JP7739780B2 - Active energy ray-curable composition and laminate - Google Patents

Description

The present invention relates to an active energy ray-curable composition and laminate containing a rosin-modified compound that exhibits good adhesion to a wide range of substrates and excellent chemical resistance of the cured coating film.

In recent years, active energy ray-curable compositions can be cured by short-term exposure to active energy rays such as ultraviolet light, visible light, and electron beams. This allows for high productivity and allows for the production of highly durable coatings, making them widely used in fields where durability is required.

However, when the substrate to be printed is plastic, active energy ray-curable compositions have the problem that they do not provide good adhesion to certain types of plastic, particularly olefin-based substrates such as polyethylene and polypropylene, which have low polarity, and polystyrene substrates, and various investigations are being conducted to address this issue.

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 in compositions with biomass-derived raw materials and increasing their proportion.

However, increasing the proportion of biomass-derived raw materials in active energy ray-curable compositions poses the problem of insufficient adhesion to the substrate or coating resistance, and various studies are being conducted to address this issue.

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, while the composition improves adhesion to acrylic and polyester substrates to some extent, it is still not sufficient, and there is a particular problem in that good adhesion cannot be obtained to olefin-based substrates such as polyethylene and polypropylene, which have low polarity, or polystyrene substrates.

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

For example, Patent Documents 3 and 4 disclose active energy ray-curable resin compositions that improve adhesion. However, while adhesion is improved, the coating film becomes flexible, and there is an issue that sufficient coating film resistance cannot be achieved. Furthermore, since biomass-derived raw materials are not used, it can be said that these compositions are not sufficiently environmentally friendly.

For example, Patent Documents 5 and 6 disclose printing ink compositions that use rosin-modified resins. However, although biomass-derived raw materials are used, there are issues in that the chemical resistance of the coating film is insufficient, and in particular, adhesion to plastic substrates such as polyethylene, polypropylene, and polystyrene is not achieved.

Japanese Patent Application Publication No. 3-215543 Japanese Patent Application Publication No. 8-143635 Japanese Patent Application Laid-Open No. 2004-339487 JP 2011-225751 A International Publication No. 2017/164246 JP 2019-116579 A

The problem that the present invention aims to solve is to provide an active energy ray-curable composition and laminate containing a rosin-modified compound that has good adhesion to a wide range of substrates and produces a cured coating film with excellent chemical resistance.

As a result of extensive research into resolving the above-mentioned problems, the inventors discovered that the above-mentioned problems could be resolved by the active energy ray-curable composition described below, leading to the completion of the present invention.

That is, the present invention provides an active energy ray-curable composition containing a (meth)acrylate compound (except when the (meth)acrylate compound 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 rosin-derived structural units in the rosin-modified compound is 20 to 80 mass % based on the total structural units constituting the rosin-modified compound.

The present invention also relates to the above-mentioned active energy ray-curable composition, characterized in that the content of the rosin-modified compound is 5 to 30 mass % based on the total mass of the active energy ray-curable composition.

The present invention also relates to the above-mentioned active energy ray-curable composition, 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.

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

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

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

The present invention also relates to a laminate having a layer of the above-mentioned active energy ray-curable ink cured by active energy rays on a substrate.

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.

The present invention also relates to the above laminate, wherein the substrate is a paper container or a plastic container.

The present invention provides an active energy ray-curable composition and laminate containing a rosin-modified compound that has good adhesion to a wide range of substrates and produces a cured coating film with excellent chemical resistance.

The following describes in detail the embodiments for implementing the present invention. Note that the present invention is not limited to the following embodiments, and can be implemented in various modifications within the scope of its gist.

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 ability to cause chemical changes, such as chemical reactions, in the irradiated object.

<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 the compound is a silicon compound), a polymerization initiator, a rosin-modified compound, and a silicon compound, wherein the rosin-modified compound contains rosin-derived structural units in an amount of 20 to 80 mass% relative to 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.

[(Meth)acrylate Compound]
The active energy ray-curable composition of the present invention contains a (meth)acrylate compound. The (meth)acrylate compound is not particularly limited, 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 or 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. 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.

