Active energy ray curable composition and laminate

Abstract

To provide an active energy ray-curable composition having excellent antibacterial property, high friction resistance, high printability, and high storage stability, and a laminate.SOLUTION: An active energy ray-curable composition includes a polymerizable compound, wax, an antibacterial agent and a polymerization inhibitor, where the content of the antibacterial agent is 0.05-15 mass% in a total amount of the composition, the wax includes one or more selected from the group consisting of polyolefin wax, paraffin wax, acryl bead wax, urethane bead wax, Fisher Tropsch wax, microcrystalline wax, vaseline, and carnauba wax, the content of the wax is 0.5-10 mass% in a total amount of the composition, and the content of the polymerization inhibitor is 0.01-3 mass% in a total amount of the composition.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable composition and a laminate having excellent antibacterial properties, high abrasion resistance, high printing suitability, and high storage stability.

Background Art

[0002] In recent years, due to the increasing awareness of public health, the demand for products with antibacterial processing (antibacterial products) has been increasing, and various antibacterial products are also on the market. General antibacterial products (for example, plastics) impart antibacterial performance by kneading an antibacterial agent into a base material. However, due to constraints such as the high price of antibacterial agents and the toxicity of some types, the products that can be used are limited. Since the antibacterial performance of an antibacterial agent is mainly exhibited by the antibacterial agent exposed on the surface, in order to maximize the effective use of the antibacterial performance while minimizing the addition amount of the antibacterial agent, coating only on the surface is one effective solution.

[0003] As methods for coating an antibacterial agent, various methods can be mentioned. Even in an active energy ray-curable composition excellent in productivity and film fastness, studies have been conducted to impart antibacterial performance. However, the antibacterial agent is an inert component in the active energy ray-curable composition, and there is a problem that the abrasion resistance of the coating film surface deteriorates when the antibacterial agent is added. In addition, the antibacterial agent itself often has poor compatibility with the active energy ray-curable composition, and there is a problem that the storage stability deteriorates.

[0004] Patent Document 1 (Japanese Patent Application Laid-Open No. 8-311373) discloses an acrylate-based polymerization composition using a silver compound as an antibacterial agent. However, there are problems such as poor abrasion resistance as a laminate and deterioration of storage stability. In addition, since the silver compound is dissolved in a solvent and used, a step of removing the solvent after applying the polymerization composition to a base material is required, resulting in a significant loss of productivity.

[0005] Patent Document 2 (Japanese Patent Publication No. 11-80642) discloses an acrylate-based polymerization composition containing an antibacterial agent and polytetrafluoroethylene particles. However, the use of polytetrafluoroethylene particles has been restricted due to recent environmental regulations, making their practical use increasingly difficult. Furthermore, polytetrafluoroethylene particles have the problem of becoming flattened during the dispersion process in the production of acrylate-based polymerization compositions, and accumulating on rollers and blankets during printing. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 8-311373 [Patent Document 2] Japanese Patent Application Publication No. 11-80642 [Overview of the project] [Problems that the invention aims to solve]

[0007] The problem that this invention aims to solve is to provide an active energy ray-curable composition and laminate having excellent antibacterial properties, high abrasion resistance, high printability, and high storage stability. [Means for solving the problem]

[0008] The inventors of this invention have conducted extensive research to solve the above problems and have come up with the following activated energy rays. Hardened composition We found that the above problems could be solved, and thus completed the present invention. .

[0009] That is, the present invention relates to an active energy ray curable composition comprising a polymerizable compound, a wax, an antibacterial agent, and a polymerization inhibitor, The amount of the antibacterial agent is 0.05 to 15% by mass of the total amount of the active energy ray curable composition. The wax comprises one or more selected from the group consisting of polyolefin wax, paraffin wax, acrylic beeswax, urethane beeswax, Fischer-Tropsch wax, microcrystalline wax, petrolatum, and carnauba wax. The wax content is 0.5 to 10% by mass of the total amount of the active energy ray curable composition. The present invention relates to an active energy ray curable composition characterized in that the polymerization inhibitor content is 0.01 to 3% by mass of the total amount of the active energy ray curable composition.

[0010] The present invention also relates to the above-mentioned active energy ray curable composition, characterized in that the antibacterial agent comprises a compound containing at least one metal element selected from the group consisting of silver, copper, zinc, and tin.

