Active energy ray-curable composition and active energy ray-curable ink

Abstract

To provide an active energy ray-curable composition excellent in storage stability, and an active energy ray-curable ink containing the active energy ray-curable composition.SOLUTION: An active energy ray-curable composition contains a rosin-based resin (A), an active energy ray-curable monomer (B), and a metal scavenger (C). In the active energy ray-curable composition, even when the rosin-based resin (A) contains metal atoms, the metal atoms are captured by the metal scavenger (C). Therefore, generation of radicals derived from metal atoms is suppressed, and thickening and gelling of the active energy ray-curable composition can be suppressed. As a result, the active energy ray-curable composition has excellent storage stability.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an actinic energy ray-curable composition and an actinic energy ray-curable ink. [Background technology]

[0002] An active energy ray-curable composition is a composition that forms a cured film upon irradiation with active energy rays, and is widely used in the fields of, for example, inks, paints, and coating agents.

[0003] In general, an active energy ray-curable composition contains a resin and an active energy ray-curable monomer that dissolves the resin. As an active energy ray-curable composition, for example, an active energy ray-curable lithographic printing ink obtained by the following method is known.

[0004] More specifically, gum rosin and maleic anhydride are first subjected to a Diels-Alder addition reaction. Tetrahydrophthalic anhydride and 1,4-dicyclohexanedimethanol are then added to the reaction mixture, and dehydration condensation occurs to obtain a resin. The resin is then mixed with trimethylolpropane triacrylate to obtain a varnish. The varnish is then mixed with a pigment to obtain an actinic radiation-curable lithographic printing ink (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2020-066649 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the above-mentioned active energy ray-curable lithographic printing inks do not have sufficient storage stability.

[0007] The present invention relates to an active energy ray-curable composition having excellent storage stability, and an active energy ray-curable ink containing the active energy ray-curable composition. [Means for solving the problem]

[0008] The present invention [1] includes an active energy ray-curable composition containing a rosin-based resin (A), an active energy ray-curable monomer (B), and a metal capture agent (C).

[0009] The present invention [2] includes the active energy ray-curable composition according to the above [1], in which the metal scavenger (C) includes a phosphorus-containing scavenger.

[0010] The present invention [3] includes an actinic ray-curable ink containing the actinic ray-curable composition described in [1] or [2] above. [Effects of the Invention]

[0011] The active energy ray-curable composition of the present invention contains a rosin resin (A), an active energy ray-curable monomer (B), and a metal capture agent (C), and therefore has excellent storage stability.

[0012] The active energy ray-curable ink of the present invention contains the above-mentioned active energy ray-curable composition, and therefore has excellent storage stability. DETAILED DESCRIPTION OF THE INVENTION

[0013] The active energy ray-curable composition of the present invention contains a rosin resin (A), an active energy ray-curable monomer (B), and a metal scavenger (C).

[0014] The rosin-based resin (A) is a resin obtained by using rosins as raw materials, that is, the raw material components of the rosin-based resin (A) contain rosins.

[0015] Examples of rosins include unmodified rosin and modified rosin.

[0016] An example of unmodified rosin is natural rosin. Natural rosin is a natural resin containing resin acid as the main component. Resin acid is a compound having a carboxyl group derived from trees. Examples of resin acids include resin acids with conjugated double bonds and resin acids without conjugated double bonds. Examples of resin acids with conjugated double bonds include abietic acid, palustric acid, neoabietic acid, and levopimaric acid. Examples of resin acids without conjugated double bonds include dehydroabietic acid, dihydroabietic acid, and tetrahydroabietic acid. More specific examples of natural rosins include tall oil rosin, gum rosin, and wood rosin. These can be used alone or in combination of two or more types.

[0017] The rosin modified product is a modified product of the unmodified rosin described above. Examples of the rosin modified product include acid-modified rosin and stabilized rosin. Acid-modified rosin can be obtained, for example, by reacting the unmodified rosin described above with a known α,β-unsaturated carboxylic acid. Stabilized rosin is a modified product obtained by stabilizing the unmodified rosin described above. The stabilization treatment is a treatment that reduces or eliminates the conjugated double bonds in the resin acid having the conjugated double bonds described above. More specific examples of the stabilization treatment include hydrogenation, disproportionation, and polymerization, and preferably hydrogenation and disproportionation. That is, examples of stabilized rosin include hydrogenated rosin obtained by hydrogenating natural rosin, disproportionated rosin obtained by disproportionating natural rosin, and polymerized rosin obtained by polymerizing natural rosin. Furthermore, stabilized rosin also includes a hydrogenated polymerized rosin. These can be used alone or in combination of two or more types.

[0018] These rosins can be used alone or in combination of two or more. Preferred examples of the rosins include natural rosin used alone and stabilized rosin used alone.