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

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, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dipropylene Bifunctional (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.

(Meth)acrylate compounds such as urethane acrylate, polyester acrylate, and epoxy acrylate can also be used.

Urethane acrylates can be obtained, for example, by reacting a diisocyanate with a (meth)acrylate having a hydroxyl group, or 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 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.

Polyester acrylate can be obtained, for example, by reacting polyester polycarboxylic acid, which is obtained by polycondensation of polybasic acid and polyhydric alcohol, with a hydroxyl group-containing (meth)acrylate, etc.

Epoxy acrylates are, for example, those obtained by esterifying the glycidyl group of an epoxy resin with (meth)acrylic acid, resulting in a (meth)acrylate group as the functional group. Examples include (meth)acrylic acid adducts of bisphenol A-type epoxy resins and (meth)acrylic acid adducts of novolac-type epoxy resins.

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

Among these, it is preferable to include a di- to hexa-functional (meth)acrylate compound from the standpoint of adhesion and chemical resistance.

Furthermore, if a monofunctional (meth)acrylate compound is contained, from the viewpoint of chemical resistance, 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.

[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.

In the present invention, the photoradical polymerization initiator is not particularly limited, and known initiators can be used. Specific examples include benzophenone compounds, dialkoxyacetophenone compounds, α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, acylphosphine oxide compounds, and thioxanthone compounds.

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

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

Examples of the α-hydroxyalkylphenone compounds include 1-hydroxycyclohexyl phenyl 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.

Examples of the above-mentioned 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.

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

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

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

Among these, it is preferable to include α-aminoalkylphenone compounds and acylphosphine oxide compounds from the standpoint of adhesion and chemical resistance.

In the present invention, the content of the polymerization initiator is preferably 0.5 to 20% by mass, and more preferably 5 to 15% by mass, relative to the total mass of the composition.

[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 the "rosin content") is 20 to 80 mass % relative to the total structural units constituting the rosin-modified compound.

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% by mass based on the total structural units constituting the rosin-modified compound, and known compounds can be used. For example, the following rosin-modified resins can be used.

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 further reacting the carboxy group of the reactant 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 a hydroxyl group of a polyol, and then adding 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 having a carboxy group, and then reacting the carboxy group of the reaction compound with a hydroxyl group of a polyol, and then subjecting the remaining hydroxyl group to an addition reaction 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, and then subjecting a hydroxyl group of the reaction compound to an addition reaction 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 an ethylenically unsaturated double bond-containing compound.
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, and then adding 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.

The conjugated rosin acid used to obtain the rosin-modified compound of the present invention is a rosin acid having a conjugated double bond. As used herein, "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 conjugated double bonds found in aromatic compounds. In other words, the term "conjugated rosin acid" used herein refers to the above rosin acids, excluding hydrogenated rosin acid and other compounds that do not have conjugated double bonds.

Specific examples of conjugated rosin acids include abietic acid and its conjugated compounds, 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 above 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 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.

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 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 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 polyols may be used alone or in combination of two or more.

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 the ethylenically unsaturated double bond-containing compound having a carboxy group include acrylic acid, methacrylic acid, β-carboxylethyl (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.

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 fewer branches 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.

Examples of ethylenically unsaturated double bond-containing compounds 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.).

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.

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. Specific examples thereof include 2-ethylhexyl (meth)acrylate, 4-tert-butylcyclohexanol (meth)acrylate, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isoamyl (meth)acrylate, and the like. ) 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 (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) bifunctional (meth)acrylate compounds such as 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 tetra-functional (meth)acrylates are more preferred, since a resin structure with fewer branches is preferred from the viewpoint of flexibility of the coating film.

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

From the viewpoint of coating film strength, the rosin content of the above rosin-modified compound is more preferably 25 to 60% by mass.

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.

In the present invention, Mw was measured by gel permeation chromatography (hereinafter referred to as "GPC"). The specific GPC measurement method is as follows. An HLC-8020 manufactured by Tosoh Corporation was used, and a calibration curve was created using a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgel Super HM-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.