[0011] The present invention also relates to the above-mentioned active energy ray curable composition, further characterized by comprising an extender pigment.

[0012] The present invention also relates to the above-mentioned active energy ray curable composition, further characterized by comprising a coloring agent.

[0013] The present invention also relates to a laminate having a substrate on which the above-mentioned active energy ray-curable composition is cured with active energy rays.

[0014] The present invention also relates to a laminate having a layer on the printed surface of a printed material on which ink has been printed, wherein the active energy ray-curable composition described above is cured with active energy rays. [Effects of the Invention]

[0015] The present invention provides an active energy ray-curable composition and laminate having excellent antibacterial properties, high abrasion resistance, high printability, and high storage stability. [Modes for carrying out the invention]

[0016] Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof and implemented.

[0017] Terms used in this specification will be explained. "(Meth)acryloyl" means acryloyl and / or methacryloyl (methacryloyl), and "(meth)acrylate" means acrylate and / or methacrylate (methacrylate). "Active energy ray" means an energy ray having a property of causing a chemical change such as a chemical reaction in an irradiated object when irradiated, such as ultraviolet rays or electron beams.

[0018] <Antibacterial agent> The antibacterial agent in the present invention is not particularly limited as long as it is a substance that exhibits antibacterial performance in a particulate form, and both inorganic and organic systems can be used. Among them, as the antibacterial agent, it is preferable to include a compound containing at least one metal element selected from the group consisting of silver, copper, zinc, and tin. Specific examples thereof include those in which metal ions such as silver, copper, zinc, and tin are supported on porous substances such as zeolite, silica gel, zirconium phosphate, titanium oxide, and alumina.

[0019] The content of the antibacterial agent is 0.05 to 15% by mass in the total amount of the composition. If the content of the antibacterial agent is less than 0.05% by mass, the antibacterial effect is not stable. If it exceeds 15% by mass, the necessary and sufficient antibacterial effect is saturated, and the antibacterial agent becomes excessive, which is disadvantageous in terms of price and printing suitability. The content of the antibacterial agent is preferably 0.1 to 10% by mass in the total amount of the composition, and more preferably 0.5 to 7% by mass in the total amount of the composition.

[0020] <Wax> In the present invention, high abrasion resistance can be maintained by adding wax. The wax includes one or more selected from the group consisting of polyolefin wax, paraffin wax, acrylic bead wax, urethane bead wax, Fischer-Tropsch wax, microcrystalline wax, petrolatum, and carnauba wax. These waxes may be used alone or in combination. Examples of the polyolefin wax include polyethylene wax, polypropylene wax, ethylene-propylene copolymer wax, oxidized polyethylene wax, and the like. Among them, since the effect of abrasion resistance can be particularly high, it is preferable that the wax includes one or more selected from the group consisting of polyolefin wax, microcrystalline wax, and petrolatum. This is presumably because these waxes are likely to be exposed on the surface. The content of these waxes is 0.5 to 10% by mass of the total amount of the active energy ray-curable composition. When the content of the wax is less than 0.5% by mass of the total amount of the composition, the abrasion resistance is not sufficiently exhibited. When it exceeds 10% by mass, the gloss and printability are impaired. The content of the wax is preferably 1 to 5% by mass in the total amount of the composition.

[0021] On the other hand, the use of polytetrafluoroethylene wax is restricted by recent environmental regulations and is becoming substantially difficult to use. In addition, polytetrafluoroethylene wax is not suitable for use because the particles are flattened in the dispersion process during the production of the acrylate-based polymerization composition, deposited on the roller or blanket during printing, and the printability is impaired.

[0022] <Polymerization inhibitor> A polymerization inhibitor is added to the active energy ray curable composition of the present invention. This makes it possible to obtain high storage stability. There are no particular restrictions on the polymerization inhibitor, and known ones can be used. Specifically, examples include hydroquinone, methyl hydroquinone, methoxyhydroquinone, tert-butylhydroquinone, and N-nitrosophenylhydroxylamine. These polymerization inhibitors may be used individually or in combination. The content of these polymerization inhibitors is 0.01 to 3% by mass of the total amount of the active energy ray-curable composition. If the content of polymerization inhibitors is less than 0.01% by mass of the total amount of the composition, the storage stability is insufficient, and if it exceeds 3% by mass, it adversely affects the curability. Furthermore, the content of polymerization inhibitors is preferably 0.03 to 2% by mass of the total amount of the active energy ray-curable composition, and particularly preferably 0.05 to 1% by mass.