[0019] Rosins usually contain metal atoms as unavoidable impurities. Examples of metal atoms include iron, copper, zinc, aluminum, and magnesium. The content of metal atoms relative to the rosin is not particularly limited, and is, for example, more than 0 ppm and 1000 ppm or less.

[0020] The rosin-based resin (A) is not particularly limited as long as it is a resin obtained using rosins as a raw material. More specific examples of the rosin-based resin (A) include rosin-modified polyester resins, rosin-modified alkyd resins, rosin-modified phenolic resins, rosin-modified acrylic resins, and epoxy-modified rosin resins. These can be used alone or in combination of two or more. A preferred example of the rosin-based resin (A) is rosin-modified polyester resin.

[0021] The rosin-modified polyester resin is, for example, a reaction product of a rosin, a carboxyl group-containing compound, and a hydroxyl group-containing compound.

[0022] Carboxy group-containing compounds include, for example, polybasic acids and monobasic acids.

[0023] Polybasic acids are compounds having two or more carboxyl groups in one molecule, and anhydrides thereof. Examples of polybasic acids include dibasic acids, tribasic acids, and tetrabasic acids. Preferred examples of polybasic acids include dibasic acids.

[0024] Dibasic acids are compounds containing two carboxyl groups in one molecule, and their anhydrides. Examples of dibasic acids include saturated dibasic acids and unsaturated dibasic acids.

[0025] Examples of saturated dibasic acids include saturated aliphatic dibasic acids (chain saturated aliphatic dibasic acids) and saturated alicyclic dibasic acids. Examples of saturated aliphatic dibasic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, ethylsuccinic acid, dimethylmalonic acid, α-methylglutaric acid, β-methylglutaric acid, 2,4-diethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, icosanedicarboxylic acid, decylsuccinic acid, dodecylsuccinic acid, and anhydrides thereof. Examples of saturated alicyclic dibasic acids include 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,4-cyclohexanediacetic acid, hexahydrophthalic acid, and anhydrides thereof. These can be used alone or in combination of two or more.

[0026] Examples of unsaturated dibasic acids include unsaturated aliphatic dibasic acids (linear unsaturated aliphatic dibasic acids), unsaturated alicyclic dibasic acids, and aromatic dibasic acids. Examples of unsaturated aliphatic dibasic acids include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, and anhydrides thereof. Examples of unsaturated alicyclic dibasic acids include tetrahydrophthalic acid, cyclopentene-1,2-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, methylcyclohexene-1,2-dicarboxylic acid, and anhydrides thereof. Examples of aromatic dibasic acids include phenylmalonic acid, phenylsuccinic acid, phthalic acid, isophthalic acid, terephthalic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, and naphthalenedicarboxylic acid. These can be used alone or in combination of two or more.

[0027] A monobasic acid is a compound having one carboxy group per molecule. Examples of monobasic acids include aliphatic monocarboxylic acids and aromatic monocarboxylic acids. Examples of aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, and tall fatty acids. Examples of aromatic monocarboxylic acids include benzoic acid, methylbenzoic acid, para-t-butylbenzoic acid, orthobenzoylbenzoic acid, and naphthoic acid. Further, examples of monocarboxylic acids include fatty acids. Examples of fatty acids include coconut oil fatty acids, soybean oil fatty acids, and palm kernel oil fatty acids. These can be used alone or in combination.

[0028] As the carboxyl group-containing compound, a polybasic acid may preferably be used alone or in combination with a monobasic acid, the ratio of which may be appropriately determined depending on the purpose and application.

[0029] Examples of the hydroxyl group-containing compound include polyols and monools.

[0030] A polyol is a compound having two or more hydroxyl groups in one molecule. Examples of polyols include dihydric alcohols, trihydric alcohols, and tetrahydric alcohols. Preferred examples of polyols include dihydric alcohols and trihydric alcohols.

[0031] Dihydric alcohols are compounds having two hydroxyl groups per molecule. Examples of dihydric alcohols include ethylene glycol, 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 4,4'-dihydroxyphenylpropane, 4,4'-dihydroxymethylmethane, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, bisphenol A, and bisphenol F. Further examples of dihydric alcohols include polyoxyalkylene diols obtained by adding alkylene oxides to these dihydric alcohols. Examples of alkylene oxides include ethylene oxide and propylene oxide. These can be used alone or in combination.

[0032] Trihydric alcohols are compounds having three hydroxyl groups in one molecule. Examples of trihydric alcohols include glycerin, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2,3,4-pentanetriol, and 1,2,5-hexanetriol. Further examples of trihydric alcohols include polyoxyalkylenetriols obtained by adding alkylene oxides to these trihydric alcohols. These can be used alone or in combination of two or more types.

[0033] A monool is a compound having one hydroxyl group per molecule. Examples of monools include methanol, ethanol, 1-propanol, 2-propanol, isopropanol, butanol, 2-ethylhexyl alcohol, alkenyl alcohol, 2-propen-1-ol, and 3,7-dimethyl-1,6-octadien-3-ol. These can be used alone or in combination of two or more.