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

[Silicon compounds]
The active energy ray-curable composition of the present invention contains a silicon compound to develop adhesion and coating film resistance. The silicon compound is a non-reactive silicon compound or a silicon (meth)acrylate. The term "non-reactive" in the non-reactive silicon compound refers to the absence of reactive groups such as (meth)acryloyl groups, allyl groups, vinyl groups, and vinyl ether groups in its structure.
(Non-reactive silicon-based compounds)
The non-reactive silicon-based compound preferably has a polyorganosiloxane skeleton, more preferably a polydimethylsiloxane structure (I).

General formula (I) Polydimethylsiloxane

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 they can control the compatibility with (meth)acrylate compounds by adjusting the type and number of alkylene oxides added to the polyether chain. Preferred alkylene oxide types are polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol copolymers.

(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 within its structure. The polyorganosiloxane skeleton preferably has the polydimethylsiloxane structure (general formula (I)). Because silicon (meth)acrylate contains (meth)acryloyl groups within its structure, it can react with the (meth)acrylate compound in the composition upon exposure to active energy rays. From the viewpoint of reactivity, the number of (meth)acryloyl groups within one molecule is preferably 1 to 10, more preferably 2 to 6.

From the viewpoint of adhesion and coating strength, the content of the silicon compound is preferably 0.1 to 10 mass% and more preferably 2 to 7 mass% relative to the total mass of the active energy ray-curable composition.

[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.

[Colorant]
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.

The above-mentioned inorganic pigments include carbon blacks such as furnace black, lamp black, acetylene black, and channel black, as well as iron oxide and titanium oxide.

The above organic pigments include soluble azo pigments such as β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid anilide, acetoacetic acid anilide, and pyrazolone; 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.

More specifically, in terms of the C.I. Color Index, black pigments include C.I. Pigment Black 1, 6, 7, 9, 10, 11, 28, 26, and 31.

Examples of white pigments include C.I. Pigment White 5, 6, 7, 12, and 28.

Examples of yellow pigments include C.I. 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.

Blue or cyan pigments include C.I. Pigment Blue 1, 2, 14, 15, 15:1, 15:2, 15:3, 15:4, 60, and 62.

Red or crimson pigments include C.I. Pigment 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, 10 8, 112, 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, C.I. Pigment Violet 19, etc.

Examples of green pigments include C.I. Pigment Green 1, 2, 3, 4, 7, 8, 10, 15, 17, 26, 36, 45, and 50.

Examples of purple pigments include C.I. Pigment Violet 1, 2, 3, 4, 5:1, 12, 13, 15, 16, 17, 19, 23, 25, 29, 31, 32, 36, 37, 39, and 42.
Examples of orange pigments include C.I. Pigment Orange 13, 16, 20, 34, 36, 38, 39, 43, 51, 61, 63, 64, and 74.

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

In the present invention, the above pigments can be used in any content as long as the desired concentration can be reproduced, and it is preferably 5 to 30% by mass, and more preferably 10 to 25% by mass, based on the total mass of the composition.

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

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.

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

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.

(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.

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.

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.

[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.

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

[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.

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

[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.

From the viewpoint of maintaining curability while improving storage stability, the content of the polymerization inhibitor is preferably 0.01 to 2% by mass relative to the total mass of the composition.

In the present invention, it is preferable that the composition be substantially free of organic solvents from the perspective of reducing the environmental impact. "Substantially free" means that the organic solvent content is less than 3% by mass, and more preferably less than 1% by mass, relative to the total mass of the composition.

(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.

<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.

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.

In the present invention, there are no particular limitations on the method for printing the active energy ray-curable composition, and any known method can be used. Specific examples include offset printing, flexographic printing, gravure printing, and screen printing.

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.

The present invention will be explained 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.

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 a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgel Super HM-M columns (manufactured by Tosoh Corporation) were used. The measurement was performed under conditions of 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-modified compound") × 100

[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 nitrogen gas into the flask 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 having a rosin content of 48.1% and 3 (meth)acroyl groups. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 4,500.

[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 nitrogen gas into the flask 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 having a rosin content of 47.0% and 3 (meth)acryloyl groups. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 3,500.