[0023] <Photopolymerization initiator> A photopolymerization initiator can be used in the active energy ray curable composition of the present invention. The photopolymerization initiator used in the present invention can be a commercially available product, but it is particularly preferable to use one or more selected from the group consisting of acylphosphine oxide-based photopolymerization initiators, dialkoxyacetophenone-based photopolymerization initiators, benzophenone-based photopolymerization initiators, and α-hydroxyalkylphenone-based photopolymerization initiators. These photopolymerization initiators may be used individually or in combination. If storage in harsh environments such as high temperatures or long-term storage is required, the photopolymerization initiator may be omitted. If no photopolymerization initiator is included, curing by electron beam is preferred.

[0024] Examples of acylphosphine oxide-based photopolymerization initiators include diphenylacylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0025] Examples of dialkoxyacetophenone-based photopolymerization initiators include 2,2-dimethoxy-2-phenylacetophenone, dimethoxyacetophenone, and diethoxyacetophenone.

[0026] Examples of benzophenone-based photopolymerization initiators include benzophenone, 4-methylbenzophenone, and 4-phenylbenzophenone.

[0027] Examples of α-hydroxyalkylphenone-based photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxymethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl]-2-methylpropan-1-one.

[0028] In the present invention, the content of the photopolymerization initiator is preferably 3 to 15% by mass, and more preferably 5 to 15% by mass, based on the total mass of the active energy ray curable composition. If the content of the photopolymerization initiator is less than 3% by mass of the total mass of the composition, the radical reaction does not proceed sufficiently and sufficient robustness as a coating film cannot be obtained. If the content of the photopolymerization initiator exceeds 15% by mass of the total mass of the composition, the content of polymerizable components becomes relatively low and sufficient robustness as a coating film cannot be obtained.

[0029] <Body pigments> In this invention, extender pigments can be used. By using extender pigments, the penetration of the antibacterial agent into the substrate is suppressed, increasing the surface exposure of the antibacterial agent, and high antibacterial activity can be obtained even with the addition of a small amount of antibacterial agent.

[0030] There are no particular limitations on the extender pigments that can be used in the present invention, and known extender pigments can be used. Specifically, calcium carbonate, magnesium carbonate, barium sulfate, silica, and the like are examples.

[0031] The extender pigment content is preferably 1 to 20% by mass, and more preferably 3 to 15% by mass, relative to the total mass of the active energy ray-curable composition. If the extender pigment content is less than 1% by mass relative to the total mass of the composition, the effect of adding the extender pigment will not be obtained. On the other hand, if the extender pigment content exceeds 20% by mass relative to the total mass of the composition, it will adversely affect gloss and printability.

[0032] <Coloring agent> In the present invention, a coloring agent can be used. There are no particular limitations on the colorants that can be used in the present invention; known pigments and dyes can be used. By using pigments, the penetration of the antibacterial agent into the substrate is suppressed, increasing the surface exposure of the antibacterial agent, and high antibacterial activity can be obtained even with the addition of a small amount of antibacterial agent. Both inorganic pigments and organic pigments can be used.

[0033] Examples of inorganic pigments include carbon blacks such as furnace black, lamp black, acetylene black, and channel black, as well as iron oxide and titanium dioxide.

[0034] Organic pigments include soluble azo pigments such as β-naphthol-based, β-oxynaphthoic acid-based, β-oxynaphthoic acid-based anilide-based, acetoacetate anilide-based, and pyrazolone-based pigments; Examples include insoluble azo pigments such as β-naphthol-based, β-oxynaphthoic acid-based anilide-based, acetoacetate anilide-based monoazo, acetoacetate anilide-based disazo, and pyrazolone-based pigments; phthalocyanine-based pigments such as copper phthalocyanine blue, halogenated (e.g., chlorinated, brominated, etc.) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, and metal-free phthalocyanines; polycyclic and heterocyclic pigments such as quinacridone-based, dioxazine-based, slene-based (pyrantrone, anthantrone, indanthrone, anthrapyrimidine, flavanthrone, thioindigo-based, anthraquinone-based, perinone-based, perylene-based, etc.), isoindolinone-based, metal complex-based, quinophthalone-based, and diketopyrrolopyrrole-based pigments; and others.