[0034] As the hydroxyl group-containing compound, preferably, a polyol is used alone or in combination with a monool, and the ratio of the polyol and the monool used in combination is appropriately set depending on the purpose and application.

[0035] The method for reacting the rosin, the carboxyl group-containing compound, and the hydroxyl group-containing compound is not particularly limited, and any known method can be used.

[0036] For example, when unmodified rosin is used as the rosin, an unsaturated dibasic acid is preferably used as the carboxyl group-containing compound, and a polyol is preferably used as the hydroxyl group-containing compound.

[0037] In such cases, rosins and unsaturated dibasic acids are first subjected to an addition reaction by a known method. In the addition reaction, for example, a Diels-Alder reaction is carried out between the conjugated double bonds contained in the resin acid of the rosins and the unsaturated bonds of the unsaturated dibasic acids. This results in a rosin modification (acid-modified rosin) having carboxy groups as the reaction product of the rosins and the unsaturated dibasic acids.

[0038] Then, in this method, the rosin modified product having a carboxy group (acid-modified rosin) and a hydroxyl group-containing compound are subjected to a dehydration condensation reaction by a known method. This results in a rosin-modified polyester resin as a reaction product of the rosin modified product having a carboxy group (acid-modified rosin) and the hydroxyl group-containing compound. More specifically, an acid-modified rosin-modified polyester resin is obtained.

[0039] In the production of the acid-modified rosin-modified polyester resin, the blending ratio of the rosins, the carboxyl group-containing compound, and the hydroxyl group-containing compound is not particularly limited and may be appropriately set depending on the purpose and application.

[0040] For example, the amount of rosins is, for example, 20 parts by mass or more, preferably 30 parts by mass or more, per 100 parts by mass of the total amount of rosins, carboxyl group-containing compounds, and hydroxyl group-containing compounds, and the amount of rosins is, for example, 80 parts by mass or less, preferably 70 parts by mass or less, per 100 parts by mass of the total amount of rosins, carboxyl group-containing compounds, and hydroxyl group-containing compounds.

[0041] The amount of the carboxyl group-containing compound is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, relative to 100 parts by mass of the total amount of the rosins, carboxyl group-containing compound, and hydroxyl group-containing compound. The amount of the carboxyl group-containing compound is, for example, 50 parts by mass or less, preferably 40 parts by mass or less, and more preferably 20 parts by mass or less, relative to 100 parts by mass of the total amount of the rosins, carboxyl group-containing compound, and hydroxyl group-containing compound.

[0042] For example, the amount of the hydroxyl group-containing compound is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, relative to 100 parts by mass of the total amount of the rosins, carboxyl group-containing compound, and hydroxyl group-containing compound. For example, the amount of the hydroxyl group-containing compound is, for example, 40 parts by mass or less, preferably 30 parts by mass or less, relative to 100 parts by mass of the total amount of the rosins, carboxyl group-containing compound, and hydroxyl group-containing compound.

[0043] Furthermore, for example, when stabilized rosin is used as the rosin, an unsaturated dibasic acid is preferably used as the carboxyl group-containing compound, and an aromatic monocarboxylic acid is used in combination as needed. Furthermore, a dihydric alcohol and a trihydric alcohol are preferably used as the hydroxyl group-containing compound.

[0044] More specifically, the content of conjugated double bonds in stabilized rosin is reduced by the stabilization treatment, and therefore, when stabilized rosin is used as the rosin, the Diels-Alder reaction between the rosin and the unsaturated dibasic acid is reduced.

[0045] Therefore, in this method, a rosin, a carboxy group-containing compound, and a hydroxy group-containing compound are subjected to a dehydration condensation reaction by a known method. More specifically, a carboxy group contained in the resin acid of the rosin, a carboxy group contained in the carboxy group-containing compound, and a hydroxy group contained in the hydroxy group-containing compound are subjected to a dehydration condensation reaction. This results in a rosin-modified polyester resin as a reaction product of the rosin, the carboxy group-containing compound, and the hydroxy group-containing compound. More specifically, a stabilized rosin-modified polyester resin is obtained.

[0046] In the production of the stabilized rosin-modified polyester resin, the blending ratio of the rosins, the carboxyl group-containing compound, and the hydroxyl group-containing compound is not particularly limited and may be appropriately set depending on the purpose and application.

[0047] For example, the amount of rosins is, for example, 20 parts by mass or more, preferably 30 parts by mass or more, per 100 parts by mass of the total amount of rosins, carboxyl group-containing compounds, and hydroxyl group-containing compounds, and the amount of rosins is, for example, 80 parts by mass or less, preferably 70 parts by mass or less, per 100 parts by mass of the total amount of rosins, carboxyl group-containing compounds, and hydroxyl group-containing compounds.

