Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

Definitions

• An embodiment of the present invention relates to an active energy ray-curable composition for use in packaging and the like, and more specifically to an active energy ray-curable composition that can provide clear printed matter (laminate having a printed layer).
• Activin energy ray curable inks are solvent-free and instantly cure and dry when exposed to active energy rays, making them environmentally friendly, easy to print, and capable of producing high-quality printed matter. For this reason, they are widely used in a wide range of fields, from printing information such as magazines and flyers to packaging for food packaging such as paper containers.
• Patent Document 1 discloses an active energy ray-curable ink that contains a metal complex and a compound with a polar group.
• the ink disclosed has been evaluated for the presence or absence of smudging during printing, but the clear prints that meet market demand have not been obtained.
• the present invention provides an active energy ray-curable composition that produces clear prints with minimal distortion of dot shapes and has excellent fluidity, and provides prints using the same.
• An active energy ray-curable composition comprising a (meth)acrylate compound (A) and a carboxylic acid or carboxylic acid anhydride (B) having a molecular weight of 500 or less and no (meth)acryloyl group, the content of the carboxylic acid or carboxylic acid anhydride (B) having a molecular weight of 500 or less and not having a (meth)acryloyl group is 3 mass % or less based on the total amount of the composition.
• the active energy ray curable composition according to [1] or [2] above, wherein the carboxylic acid or carboxylic acid anhydride (B) having a molecular weight of 500 or less and no (meth)acryloyl group includes at least one selected from the group consisting of tertiary butyl benzoic acid, benzoic acid, methyl benzoic acid, maleic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, abietic acid, dehydroabietic acid, and trimellitic anhydride.
• the carboxylic acid or carboxylic acid anhydride (B) having a molecular weight of 500 or less and no (meth)acryloyl group includes at least one selected from the group consisting of tertiary butyl benzoic acid, benzoic acid, methyl benzoic acid, maleic anhydride
• the present invention provides an active energy ray-curable composition that produces clear prints with minimal distortion of dot shapes and has excellent fluidity, and can provide prints using the same.
• (Meth)acrylate refers to acrylate and/or methacrylate.
• Active energy rays refers to energy rays such as ultraviolet rays that have the property of causing chemical changes such as chemical reactions in irradiated substances. Additionally, “PO” stands for “propylene oxide” and “EO” stands for “ethylene oxide.”
• composition An active energy ray-curable composition (hereinafter, also referred to as "composition") according to one embodiment of the present invention contains a (meth)acrylate compound (A).
• the (meth)acrylate compound (A) is a compound having one or more (meth)acryloyl groups in the molecule. Specific examples of the (meth)acrylate compound (A) include the following.
• urethane acrylate polyester acrylate, epoxy acrylate, etc. can also be used as the (meth)acrylate compound (A).
• the urethane acrylate may be, for example, one obtained by reacting a diisocyanate with a (meth)acrylate having a hydroxyl group, or one obtained by reacting an isocyanate group-containing urethane prepolymer obtained by reacting a polyol with a polyisocyanate under conditions of an excess of isocyanate groups with a (meth)acrylate having a hydroxyl group.
• it can also be obtained by reacting a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol with a polyisocyanate under conditions of an excess of hydroxyl groups with a (meth)acrylate having an isocyanate group.
• Polyester acrylate can be obtained, for example, by reacting polyester polycarboxylic acid obtained by polycondensation of polybasic acid and polyhydric alcohol with hydroxyl group-containing (meth)acrylate, etc.
• Epoxy acrylates can be, for example, those in which the glycidyl group of an epoxy resin is esterified with (meth)acrylic acid to make the functional group a (meth)acrylate group, such as a (meth)acrylic acid adduct to a bisphenol A type epoxy resin, or a (meth)acrylic acid adduct to a novolac type epoxy resin.
• the (meth)acrylate compound (A) may be used alone or in combination of two or more. In some embodiments, from the viewpoint of the coating film strength after curing, it is preferable to use a (meth)acrylate compound having two or more (meth)acryloyl groups as the (meth)acrylate compound (A), and it is even more preferable to use a (meth)acrylate compound having three or more (meth)acryloyl groups.
• the (meth)acrylate compound (A) preferably includes at least one selected from the group consisting of tripropylene glycol di(meth)acrylate, EO-modified (3) trimethylolpropane tri(meth)acrylate, PO-modified (3) trimethylolpropane tri(meth)acrylate, PO-modified (3) glycerin triacrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, and more preferably includes two or more selected from the group consisting of tripropylene glycol di(meth)acrylate, EO-modified (3) trimethylolpropane tri(meth)acrylate, PO-modified (3) glycerin triacrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.