[0035] More specifically, using the CI color index, examples of black pigments include CIPigment Black 1, 6, 7, 9, 10, 11, 28, 26, and 31.

[0036] Examples of white pigments include CIPigment White 5, 6, 7, 12, and 28.

[0037] Examples of yellow pigments include CIPigment 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.

[0038] Examples of blue or cyan pigments include CIPigment Blue 1, 2, 14, 15, 15:1, 15:2, 15:3, 15:4, 60, and 62.

[0039] As red or crimson pigments, CIPigment RED 1, 3, 5, 19, 21, 22, 31, 38, 42, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 50, 52, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 83, 90, 104, 108, 11 Examples include 2, 114, 122, 144, 146, 148, 149, 150, 166, 168, 169, 170, 172, 173, 176, 177, 178, 184, 185, 187, 193, 202, 209, 214, 242, 254, 255, 264, 266, 269, and CIPigment Violet 19.

[0040] Examples of green pigments include CIPigment Green 1, 2, 3, 4, 7, 8, 10, 15, 17, 26, 36, 45, and 50.

[0041] Examples of purple pigments include CIPigment Violet 1, 2, 3, 4, 5:1, 12, 13, 15, 16, 17, 19, 23, 25, 29, 31, 32, 36, 37, 39, and 42.

[0042] Examples of orange pigments include CIPigment Orange 13, 16, 20, 34, 36, 38, 39, 43, 51, 61, 63, 64, and 74.

[0043] In this invention, the coloring agent may be used alone or in combination of two or more types. The amount of coloring agent added is preferably 1 to 60% by mass. If the amount is less than this range, the coloring effect will not be obtained. If the amount is more than this range, there is a risk of impairing printability.

[0044] <Polymerizable compound> In the present invention, the active energy ray curable composition includes a polymerizable compound. There are no particular restrictions on the polymerizable compound that can be used in combination with the present invention; known compounds can be used.

[0045] A radical polymerizable compound (hereinafter referred to as "radical polymerizable compound (Z)") that is preferably used as a polymerizable compound is a compound having an ethylenically unsaturated bond that can be radically polymerized. It is sufficient if the compound has at least one ethylenically unsaturated bond in its molecule, and this includes compounds in chemical forms such as monomers, oligomers, and polymers. A radical polymerizable compound (Z) may be used alone or in combination of two or more types.

[0046] Examples of radical polymerizable compounds (Z) include unsaturated carboxylic acids such as (meth)acrylic acid, itaconic acid, and maleic acid, and their salts; anhydrides having ethylenically unsaturated groups; acrylonitonyl; styrene; and various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes.

[0047] Examples of radical polymerizable compounds (Z) include, specifically, 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-trimethylcyclohexanol (meth)acrylate, and cyclohexyl Monofunctional radical polymerizable compounds such as methyl(meth)acrylate, isobornyl(meth)acrylate, norbornyl(meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentenyl(oxyethyl)(meth)acrylate, 1,4-cyclohexanedimethanol(meth)acrylate, cyclic trimethylolpropaneformal(meth)acrylate, benzyl(meth)acrylate, EO-modified (2)nonylphenol acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, acryloylmorpholin, N-vinylcarbazole, 1-vinylimidazole, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and N-vinylformamide. 1,3-Butylene glycol di(meth)acrylate, 1,4-Butanediol di(meth)acrylate, 3-Methyl-1,5-Pentanediol di(meth)acrylate, 1,6-Hexanediol di(meth)acrylate, 1,9-Nonanediol di(meth)acrylate, 1,10-Decanediol di(meth)acrylate, 1,2-Dodecanediol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, Polyethylene glycol (200) di(meth)acrylate, Polyethylene glycol (300) di(meth)acrylate, Polyethylene glycol (400) di(meth)acrylate, Polyethylene glycol (600) di(meth)acrylate, Neopentyl glycol di(meth)acrylate, Dipropyl Difunctional radical polymerizable compounds such as benzoglycol 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, dimethylol tricyclodecane di(meth)acrylate, EO-modified (4) bisphenol A di(meth)acrylate, PO-modified (4) bisphenol A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, dicyclopentanyl di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate, Trifunctional radical polymerizable 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 isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. Tetrafunctional radical polymerizable compounds such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate, Pentafunctional radical polymerizable compounds such as dipentaerythritol penta(meth)acrylate, Examples include hexafunctional radical polymerizable compounds such as dipentaerythritol hexa(meth)acrylate.