[0048] Furthermore, the amount of the carboxyl group-containing compound is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, relative to 100 parts by mass of the total amount of the rosins, carboxyl group-containing compound, and hydroxyl group-containing compound. Furthermore, the amount of the carboxyl group-containing compound is, for example, 50 parts by mass or less, preferably 40 parts by mass or less, relative to 100 parts by mass of the total amount of the rosins, carboxyl group-containing compound, and hydroxyl group-containing compound.

[0049] For example, the amount of the hydroxyl group-containing compound is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, relative to 100 parts by mass of the total amount of the rosins, carboxyl group-containing compound, and hydroxyl group-containing compound. For example, the amount of the hydroxyl group-containing compound is, for example, 40 parts by mass or less, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, relative to 100 parts by mass of the total amount of the rosins, carboxyl group-containing compound, and hydroxyl group-containing compound.

[0050] As the rosin-based resin (A), preferably, a rosin-modified polyester resin is used, and more preferably, an acid-modified rosin-modified polyester resin and a stabilized rosin-modified polyester resin are used.

[0051] The rosin-based resin (A) can be used alone or in combination of two or more types. For example, an acid-modified rosin-modified polyester resin may be used alone, or a stabilized rosin-modified polyester resin may be used alone, or these may be used in combination. Preferably, an acid-modified rosin-modified polyester resin is used alone. Also preferably, a stabilized rosin-modified polyester resin is used alone.

[0052] In the rosin-based resin (A), the content ratios of the skeleton derived from rosins, the skeleton derived from a carboxy group-containing compound, and the skeleton derived from a hydroxy group-containing compound are not particularly limited and may be appropriately set depending on the purpose and application.

[0053] For example, the content of the rosin-derived skeleton relative to the total amount of the rosin-based resin (A) is, for example, 20% by mass or more, preferably 30% by mass or more, and the content of the rosin-derived skeleton relative to the total amount of the rosin-based resin (A) is, for example, 80% by mass or less, preferably 70% by mass or less.

[0054] The content of the skeleton derived from the carboxyl group-containing compound relative to the total amount of the rosin resin (A) is, for example, 5% by mass or more, or preferably 10% by mass or more, and the content of the skeleton derived from the carboxyl group-containing compound relative to the total amount of the rosin resin (A) is, for example, 50% by mass or less, or preferably 40% by mass or less.

[0055] The content of the skeleton derived from the hydroxyl group-containing compound relative to the total amount of the rosin resin (A) is, for example, 5% by mass or more, preferably 10% by mass or more, and the content of the skeleton derived from the hydroxyl group-containing compound relative to the total amount of the rosin resin (A) is, for example, 40% by mass or less, preferably 30% by mass or less.

[0056] The active energy ray-curable monomer (B) is a compound having one or more photopolymerizable groups that can be polymerized by irradiation with active energy rays. More specifically, the active energy ray-curable monomer (B) may be a photopolymerizable functional group-containing compound. Examples of the photopolymerizable functional group-containing compound include a photopolymerizable monofunctional compound having one photopolymerizable group in one molecule, and a photopolymerizable polyfunctional compound having two or more photopolymerizable groups in one molecule.

[0057] Examples of the photopolymerizable monofunctional compound include styrenes and mono(meth)acrylates. Examples of the styrenes include styrene, α-methylstyrene, and vinyltoluene. Examples of mono(meth)acrylates include 2-hydroxyethyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, cyclohexyl(meth)acrylate, isooctyl(meth)acrylate, isomyristyl(meth)acrylate, isostearyl(meth)acrylate, isobornyl(meth)acrylate, ethoxydiethylene glycol(meth)acrylate, 2-ethylhexylcarbitol(meth)acrylate, neopentyl glycol benzoate(meth)acrylate, nonylphenoxypolyethylene glycol(meth)acrylate, epichlorohydrin (ECH)-modified phenoxy(meth)acrylate, phenoxyethyl(meth)acrylate, paracumylphenol ethylene oxide-modified(meth)acrylate, vinylpyrrolidone, vinylcaprolactam, and acryloylmorpholine. Incidentally, (meth)acrylate refers to acrylate and / or methacrylate.

[0058] Examples of photopolymerizable polyfunctional compounds include photopolymerizable bifunctional compounds having two photopolymerizable groups in one molecule, photopolymerizable trifunctional compounds having three photopolymerizable groups in one molecule, photopolymerizable tetrafunctional compounds having four photopolymerizable groups in one molecule, photopolymerizable pentafunctional compounds having five photopolymerizable groups in one molecule, and photopolymerizable hexafunctional compounds having six photopolymerizable groups in one molecule.

[0059] Examples of the photopolymerizable bifunctional compound include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dicyclopentadiene di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, pentaerythritol di(meth)acrylate, bisphenol A ethylenediamine diol, oxide addition diacrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, divinylbenzene, butanediol-1,4-divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether dipropylene glycol divinyl ether, hexanediol divinyl ether, triethylene glycol divinyl ether, phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer (trade name "AH-600" manufactured by Kyoeisha Chemical Co., Ltd.), phenyl glycidyl ether acrylate toluene diisocyanate urethane prepolymer (trade name "AT-600" manufactured by Kyoeisha Chemical Co., Ltd.), and alkylene oxide-modified versions of these.