• the (meth)acrylate compound (A) preferably includes two or more selected from the group consisting of EO-modified (3) trimethylolpropane tri(meth)acrylate, PO-modified (3) trimethylolpropane tri(meth)acrylate, PO-modified (3) glycerin triacrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.
• the (meth)acrylate compound (A) preferably includes at least one selected from EO-modified (3) trimethylolpropane tri(meth)acrylate, PO-modified (3) trimethylolpropane tri(meth)acrylate, and PO-modified (3) glycerin triacrylate, and at least one selected from the group consisting of ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.
• the (meth)acrylate compound (A) preferably includes EO-modified (3) trimethylolpropane tri(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate.
• the content of the (meth)acrylate compound (A) is preferably 20 to 95% by mass, more preferably 25 to 90% by mass, based on the total amount of the composition.
• the content of the carboxylic acid or carboxylic acid anhydride (B) having a molecular weight of 500 or less and not having a (meth)acryloyl group is 3 mass % or less based on the total amount of the composition.
• the carboxylic acid or carboxylic anhydride (B) having no (meth)acryloyl group and a molecular weight of 500 or less may specifically be a compound having one or more carboxylic acids described below.
• compounds having one carboxylic acid include aromatic monobasic acids such as benzoic acid, methylbenzoic acid, tert-butylbenzoic acid, naphthoic acid, and orthobenzoylbenzoic acid; resin acids such as abietic acid, neoabietic acid, palustric acid, dehydroabietic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, and communic acid; stearic acid, palmitic acid, oleic acid, and linoleic acid.
• Examples of compounds having two or more carboxylic acids include 1,2,3,6-tetrahydrophthalic acid, 3-methyl-1,2,3,6-tetrahydrophthalic acid, 4-methyl-1,2,3,6-tetrahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, alkenylsuccinic acids such as dodecenylsuccinic acid and pentadecenylsuccinic acid, o-phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, isocrotonic acid, dihydroagatoic
• Carboxylic acids or carboxylic anhydrides (B) having no (meth)acryloyl group and a molecular weight of 500 or less may be used alone or in combination of two or more.
• the molecular weight of the compound By having the molecular weight of the compound be 500 or less, it is possible to achieve clarity of the printed paper surface without impairing the fluidity of the composition.
• the molecular weight of the compound may be 400 or less, 350 or less, or 300 or less. In some embodiments, the molecular weight of the compound may be 284.5 or less. Although not particularly limited, the molecular weight of the compound may be 50 or more.
• the carboxylic acid or carboxylic anhydride (B) having no (meth)acryloyl group and a molecular weight of 500 or less contains a carboxylic acid compound having a cyclic hydrocarbon structure in its structure (molecule).
• the cyclic hydrocarbon structure may be either an aromatic ring or an alicyclic structure.
• compounds having one carboxylic acid include aromatic monobasic acids such as benzoic acid, methylbenzoic acid, tertiary butylbenzoic acid, naphthoic acid, and orthobenzoylbenzoic acid, and resin acids such as abietic acid, neoabietic acid, palustric acid, dehydroabietic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, and communic acid.
• aromatic monobasic acids such as benzoic acid, methylbenzoic acid, tertiary butylbenzoic acid, naphthoic acid, and orthobenzoylbenzoic acid
• resin acids such as abietic acid, neoabietic acid, palustric acid, dehydroabietic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, and communic acid.
• compounds having two or more carboxylic acids include 1,2,3,6-tetrahydrophthalic acid, 3-methyl-1,2,3,6-tetrahydrophthalic acid, 4-methyl-1,2,3,6-tetrahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, o-phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, maleic acid, fumaric acid, dihydroagatoic acid, and acid anhydrides thereof.
• At least one selected from the group consisting of maleic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, and trimellitic anhydride can be preferably used.
• the carboxylic acid or carboxylic anhydride (B) having no (meth)acryloyl group and a molecular weight of 500 or less is preferably a carboxylic acid compound having a cyclic hydrocarbon structure in the molecule.
• the carboxylic acid compound having a cyclic hydrocarbon structure is preferably one or more selected from the group consisting of tertiary butyl benzoic acid, benzoic acid, methyl benzoic acid, abietic acid, dehydroabietic acid, maleic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, and trimellitic anhydride.
• the carboxylic acid compound having a cyclic hydrocarbon structure is more preferably one or more selected from the group consisting of benzoic acid, abietic acid, dehydroabietic acid, maleic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, isophthalic acid, and terephthalic acid.