[0048] Furthermore, as the radical polymerizable compound (Z), urethane acrylates such as aliphatic urethane acrylates and aromatic urethane acrylates, polyester acrylates, polyether acrylates, epoxy acrylates, etc., can be used.

[0049] <Resin> In the present invention, the active energy ray curable composition may contain a resin. Examples of resins contained in the present invention include polyvinyl chloride, acrylic resin, epoxy resin, polyester resin, polyurethane resin, cellulose derivatives (e.g., ethylcellulose, 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. Furthermore, these resins can also be modified before use. Specifically, examples include chlorination, bromination, amine modification, and carboxylic acid modification. The resin may be used alone or in combination of two or more types.

[0050] From the viewpoint of compatibility and curability, the resin preferably has a weight-average molecular weight (hereinafter also referred to as Mw) of 1,000 to 100,000, and more preferably 2,000 to 70,000. Furthermore, from the viewpoint of chemical resistance, the glass transition temperature (hereinafter also referred to as Tg) is preferably 50 to 150°C, and more preferably 60 to 120°C.

[0051] In this invention, Mw was measured by gel permeation chromatography (hereinafter referred to as "GPC"). The specific measurement method for GPC is as follows: A Tosoh HLC-8020 was used, and a calibration curve was prepared using standard polystyrene samples. Tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M columns (Tosoh Corporation) were used. The measurement was performed at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40°C.

[0052] The glass transition temperature can be calculated from the glass transition temperature of the homopolymer monomers constituting the resin, or it can be measured experimentally. One method of calculation from the glass transition temperature of the homopolymer monomers is, for example, using the FOX equation. Another method of experimental measurement is to obtain it by measuring a DSC curve using a differential scanning calorimeter.

[0053] <Other ingredients> In the present invention, the active energy ray curable composition may optionally contain leveling agents, antistatic agents, surfactants, defoaming agents, ultraviolet absorbers, antioxidants, etc., to the extent that the effects of the present invention are not reduced.

[0054] <Laminate> The laminate in this invention is obtained by printing an active energy ray-curable composition onto a substrate or onto the printed surface of a printed material on which ink has been printed on a substrate. There are no particular restrictions on the substrate, and known substrates can be used. Specifically, examples 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; and plastic films such as PET (polyethylene terephthalate), PP (polypropylene), and OPP (biaxially oriented polypropylene). Furthermore, any ink suitable for known printing methods such as offset printing, gravure printing, flexographic printing, and inkjet printing can be used as the ink printed on the substrate.

[0055] Methods for printing or coating the active energy ray-curable composition of the present invention onto a substrate or onto the printed surface of a printed material on a substrate include roll coaters, gravure coaters, flexographic 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 (conventional lithographic printing using dampening solution and waterless lithographic printing without dampening solution), flexographic printing, gravure printing, screen printing, and inkjet printing.

[0056] In the present invention, there are no particular restrictions on the method of curing the active energy ray-curable composition, and known active energy ray sources can be used. Specifically, 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. [Examples]

[0057] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these. In the examples and comparative examples, "parts" refers to "parts by mass," and "%" refers to "mass%."

[0058] [Method for producing an active energy ray curable composition] Example 1 40.5 parts epoxy resin varnish, 40.0 parts DPHA, 10.0 parts TMP(EO)TA, 5.0 parts TPO, 0.5 parts H-BHT, 3.0 parts polyethylene wax, and 1.0 part antibacterial agent (AW10D manufactured by Sinanen Zeomic) were measured out, stirred while heated to 60°C, and after confirming that the mixture was homogeneous, it was dispersed using a three-roll roller and filtered to obtain an activated energy ray curable composition.

[0059] Examples 2-21, Comparative Examples 1-8 Examples 2-21 and Comparative Examples 1-8 were obtained using the same method as in Example 1, except that the types and amounts of raw materials listed in Table 1 were used. Unless otherwise specified, the numerical values ​​represent "parts by mass," and blank spaces indicate that the ingredient was not included.

