRAMER M220: Tripropylene glycol diacrylate, manufactured by Toyo Chemicals Co., Ltd. MIRAMER M3130: Toyo Chemicals Co., Ltd., trimethylolpropane EO-modified triacrylate MIRAMER M600: Dipentaerythritol hexaacrylate, manufactured by Toyo Chemicals Co., Ltd. [Polymerization initiator] Omnirad379EG: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl-1-butanone, manufactured by iGM RESINS KAYACURE DETX-S: 2,3-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd. [Polymerization inhibitor] Hydroquinone: Hydroquinone manufactured by Ube Industries, Ltd. [Silicon compounds] TegoRad2700: EVONIK silicone acrylate (acryloyl group 6) TegoRad2500: EVONIK silicone acrylate (acryloyl group 2) TegoRad2300: EVONIK silicone acrylate (acryloyl group 2) TegoRad2100: EVONIK silicone acrylate (acryloyl group 5) KP101: Polyether-modified silicone compound manufactured by Shin-Etsu Silicone SH28PA: Silicone oil manufactured by Toray Dow Corning TSF451-100: Momentive Japan silicone oil TSF451-100M: Momentive Japan silicone oil

[0118] The resulting compositions were evaluated by the following methods. The evaluation results for Examples 1 to 31 and Comparative Examples 1 to 8 are shown in Table 3.

[0119] [How to create a test sample] Using an RI tester (manufactured by Tester Sangyo Co., Ltd.), a solid image was printed using 0.25 ml of the resulting composition onto the substrates Denka styrene sheet (manufactured by Denka Co., Ltd.), PET sheet (manufactured by Mineron Chemical Industry Co., Ltd.), and expanded polystyrene (manufactured by Tomei Chemical Industry Co., Ltd.). The composition was then cured at a conveyor speed of 60 m / min using an LED lamp ("XP-9" manufactured by Air Motion Systems Co., Ltd., irradiation distance 10 mm, output 70%) to prepare a test sample. The RI tester is a testing machine that prints ink onto paper or film, and allows adjustment of the amount of ink transfer and printing pressure.

[0120] [Adhesion] Adhesive tape (Nichiban Cellotape (registered trademark), 18 mm wide) was applied to the printed layer of the test sample prepared by the above method, and the tape was peeled off in the vertical direction. The adhesion to the substrate was evaluated based on the percentage of the area of ​​the ink coating that had peeled off. A score of 3 or higher was considered to be at a level that is acceptable for practical use. 5: No peeling of the ink film 4: Less than 10% of the ink film has peeled off 3: Ink film peeling is 10% or more but less than 30% 2: Ink film peeling is 30% or more but less than 70% 1: 70% or more of the ink film has peeled off

[0121] [Chemical resistance] The coating film of the test sample prepared by the above method was rubbed back and forth 100 times with a cotton swab soaked in 99.5% ethanol, and the number of times the substrate was exposed was evaluated. A score of 3 or higher was considered to be at a level that is acceptable for practical use. 5: Over 100 times 4:75+ times 3:50+ times 2:25 or more times 1:24 times or less

[0122] [Table 3]

[0123] As shown in Table 3, Examples 1 to 31, which are active energy ray-curable compositions containing a (meth)acrylate compound, a polymerization initiator, a rosin-modified compound, and a silicon compound, and characterized in that the proportion of rosin-derived structural units in the rosin-modified compound is 20 to 80 mass % relative to all structural units constituting the rosin-modified compound, were all good and practically problem-free in terms of adhesion, chemical resistance, and printability. In Comparative Examples 1 and 3, in which the proportion of rosin-derived structural units was 20 mass% or less relative to the total structural units constituting the rosin-modified polyester compound, the adhesion was poor, while in Comparative Example 2, in which the proportion of rosin-derived structural units was 80 mass% or more relative to the total structural units constituting the rosin-modified polyester compound, the adhesion and chemical resistance were poor. In Comparative Examples 4, 5, 7, and 8, in which the silicon compound content was less than 0.1%, the adhesion and chemical resistance were poor. In Comparative Example 6, in which the silicon compound content was 10% or more, no transfer to the substrate occurred, and therefore the adhesion and chemical resistance could not be evaluated.

Claims

1. An active energy ray-curable composition comprising a (meth)acrylate compound (except when it is a silicon compound), a polymerization initiator, a rosin-modified polyester compound, and a silicon compound, the proportion of structural units derived from conjugated rosin acid in the rosin-modified polyester compound is 20 to 80% by mass based on the total structural units constituting the rosin-modified polyester compound; The silicon compound contains a non-reactive silicon-based compound having a polyorganosiloxane skeleton and / or a silicon (meth)acrylate, the content of the (meth)acrylate compound is 20 to 60% by mass relative to the total mass of the active energy ray-curable composition, the content of the polymerization initiator is 0.5 to 20% by mass relative to the total mass of the active energy ray-curable composition, the content of the rosin-modified polyester compound is 5 to 40% by mass based on the total mass of the active energy ray-curable composition, The active energy ray-curable composition is characterized in that the content of the silicon compound is 0.1 to 10 mass % based on the total mass of the active energy ray-curable composition.

2. 2. The active energy ray-curable composition according to claim 1, wherein the silicon compound comprises silicon (meth)acrylate.

3. An active energy ray-curable varnish comprising the active energy ray-curable composition according to claim 1 or 2.

4. An actinic ray-curable ink comprising the actinic ray-curable composition according to claim 1 or 2 and a colorant.

5. A laminate having a layer of the actinic ray-curable ink according to claim 4 cured by actinic ray on a substrate.

6. A laminate comprising a layer of the actinic ray-curable varnish according to claim 3 cured by actinic rays on a substrate or on the printed surface of a substrate having ink printed thereon.

7. 7. The laminate according to claim 5, wherein the substrate is a paper container or a plastic container.

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