• the carboxylic acid compound having the cyclic hydrocarbon structure may be a compound having one carboxylic acid, of which benzoic acid, abietic acid, and dehydroabietic acid are preferred, with benzoic acid and dehydroabietic acid being more preferred.
• the carboxylic acid compound having the cyclic hydrocarbon structure may be a compound having two or more carboxylic acids, of which 1,2,3,6-tetrahydrophthalic anhydride and phthalic anhydride are preferred.
• the content of the carboxylic acid or carboxylic anhydride (B) having no (meth)acryloyl group and having a molecular weight of 500 or less is 3 mass % or less based on the total amount of the composition. If it exceeds 3 mass %, the compatibility with the (meth)acrylate compound (A) tends to deteriorate, and the flowability tends to deteriorate.
• the content of the carboxylic acid or carboxylic anhydride (B) having no (meth)acryloyl group and having a molecular weight of 500 or less may be 0.0005% by mass or more, 0.001% by mass or more, or 0.003% by mass or more, and may be 3% by mass or less, 2% by mass or less, or 1% by mass or less.
• the content of (B) is preferably 0.001% by mass to 2% by mass, and more preferably 0.003% by mass to 1% by mass.
• the composition of the present embodiment preferably contains a resin (C).
• the resin (C) By containing the resin (C), the fluidity becomes favorable.
• the resin (C) preferably has excellent compatibility with the (meth)acrylate compound.
• Specific examples of the resin (C) include diallyl phthalate resin, rosin-modified resin, polyvinyl chloride, poly(meth)acrylic acid ester, 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, alkyd resin, petroleum resin, urea resin, synthetic rubber such as butadiene-acrylonitrile copolymer, and the like.
• one or more resins selected from the group consisting of diallyl phthalate resins, rosin-modified resins, epoxy resins, polyester resins, polyurethane resins, alkyd resins, and petroleum resins.
• the content of resin (C) is preferably 2 to 40 mass% and more preferably 3 to 30 mass% based on the total amount of the composition. In some embodiments, the content of resin (C) may be 10 to 30 mass% or 10 to 20 mass% based on the total amount of the composition.
• the weight average molecular weight of resin (C) is preferably 1,000 to 50,000, more preferably 1,500 to 40,000, from the viewpoints of compatibility with the (meth)acrylate compound and flowability.
• a colorant (D) can also be used.
• the colorant (D) at least one of a pigment and a dye can be used, but from the viewpoint of light resistance, it is preferable to use a pigment.
• the pigment is not particularly limited, and any known pigment can be used. Both inorganic and organic pigments can be used.
• Inorganic pigments include carbon blacks such as furnace black, lamp black, acetylene black, and channel black, as well as iron oxide and titanium oxide.
• Organic pigments include soluble azo pigments such as ⁇ -naphthol, ⁇ -oxynaphthoic acid, ⁇ -oxynaphthoic acid anilide, acetoacetate anilide, and pyrazolone; insoluble azo pigments such as ⁇ -naphthol, ⁇ -oxynaphthoic acid anilide, acetoacetate anilide monoazo, acetoacetate anilide disazo, and pyrazolone; copper phthalocyanine blue, halogenated (e.g., chlorinated or brominated) copper phthalocyanine blue, sulfur Phthalocyanine pigments such as copper phthalocyanine blue and metal-free phthalocyanine; polycyclic and heterocyclic pigments such as quinacridone, dioxazine, threne (pyranthrone, anthanthrone, indanthrone, anthrapyrimidine, flavanthrone, thioindi
• black pigments include C.I. Pigment Black 1, 6, 7, 9, 10, 11, 28, 26, 31, etc.
• White pigments include C.I. Pigment White 5, 6, 7, 12, and 28.
• yellow pigments examples 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, 62, etc.
• 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, 108, 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.
• Green pigments include C.I. Pigment Green 1, 2, 3, 4, 7, 8, 10, 15, 17, 26, 36, 45, and 50.
• purple pigments examples 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.
• Orange pigments include C.I. Pigment Orange 13, 16, 20, 34, 36, 38, 39, 43, 51, 61, 63, 64, 74, and the like.
• the above pigments may be used alone or in combination of two or more.
• the colorant can be used in any content as long as the desired concentration can be reproduced, and it is preferable that the content be 5 to 60% by weight based on the total weight of the composition.
• the composition of the present embodiment may further contain fine particles.
• fine particles When fine particles are used, effects such as adjusting the flowability of the composition, preventing misting, and preventing penetration into a printing substrate such as paper can be added.
• the fine particles may be fine particles such as an extender pigment, silicone, and glass beads, but the use of an extender pigment is preferred.