[0060] [Table 1]

[0061] [Table 1]

[0062] The details of the raw materials listed in Table 1 are as follows: Epoxy resin varnish: Banbeam UV103D (manufactured by Harima Chemicals Co., Ltd.) DPHA: Ditrimethylolpropane hexaacrylate (Sartomer DPHA) TMP(EO)TA: Ethylene oxide-modified trimethylolpropane triacrylate (Sartomer SR454) Calcium carbonate: Hakuenka O (made by Shiraishi Calcium) Dry silica: Rheoroseal MT-10C (manufactured by Tokuyama) Carbon Black: Mogul E (Cabot) Titanium dioxide: CR-90 (manufactured by Ishihara Sangyo Co., Ltd.) Polyethylene wax: T-wax compound (manufactured by Toshin Yushi Co., Ltd.) Vaseline: White Protopet 1S (Sonneborn) Microcrystalline wax: Hi-Mic-1070 (manufactured by Nippon Seiro Co., Ltd.) PTFE wax: KTL-4N (manufactured by Kitamura) TPO:2,4,6-trimethylbenzoyl-diphenylphosphine oxide H-BHT: 2,6-di-tert-butyl-4-methylphenol Q-1301: N-nitrosophenylhydroxylamine aluminum salt Antibacterial agent A: AW10D (Sinanen Zeomic silver / zeolite) Antimicrobial agent B: Novalon AG300 (manufactured by Toagosei, silver / zirconium phosphate) Antibacterial agent C: Novalon VZF101 (manufactured by Toagosei, zinc / zirconium phosphate)

[0063] [Method for preparing test samples for antimicrobial activity evaluation] The active energy ray-curable compositions obtained in Examples 1-17 and Comparative Examples 1-7 were printed as solid images on PET film with a volume of 0.25 ml using an RI tester (manufactured by Tester Sangyo Co., Ltd.). Subsequently, the active energy ray-curable compositions were cured using a conveyor speed of 60 m / min and a high-pressure mercury lamp (manufactured by I-Graphics Co., Ltd., irradiation distance of 10 mm, output of 160 W / cm) to prepare test samples for antibacterial evaluation. Similarly, the active energy ray-curable compositions obtained in Examples 18-21 were printed as solid images on PET film with a volume of 0.25 ml using an RI tester (manufactured by Tester Sangyo Co., Ltd.). Subsequently, the active energy ray-curable compositions were cured using an electron beam irradiation machine EC250 / 15 / 180L manufactured by Iwasaki Electric Co., Ltd., under conditions of acceleration voltage of 110 kV and electron dose of 30 kGy to prepare test samples for antibacterial evaluation.

[0064] [Antibacterial] The antibacterial properties of the compositions printed on PET film were evaluated according to the method specified in JIS-Z2801. 5. Antibacterial activity value of 5 or higher 4. Antibacterial activity value is 4 or higher but less than 5. 3. Antibacterial activity value is 3 or higher but less than 4. 2. Antibacterial activity value is between 2 and 3. 1. Antibacterial activity value is less than 2.

[0065] [Method for preparing abrasion-resistant samples] The active energy ray-curable compositions obtained in Examples 1-17 and Comparative Examples 1-7 were printed as solid images on PET films with a volume of 0.25 ml using an RI tester (manufactured by Tester Sangyo Co., Ltd.). Subsequently, the active energy ray-curable compositions were cured using a conveyor speed of 60 m / min and a high-pressure mercury lamp (manufactured by I-Graphics Co., Ltd., irradiation distance of 10 mm, output of 160 W / cm) to prepare abrasion resistance test samples. Similarly, the active energy ray-curable compositions obtained in Examples 18-21 were printed as solid images on PET films with a volume of 0.25 ml using an RI tester (manufactured by Tester Sangyo Co., Ltd.). Subsequently, the active energy ray-curable compositions were cured using an electron beam irradiation machine EC250 / 15 / 180L manufactured by Iwasaki Electric Co., Ltd., under conditions of acceleration voltage of 110 kV and electron dose of 30 kGy to prepare abrasion resistance test samples.

[0066] [Abrasion resistance] The abrasion resistance of compositions printed on PET film was evaluated using a JSPS-type abrasion fastness tester (manufactured by Tester Sangyo Co., Ltd.) under the conditions of a weight of 500g and 500 cycles of friction. 5. It doesn't get scratched at all. 4...The scratches are barely visible. 3. The scratches are visible. 2. The base coat is slightly visible. 1. The base layer is clearly visible.