[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 having 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.

[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 having 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 2,100.

[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 to obtain 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.

[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. Subsequently, 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 a 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.

[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 having 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 4,000.

[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 having 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 2,100.

[Rosin Varnish A]
A four-necked 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, thereby obtaining rosin varnish A.

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 listed in Table 1 were used. The diallyl phthalate resin used in varnish I was Daiso DAP A manufactured by Osaka Soda Co., Ltd.

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 Omnirad 379EG, 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 having a biomass content of 13.5%.

[Method of producing active energy ray-curable compositions 2 to 35]
Except for changing the raw materials and amounts shown in Table 2, active energy ray-curable compositions 2 to 35 were obtained in the same manner as active energy ray-curable composition 1. Note that, unless otherwise specified, the numerical values in the table represent "parts by mass," and blank spaces indicate that no compound 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.

The abbreviations in Table 2 are as follows:
[Pigment]
LIONOL BLUE FG-7330: C.I. Pigment Blue 15:3, manufactured by Toyocolor Co., Ltd.
[Pigment dispersant]
AJISPER PB821: Ajinomoto Fine-Techno Co., Ltd., comb-shaped dispersant containing a basic functional group [(meth)acrylate compound]
Aronix M-315: manufactured by Toagosei Co., Ltd., tris(2-hydroxyethyl) isocyanurate triacrylate; Ebecryl 1142: manufactured by Daicel-Orkunex Corporation, ditrimethylolpropane tetraacrylate; MIRAMER M220: manufactured by Toyo Chemicals Co., Ltd., tripropylene glycol diacrylate; MIRAMER M3130: manufactured by Toyo Chemicals Co., Ltd., trimethylolpropane EO-modified triacrylate; MIRAMER M600: manufactured by Toyo Chemicals Co., Ltd., dipentaerythritol hexaacrylate [polymerization initiator]
Omnirad 379EG: 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]
TegoRad 2700: Silicone acrylate (acryloyl group 6) manufactured by EVONIK
TegoRad 2500: Silicone acrylate (acryloyl group 2) manufactured by EVONIK
TegoRad 2300: Silicone acrylate (acryloyl group 2) manufactured by EVONIK
TegoRad 2100: Silicone acrylate (acryloyl group 5) manufactured by EVONIK
KP101: Polyether-modified silicone compound manufactured by Shin-Etsu Silicone SH28PA: Silicone oil manufactured by Toray Dow Corning TSF451-100: Silicone oil manufactured by Momentive Japan TSF451-100M: Silicone oil manufactured by Momentive Japan

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

[How to prepare test samples]
Using an RI tester (manufactured by Tester Sangyo Co., Ltd.), a solid image was printed in a volume of 0.25 ml onto the substrates of 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 on paper or film, and is capable of adjusting the amount of ink transfer and printing pressure.

[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 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 rating of 3 or higher was considered to be at a level that is acceptable for practical use.
5: No peeling of ink film 4: Peeling of ink film is less than 10% 3: Peeling of ink film is 10% or more but less than 30% 2: Peeling of ink film is 30% or more but less than 70% 1: Peeling of ink film is 70% or more

[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 until the substrate was exposed was evaluated. A score of 3 or more was evaluated as a level that is acceptable for practical use.
5: 100 times or more 4: 75 times or more 3: 50 times or more 2: 25 times or more 1: 24 times or less

As shown in Table 3, Examples 1 to 31, which were active energy ray-curable compositions containing a (meth)acrylate 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 was 20 to 80 mass % relative to all structural units constituting the rosin-modified compound, were all good and had no practical problems 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 (7)

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. The active energy ray-curable composition according to claim 1 , wherein the silicon compound comprises silicon (meth)acrylate. An active energy ray-curable varnish comprising the active energy ray-curable composition according to claim 1 or 2 . An actinic ray-curable ink comprising the actinic ray-curable composition according to claim 1 or 2 and a colorant. A laminate having a layer of the actinic ray-curable ink according to claim 4 cured by actinic ray on a substrate. 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. The laminate according to claim 5 , wherein the substrate is a paper container or a plastic container.