• extender pigment examples include lime carbonate powder, precipitated calcium carbonate, precipitated barium sulfate, gypsum, clay (China Clay), titanium oxide, silica, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, aluminum stearate, calcium stearate, calcium carbonate, magnesium carbonate, barite powder, and abrasive powder.
• the above-mentioned extender pigments can also be used as white pigments (colorants).
• the content of the extender pigment is not particularly limited. Any content of the extender pigment may be used as long as it is possible to impart the desired effects, such as adjusting flowability, preventing misting, and preventing penetration into printing substrates such as paper. In some embodiments, the content of the extender pigment is preferably 0.1 to 10% by mass based on the total mass of the composition.
• the composition of the present embodiment may further contain various additives such as an anti-friction agent, an anti-blocking agent, a slipping agent, etc.
• the various additives can be added to the composition by a conventional method. When various additives are added to the composition, it is preferable to adjust the amount of each additive to a range that does not inhibit the effects of other materials.
• the amount of each additive is preferably 20 mass % or less based on the total amount of the composition.
• the composition of the present embodiment may contain a photopolymerization initiator.
• the polymerization initiator in the present invention may be any compound that undergoes a chemical change and generates radicals through the action of light or through interaction with the electronically excited state of the sensitizing dye. Among them, a photoradical polymerization initiator is preferable from the viewpoint of being able to initiate polymerization by exposure to light.
• the photopolymerization initiator that can be used in this embodiment is not particularly limited, and any known photopolymerization initiator can be used. Specific examples include benzophenone-based compounds, dialkoxyacetophenone-based compounds, ⁇ -hydroxyalkylphenone-based compounds, ⁇ -aminoalkylphenone-based compounds, acylphosphine oxide-based compounds, and thioxanthone-based compounds.
• the photopolymerization initiator may be used alone or in combination of two or more kinds.
• benzophenone compounds include benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, and [4-(methylphenylthio)phenyl]-phenylmethanone.
• dialkoxyacetophenone compounds examples include 2,2-dimethoxy-2-phenylacetophenone, dimethoxyacetophenone, and diethoxyacetophenone.
• Examples of the ⁇ -hydroxyalkylphenone compounds include 1-hydroxy-cyclohexyl 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 ⁇ -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-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one.
• thioxanthone compounds examples include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone.
• the content of the photopolymerization initiator is preferably 1 to 20% by mass, and more preferably 5 to 15% by mass, based on the total amount of the composition (ink).
• the photopolymerization initiator preferably contains an ⁇ -aminoalkylphenone compound and a thioxanthone compound.
• the photopolymerization initiator preferably contains, for example, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one and 2,4-diethylthioxanthone.
• the composition of the present embodiment may contain a photopolymerization inhibitor, which can provide excellent storage stability.
• Nitroso compounds include nitrosobenzene, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, picric acid, cupferron, butyraldoxime, methyl ethyl ketoxime, and cyclohexanone oxime.
• Phenol compounds include (alkyl)phenols, p-methoxyphenol, o-isopropylphenol, catechol, resorcinol, t-butylcatechol, pyrogallol, dibutylcresol, and guaiacol.
• Quinone compounds include hydroquinone, t-butylhydroquinone, p-benzoquinone, and 2,5-di-tert-butyl-p-benzoquinone.
• Piperidine compounds include phenothiazine, etc.
• the photopolymerization inhibitor can be used in combination with photopolymerization inhibitors other than the above-mentioned nitroso compounds, phenol compounds, quinone compounds, and piperidine compounds (also referred to as "other photopolymerization inhibitors").
• photopolymerization inhibitors include 1,1-picrylhydrazyl, dithiobenzoyl disulfide, N-(3-oxyanilino-1,3-dimethylbutylidene)aniline oxide, cyclohexanone oxime cresol, etc.
• the content of the photopolymerization inhibitor is preferably 0.05 to 5.0% by mass, and more preferably 0.1 to 1.0% by mass, based on the total mass of the composition.
• the active energy ray-curable composition of the present embodiment preferably does not substantially contain an organic solvent.
• substantially does not contain means that it is not intentionally added and the content due to unintentional addition is less than 1 mass%. Unintentional addition includes cases where it is contained in trace amounts in each raw material, or contamination during the composition production process and the print production process.
• Representative organic solvents used as viscosity modifiers for printing inks are of concern as they contain MOSH/MOAH, which are persistent organic pollutants.
• the absence of volatile components Non-VOC is expected to reduce the environmental load and improve work safety, so it is preferable that the composition according to one embodiment of the present invention is substantially free of organic solvents.