[0067] [Method for preparing test samples for gloss evaluation] The active energy ray-curable compositions obtained in Examples 1-17 and Comparative Examples 1-7 were printed as solid images on art paper (Mitsubishi Paper Mills Limited, Tokubishi Art N) with a thickness of 0.25 ml using an RI tester (manufactured by Tester Sangyo Co., Ltd.). Subsequently, the active energy ray-curable compositions were cured using a conveyor speed of 60 m / min and a high-pressure mercury lamp (manufactured by I-Graphics Co., Ltd., irradiation distance 10 mm, output 160 W / cm) to prepare test samples for gloss evaluation. Similarly, the active energy ray-curable compositions obtained in Examples 18-21 were printed as solid images on art paper (Mitsubishi Paper Mills Limited, Tokubishi Art N) with a thickness of 0.25 ml using an RI tester (manufactured by Tester Sangyo Co., Ltd.). Subsequently, the active energy ray-curable compositions were cured using an electron beam irradiation machine EC250 / 15 / 180L manufactured by Iwasaki Electric Co., Ltd. under conditions of acceleration voltage of 110 kV and electron dose of 30 kGy to prepare test samples for gloss evaluation.

[0068] The gloss of the obtained test samples was measured using a gloss meter (GLOSS METER GM-26D, manufactured by Murakami Color Research Institute, incident angle 60°). 5. Gloss value of 40 or higher 4. Gloss value between 38 and 40. 3. Gloss value between 36 and 38 2. Gloss value between 34 and 36 1. Gloss value less than 34

[0069] [Printability] The active energy ray-curable compositions obtained in Examples 1-21 and Comparative Examples 1-7 were used to print 10,000 sheets of coated cardboard on a UV offset printing press (Komori Corporation). The deposition state of the varnish on the metering roller was then observed. *The evaluation of the metering roller does not require curing, so UV / EB is irrelevant. 5. Almost no composition adheres to the measuring roller. 4. The composition is adhering to the end of the measuring roller. 3. The composition is adhering to the entire measuring roller. 2. The composition is thickly adhered to the entire measuring roller. 1. The composition adheres thickly to the entire measuring roller, causing stains on the paper.

[0070] [Storage stability] The obtained active energy ray-curable composition was filled into a glass bottle, degassed and stirred, and then left to stand in a 100°C oven. After a certain period, the storage stability of the composition was evaluated by inserting a rod into the composition. If the storage stability of the composition deteriorates and polymerization occurs, the rod can no longer be inserted (gelation). The longer the period during which the rod can be inserted, the better the storage stability. The rod can still be inserted even after 5 to 12 days have passed. The rod can be inserted for up to 4-10 days (it can no longer be inserted after 11-12 days). The rod can be inserted for up to 3-8 days (it can no longer be inserted after 9-10 days). The rod can be inserted for up to 2-6 days (it can no longer be inserted after 7-8 days). The rod can be inserted for up to 1-4 days (it will no longer be possible to insert the rod after 5-6 days).

[0071] [Table 2]

[0072] Based on the above, by using the active energy ray curable composition of the present invention, it is possible to provide an active energy ray curable composition and laminate that exhibit excellent antibacterial properties with a small amount of antibacterial agent added, and that have high gloss and film durability.

Claims

1. A laminate having a layer on the printed surface of a printed material on which ink has been printed on a substrate, wherein an active energy ray-curable composition has been printed and cured with active energy rays, The active energy ray curable composition comprises a polymerizable compound, a wax, an antibacterial agent, a polymerization inhibitor, and an extender pigment. The amount of the antibacterial agent is 0.05 to 15% by mass of the total amount of the active energy ray curable composition. The wax comprises one or more selected from the group consisting of polyolefin wax, paraffin wax, acrylic beeswax, urethane beeswax, Fischer-Tropsch wax, microcrystalline wax, petrolatum, and carnauba wax. The wax content is 0.5 to 10% by mass of the total amount of the active energy ray curable composition. The polymerization inhibitor content is 0.01 to 3% by mass of the total amount of the active energy ray curable composition. A laminate characterized in that the extender pigment content is 1 to 20% by mass of the total amount of the active energy ray curable composition.

2. The laminate according to claim 1, characterized in that the antibacterial agent contains a compound containing at least one metal element selected from the group consisting of silver, copper, zinc, and tin.

3. The laminate according to claim 1 or 2, further characterized by containing a coloring agent.

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