[0060] Examples of photopolymerizable trifunctional compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris((meth)acryloxyethyl)isocyanurate, tri(meth)acrylate of alkylene oxide modified isocyanuric acid, and alkylene oxide modified versions of these.

[0061] Examples of photopolymerizable tetrafunctional compounds include ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and alkylene oxide modified versions of these compounds.

[0062] Examples of photopolymerizable pentafunctional compounds include dipentaerythritol penta(meth)acrylate and alkylene oxide modified products thereof.

[0063] Examples of photopolymerizable hexafunctional compounds include dipentaerythritol hexa(meth)acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (trade name "UA-306H" manufactured by Kyoeisha Chemical Co., Ltd.), caprolactone-modified dipentaerythritol hexa(meth)acrylate, and alkylene oxide-modified versions of these compounds.

[0064] These active energy ray-curable monomers (B) can be used alone or in combination of two or more. As the active energy ray-curable monomer (B), a photopolymerizable trifunctional compound is preferably used, and trimethylolpropane tri(meth)acrylate (TMPT(M)A) is more preferably used.

[0065] The metal scavenger (C) is a compound capable of capturing metal atoms contained in rosins. Examples of the metal scavenger (C) include a carboxy group-containing scavenger, an aminocarboxy group-containing scavenger, and a phosphorus-containing scavenger.

[0066] Examples of carboxyl group-containing scavenger include oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, gluconic acid, oxalacetic acid, and salts thereof. These can be used alone or in combination of two or more. A preferred carboxyl group-containing scavenger is gluconic acid.

[0067] Examples of aminocarboxy group-containing scavengers include trinitric acid, ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, nitrilotriacetic acid, N-hydroxyethylenediamine-N,N',N'-triacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, tetraethylenetetraminehexaacetic acid, hydroxyethyliminodiacetic acid, N,N-di(2-hydroxyethyl)glycine, iminodiacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, and salts thereof. These can be used alone or in combination of two or more.

[0068] Examples of phosphorus-containing scavengers include phosphate group-containing scavengers and phosphonic acid group-containing scavengers. Examples of phosphate group-containing scavengers include pyrophosphoric acid, polyphosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, hexametaphosphoric acid, phytic acid, and salts thereof. Examples of phosphonic acid group-containing scavengers include phosphonic acid, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid (etidronic acid), ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and salts thereof. These can be used alone or in combination of two or more. Preferred examples of phosphorus-containing scavengers include phosphate group-containing scavengers and phosphonic acid group-containing scavengers, and more preferred examples include phytic acid, etidronic acid, and salts thereof.

[0069] The metal capture agent (C) can be used alone or in combination of two or more kinds. From the viewpoint of compatibility with the rosin-based resin (A) and the active energy ray-curable monomer (B), a phosphorus-containing capture agent is preferably used as the metal capture agent (C).

[0070] The active energy ray-curable composition can be obtained by mixing the rosin resin (A), the active energy ray-curable monomer (B), and the metal capture agent (C) by a known method.

[0071] The blending ratio of the rosin-based resin (A), the active energy ray-curable monomer (B), and the metal capture agent (C) is appropriately set depending on the purpose and application. For example, the mass ratio of the three components, rosin-based resin (A), the active energy ray-curable monomer (B), and the metal capture agent (C), is as follows:

[0072] That is, the amount of the rosin resin (A) is, for example, 20 parts by mass or more, preferably 30 parts by mass or more, and more preferably 35 parts by mass or more, per 100 parts by mass of the total amount of the rosin resin (A), the active energy ray-curable monomer (B), and the metal capture agent (C). Also, the amount of the rosin resin (A) is, for example, 80 parts by mass or less, preferably 60 parts by mass or less, and more preferably 45 parts by mass or less, per 100 parts by mass of the total amount of the rosin resin (A), the active energy ray-curable monomer (B), and the metal capture agent (C).

[0073] Furthermore, the amount of the active energy ray-curable monomer (B) is, for example, 20 parts by mass or more, preferably 40 parts by mass or more, and more preferably 55 parts by mass or more, relative to 100 parts by mass of the total amount of the rosin-based resin (A), the active energy ray-curable monomer (B), and the metal capture agent (C). Furthermore, the amount of the active energy ray-curable monomer (B) is, for example, 80 parts by mass or less, preferably 70 parts by mass or less, and more preferably 65 parts by mass or less, relative to 100 parts by mass of the total amount of the rosin-based resin (A), the active energy ray-curable monomer (B), and the metal capture agent (C).