• One embodiment of the present invention relates to a laminate having a substrate and a layer formed from a cured product of the composition of the above embodiment.
• the laminate of the present embodiment is obtained by forming a printed layer on the substrate by printing or coating the composition of the present embodiment described above, and then curing the printed layer with active energy rays.
• the active energy rays typically include ultraviolet rays, electron beams, X-rays, ionizing radiation such as ⁇ -rays, ⁇ -rays, and ⁇ -rays, microwaves, high frequency waves, etc.
• the active energy rays are not limited to these, and may be any energy species capable of generating radical active species, including visible light, infrared light, and laser beams.
• sources of ultraviolet rays include LEDs, ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, metal halide lamps, xenon lamps, carbon arc lamps, helium-cadmium lasers, YAG lasers, excimer lasers, and argon lasers.
• substrates there are no particular limitations on the substrate that can be used in the structure of this embodiment, and any known substrate can be used.
• Specific examples of substrates include coated papers such as art paper, coated paper, and cast paper; uncoated papers such as fine paper, medium-quality paper, and newsprint; synthetic papers such as Yupo paper; plastic films such as PET (polyethylene terephthalate), PP (polypropylene), and OPP (biaxially oriented polypropylene); metal foils; and metal plates used in containers such as cans.
• the substrate may be paper such as fine paper, coated paper, art paper, construction paper, thin paper, cardboard, or various synthetic papers used for printing catalogs, posters, flyers, CD jackets, direct mail, and pamphlets, as well as packaging for cosmetics, beverages, medicines, toys, devices, etc.
• the substrate may be a film, sheet, or cellophane of polyester resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methacrylic acid copolymer, nylon, polylactic acid, polycarbonate, or the like.
• the substrate may be a metal foil such as aluminum foil, a metal plate such as steel, copper, stainless steel, stainless steel, aluminum, tin-plated steel plate, or tin-free steel, or a metal base plate having a base coat (primer) layer provided on the metal plate.
• a metal foil such as aluminum foil
• a metal plate such as steel, copper, stainless steel, stainless steel, aluminum, tin-plated steel plate, or tin-free steel
• a metal base plate having a base coat (primer) layer provided on the metal plate.
• Methods for printing or coating the composition of this embodiment on a substrate include roll coaters, gravure coaters, flexo coaters, air doctor coaters, blade coaters, air knife coaters, squeeze coaters, impregnation coaters, transfer roll coaters, kiss coaters, curtain coaters, cast coaters, spray coaters, die coaters, offset printing (normal lithographic printing using dampening water and waterless lithographic printing not using dampening water), flexo printing, gravure printing, screen printing, and the like.
• offset printing normal lithographic printing using dampening water and waterless lithographic printing not using dampening water
• flexo printing gravure printing
• screen printing and the like.
• the composition of this embodiment can be suitably used as a printing ink.
• the composition of the present embodiment can be suitably used to form a printed layer on various substrates, and can provide printed materials such as various printed materials for books, various printed materials for packaging such as paper, various printed materials for plastics, printed materials for stickers/labels, fine art printed materials, and metal printed materials (fine art printed materials, printed materials for beverage cans, printed materials for canned food such as canned goods, etc.).
• the composition of the present embodiment can be used as a top coat for printed matter that requires high gloss, heat resistance, scratch resistance, etc.
• the layer (cured layer) formed from the cured product of the composition of the present embodiment has excellent heat resistance and scratch resistance.
• a printed layer for packaging food, medicine, cosmetics, etc. which require labeling immediately after high-temperature filling processing and resistance to label rubbing during the filling line process and transportation during logistics, such as cosmetic boxes, paper containers, labels, catalogs, shopping bags, book covers, posters, etc.
• Actio-energy ray-curable compositions of Examples 1 to 68 and Comparative Examples 1 to 8 were obtained by milling in a three-roll mill according to the compositions in Table 1. The evaluation results of the obtained active energy ray-curable compositions are also shown in Table 1.
• Printing was carried out at a speed of 10,000 sheets/hour under the following conditions using an offset sheet-fed printing machine LITHRONE L426 ( Komori Corporation). The extent to which 50% dots on the plate surface expanded (dot gain) during continuous printing of 5,000 sheets was compared. A dot gain rating of "2" or higher is a practically acceptable level. A rating of "3" or higher is even more preferable, as it provides clear printed matter. (Evaluation Criteria) 5: Dot gain less than 17%, extremely clear prints that far exceed market demand can be provided. 4: Dot gain 17% or more but less than 19%, clear prints that fully meet market demand can be provided.

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