[0074] The amount of the metal capture agent (C) is, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more, relative to 100 parts by mass of the total amount of the rosin resin (A), the active energy ray-curable monomer (B), and the metal capture agent (C). The amount of the metal capture agent (C) is, for example, 5 parts by mass or less, preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the total amount of the rosin resin (A), the active energy ray-curable monomer (B), and the metal capture agent (C).

[0075] For example, the mass ratio of the two components, the rosin resin (A) and the active energy ray-curable monomer (B), is as follows:

[0076] That is, the amount of the rosin resin (A) is, for example, 20 parts by mass or more, preferably 30 parts by mass or more, and more preferably 35 parts by mass or more, per 100 parts by mass of the total of the rosin resin (A) and the active energy ray-curable monomer (B). Also, the amount of the rosin resin (A) is, for example, 80 parts by mass or less, preferably 60 parts by mass or less, and more preferably 45 parts by mass or less, per 100 parts by mass of the total of the rosin resin (A) and the active energy ray-curable monomer (B).

[0077] Furthermore, the amount of the active energy ray-curable monomer (B) is, for example, 20 parts by mass or more, preferably 40 parts by mass or more, and more preferably 55 parts by mass or more, relative to 100 parts by mass of the total of the rosin resin (A) and the active energy ray-curable monomer (B). Furthermore, the amount of the active energy ray-curable monomer (B) is, for example, 80 parts by mass or less, preferably 70 parts by mass or less, and more preferably 65 parts by mass or less, relative to 100 parts by mass of the total of the rosin resin (A) and the active energy ray-curable monomer (B).

[0078] The ratio of the metal capture agent (C) to the rosin resin (A) and the active energy ray-curable monomer (B) is as follows:

[0079] That is, the amount of the metal capture agent (C) is, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more, relative to 100 parts by mass of the total of the rosin resin (A) and the active energy ray-curable monomer (B). Also, the amount of the metal capture agent (C) is, for example, 5 parts by mass or less, preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the total of the rosin resin (A) and the active energy ray-curable monomer (B).

[0080] The active energy ray-curable composition may contain known additives as needed.

[0081] Examples of additives include polymerization inhibitors, fillers, thickeners, foaming agents, antioxidants, light stabilizers, heat stabilizers, and flame retardants. These can be used alone or in combination of two or more. A preferred additive is a polymerization inhibitor.

[0082] Examples of the polymerization inhibitor include hydroquinone, methoxyphenol, methylhydroquinone, 2-tertiary butylhydroquinone, p-benzoquinone, tertiary butyl p-benzoquinone, and phenothiazine. These polymerization inhibitors can be used alone or in combination of two or more. A preferred polymerization inhibitor is hydroquinone.

[0083] These additives can be used alone or in combination of two or more. The amount and timing of addition of the additives are not particularly limited and can be appropriately determined depending on the purpose and application.

[0084] Such an active energy ray-curable composition contains a rosin resin (A), an active energy ray-curable monomer (B), and a metal capture agent (C), and therefore the active energy ray-curable composition has excellent storage stability.

[0085] More specifically, when an active energy ray-curable composition contains a rosin-based resin (A) and an active energy ray-curable monomer (B), the active energy ray-curable composition is usually prone to thickening and gelation upon storage.

[0086] The mechanism is presumed to be as follows. Specifically, the rosin-based resin (A) contains double bonds derived from the raw material rosins. Therefore, storage of the active energy ray-curable composition may oxidize the double bonds and generate peroxides. Furthermore, the rosins used as raw materials for the rosin-based resin (A) may contain metal atoms (such as iron). In other words, the rosin-based resin (A) may contain metal atoms.

[0087] Therefore, peroxides generated by storage of the rosin-based resin (A) may be decomposed by metal atoms, resulting in the generation of radicals, which may then polymerize the active energy ray-curable composition, causing it to thicken and gel.

[0088] In contrast, the active energy ray-curable composition of the present invention contains a rosin resin (A) and an active energy ray-curable monomer (B), and further contains a metal capture agent (C).

[0089] In such an active energy ray-curable composition, even when the rosin resin (A) contains metal atoms, the metal atoms are captured by the metal capture agent (C), thereby suppressing the generation of radicals derived from the metal atoms and inhibiting polymerization of the active energy ray-curable composition.

[0090] As a result, thickening and gelation of the active energy ray-curable composition can be suppressed. That is, the active energy ray-curable composition has excellent storage stability.

[0091] Such an active energy ray-curable composition forms a cured film upon irradiation with active energy rays. Therefore, the active energy ray-curable composition is suitably used in, for example, the fields of inks, paints, and coating agents. In particular, the active energy ray-curable composition is suitably used as a varnish for an active energy ray-curable ink.

[0092] That is, the active energy ray-curable ink contains the above-mentioned active energy ray-curable composition. The active energy ray-curable ink may also contain a pigment, if necessary.

[0093] Pigments are not particularly limited, but include inorganic and organic pigments. Examples of inorganic pigments include yellow lead, zinc yellow, Prussian blue, barium sulfate, cadmium red, titanium oxide, zinc white, red iron oxide, alumina white, calcium carbonate, ultramarine, carbon black, graphite, aluminum powder, and red iron oxide. Examples of organic pigments include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, threne pigments, thioindigo pigments, anthraquinone pigments, perinone pigments, perylene pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, metal complex pigments, and quinophthalone pigments. These pigments can be used alone or in combination.

[0094] In the active energy ray-curable ink, the content ratio of the pigment is not particularly limited and is appropriately set depending on the purpose and use. For example, the content ratio of the pigment is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, relative to 100 parts by mass of the total amount of the active energy ray-curable composition. Furthermore, the content ratio of the pigment is, for example, 250 parts by mass or less, preferably 150 parts by mass or less, relative to 100 parts by mass of the total amount of the active energy ray-curable composition.

[0095] Furthermore, for example, the amount of the active energy ray-curable composition is, for example, 30 parts by mass or more, preferably 40 parts by mass or more, per 100 parts by mass of the total amount of the active energy ray-curable composition and the pigment. Furthermore, the amount of the active energy ray-curable composition is, for example, 95 parts by mass or less, preferably 90 parts by mass or less, per 100 parts by mass of the total amount of the active energy ray-curable composition and the pigment. Furthermore, the amount of the pigment is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, per 100 parts by mass of the total amount of the active energy ray-curable composition and the pigment. Furthermore, the amount of the pigment is, for example, 70 parts by mass or less, preferably 60 parts by mass or less, per 100 parts by mass of the total amount of the active energy ray-curable composition and the pigment.

[0096] Furthermore, the active energy ray-curable ink may further contain an active energy ray-curable monomer (B) in addition to the active energy ray-curable composition, if necessary.

[0097] In the active energy ray-curable ink, the content ratio of the active energy ray-curable monomer (B) is not particularly limited and is appropriately set depending on the purpose and application. For example, the content ratio of the active energy ray-curable monomer (B) is, for example, 1 part by mass or more, preferably 2 parts by mass or more, per 100 parts by mass of the total amount of the active energy ray-curable composition. Furthermore, the content ratio of the active energy ray-curable monomer (B) is, for example, 45 parts by mass or less, preferably 35 parts by mass or less, per 100 parts by mass of the total amount of the active energy ray-curable composition.

[0098] Furthermore, the active energy ray-curable ink may further contain a known photopolymerization initiator, if necessary.

[0099] The photopolymerization initiator is not particularly limited, and examples thereof include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, benzophenone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methyl-propan-1-one. These can be used alone or in combination of two or more.

[0100] In the active energy ray-curable ink, the content ratio of the photopolymerization initiator is not particularly limited and is appropriately set depending on the purpose and application. For example, the content ratio of the photopolymerization initiator is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, relative to 100 parts by mass of the total amount of the active energy ray-curable composition. Furthermore, the content ratio of the photopolymerization initiator is, for example, 20 parts by mass or less, preferably 15 parts by mass or less, relative to 100 parts by mass of the total amount of the active energy ray-curable composition.

[0101] The active energy ray-curable ink may further contain known additives as needed. Examples of additives include curing accelerators, fillers, thickeners, foaming agents, antioxidants, light stabilizers, heat stabilizers, and flame retardants. These may be used alone or in combination of two or more. The amount and timing of addition of the additives are not particularly limited and may be appropriately determined depending on the purpose and application.

[0102] Such an active energy ray-curable ink contains the above-mentioned active energy ray-curable composition, and therefore has excellent storage stability.

[0103] The above-mentioned active energy ray-curable composition and active energy ray-curable ink are widely used in the field of printing. More specifically, in printing, the active energy ray-curable composition or the active energy ray-curable ink is applied to a substrate by a known method.

[0104] The substrate is not particularly limited and examples thereof include uncoated paper, coated paper, paperboard, synthetic paper, aluminum-deposited paper, and plastic sheets. These may be used alone or in combination of two or more.

[0105] The application method is not particularly limited, and any known printing method can be used, including, for example, screen printing, offset printing, flexographic printing, and roll printing.

[0106] This results in a coating film of the active energy ray-curable composition or the active energy ray-curable ink. The coating film is then cured by irradiating it with active energy rays. Examples of active energy rays include ultraviolet rays and electron beams.

[0107] When curing with ultraviolet light, an ultraviolet light irradiation device can be used as a light source. Examples of ultraviolet light irradiation devices include a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp. The irradiation conditions are adjusted as necessary. Examples of the irradiation conditions include the ultraviolet light irradiation amount, the light amount of the ultraviolet light irradiation device, and the arrangement of the light source.

[0108] More specifically, when a high-pressure mercury lamp is used, for example, a substrate coated with an active energy ray-curable composition or an active energy ray-curable ink is irradiated with a luminous intensity of 80 to 1000 W / cm. 2For one lamp of about 1000 kV, the substrate is conveyed at a conveying speed of 5 to 50 m / min. When curing with an electron beam, the substrate coated with the coating agent is conveyed at a conveying speed of 5 to 50 m / min using an electron beam accelerator having an acceleration voltage of 10 to 300 kV, for example.

[0109] The active energy ray-curable composition or the active energy ray-curable ink is crosslinked and cured by irradiation with the active energy ray, resulting in a cured film as a cured product of the active energy ray-curable ink.

[0110] As described above, the above-described active energy ray-curable composition and active energy ray-curable ink are suitably used to obtain printed matter by known printing methods. [Example]

[0111] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. Note that "parts" and "%" are by mass unless otherwise specified. Furthermore, specific numerical values ​​such as blending ratios (content ratios), physical property values, and parameters used in the following description can be substituted with the corresponding upper limit values ​​(numeric values ​​defined as "equal to or less than") or lower limit values ​​(numeric values ​​defined as "equal to or more than" or "exceeding") of the blending ratios (content ratios), physical property values, parameters, etc. described in the above "Form for Carrying Out the Invention."

[0112] Preparation Example 1 (Acid-modified rosin-modified polyester resin) A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 54 parts by mass of gum rosin and 18 parts by mass of maleic anhydride. While blowing nitrogen gas into the flask, the flask was heated to 180°C for 1 hour to allow the Diels-Alder reaction to occur. Then, 28 parts by mass of 1,4-cyclohexanedimethanol was added to the flask, and a dehydration condensation reaction was carried out at 250°C. This resulted in a polyester resin modified with acid-modified rosin. This was designated rosin-based resin (A1).

[0113] Preparation Example 2 (Stabilized Rosin-Modified Polyester Resin) A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 53 parts by mass of disproportionated rosin, 5 parts by mass of benzoic acid, 5 parts by mass of maleic anhydride, 18 parts by mass of tetrahydrophthalic anhydride, 6 parts by mass of propylene glycol, and 13 parts by mass of glycerin. While blowing nitrogen gas into the flask, the flask was heated to 260°C to cause dehydration condensation. This resulted in a polyester resin modified with stabilized rosin (disproportionated rosin). This was designated rosin-based resin (A2).

[0114] Preparation Example 3 (Diallyl Phthalate Resin) A diallyl phthalate resin (product name "Daiso DAP A", manufactured by Osaka Soda Co., Ltd.) was prepared. This was designated as a non-rosin-based resin (A3).

[0115] Examples 1 to 4, Comparative Examples 1 and 2, and Reference Example 1 Based on the formulation shown in Table 1, an active energy ray-curable ink composition was obtained.

[0116] That is, according to the formulation shown in Table 1, a rosin-based resin or a non-rosin-based resin, an active energy ray-curable monomer, a metal capture agent, and hydroquinone (polymerization inhibitor) were mixed and heated to 110° C. to dissolve the mixture, thereby obtaining an active energy ray-curable composition.

[0117] In each example and comparative example, trimethylolpropane triacrylate (TMPTA) was used as the active energy ray curable monomer. In each example, gluconic acid, etidronic acid and phytic acid were used as the metal capture agent. In each comparative example and reference example, no metal capture agent was used.

[0118] <Evaluation> The active energy ray-curable composition was placed in a glass bottle and stored in an oven at 100°C. The time until the active energy ray-curable composition gelled was measured. The storage stability was evaluated according to the following criteria. From the viewpoint of practicality, a score of 3 or more was required.

[0119] 5 points: No gelation was observed for 100 hours or more. 4 points: Gelation was observed after 75 hours or more but less than 100 hours. 3 points: Gelation was observed between 50 hours and 75 hours. 2 points: Gelation was observed after 25 hours or more but less than 50 hours. Score 1: Gelation was observed in less than 25 hours.

[0120] [Table 1]

[0121] Details of the abbreviations in the table are given below. TMPTA: Trimethylolpropane triacrylate HQ: Hydroquinone

Claims

1. A rosin-based resin (A), an active energy ray-curable monomer (B); a metal capture agent (C); Contains the rosin-based resin (A) contains a rosin-modified polyester resin, the metal capture agent (C) contains at least one selected from the group consisting of a carboxy group-containing capture agent and a phosphorus-containing capture agent, per 100 parts by mass of the total amount of the rosin-based resin (A) and the active energy ray-curable monomer (B), the amount of the rosin-based resin (A) is 20 parts by mass or more and 80 parts by mass or less, the amount of the active energy ray-curable monomer (B) is 20 parts by mass or more and 80 parts by mass or less; The amount of the metal capture agent (C) is 0.001 parts by mass or more and 5 parts by mass or less. , an active energy ray curable composition.

2. The active energy ray-curable composition according to claim 1 , wherein the metal scavenger (C) comprises a phosphorus-containing scavenger.

3. An actinic ray-curable ink comprising the actinic ray-curable composition according to claim 1 or 2.

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