Active energy ray-curable composition and laminate

Abstract

To provide an active energy ray-curable composition using a bio-based organic wax having excellent curability, leveling properties, and small environmental load.SOLUTION: There is provided an active energy ray-curable composition which comprises a bio-based organic wax and a (meth)acrylate compound, wherein the bio-based organic wax has a melting point of 40°C or more, the bio-based organic wax has an iodine value of 1 or more, and when the specific gravity of the methacrylate compound is defined as A and the specific gravity of the bio-based organic wax is defined as B, A-B>0.11.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an active energy ray-curable composition and a laminate having excellent curability and leveling properties. [Background technology]

[0002] Compared to oxidative polymerization, penetration drying, and hot air drying oil-based inks, active energy ray curing inks are convenient because they cure instantly, can form strong cured films, and are non-VOC, containing no petroleum-based volatile compounds, so they are widely used in the packaging printing industry for applications ranging from beverage and food packaging, pharmaceutical packaging, and cosmetic packaging to general paper containers. For this reason, they require high coating resistance to protect the substrate and printed layer, gloss to provide aesthetic appeal, and processability.

[0003] In particular, in the food packaging field, electron beam (hereinafter also referred to as "EB") curable ink has been proposed as the ideal form of active energy ray curable ink, as it does not contain photopolymerization initiators and takes into consideration safety and security for humans and the environment. However, due to the large initial capital investment required, it cannot be said to be common, and ultraviolet ray (hereinafter also referred to as "UV") curable ink is more common on the market.

[0004] In recent years, it is known that there has been a gradual shift to LED curing systems that use UV-LED light sources that are energy-saving and suppress the generation of ozone and heat, energy-saving UV systems that use a single metal halide lamp that eliminates the infrared range that generates heat and the ultraviolet range that generates ozone, and energy-saving UV systems that reduce the number of UV lamps from the usual 3 to 4 to just 1.

[0005] Energy-saving UV-curable inks designed to accommodate these new systems have been increasingly replacing general oil-based inks in commercial printing in recent years, but at the same time, energy-saving UV-curable inks are expected to have the same performance as general oil-based inks in terms of printability and print quality.

[0006] On the other hand, there is a demand for reducing the amount of fossil resource-derived components in printing inks. The Japan Printing Ink Makers Association has also established the Ink Green Mark (hereinafter referred to as IG Mark) system as an activity to reduce the environmental impact, and is engaged in activities to rank the degree of environmental friendliness according to the ratio of components derived from biomass among the components contained in ink compositions, using this ratio as an indicator. There is also the Biomass Mark system by the Japan Organics Resources Association. These systems promote the replacement of fossil resource-derived components contained in ink compositions with biomass-derived components with the aim of building a recycling-oriented society. Biomass is an organic compound obtained from plants and other living things through photosynthesis from carbon dioxide and water, and is a sustainable and renewable resource that can be used to turn back into carbon dioxide and water.

[0007] Patent Document 1 discloses an active energy ray-curable composition that uses a wax that is liquid at 25° C. However, the use of a liquid wax has problems such as poor blocking properties as a laminate and deterioration in storage stability.

[0008] Patent Document 2 discloses an oil-based heat-set type lithographic printing composition containing rice wax, a binder resin, and vegetable oils. However, compared to active energy ray-curable compositions, oil-based heat-set type lithographic printing compositions have a problem with abrasion resistance due to the characteristics of the curing method. In addition, biologically derived organic waxes, including rice wax, are oil-based components and therefore have good compatibility with oil-based inks, but their use in active energy ray-curable compositions that do not contain vegetable oils and contain a large amount of highly polar (meth)acrylate compounds has been avoided due to concerns about separation, etc. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] JP 2016-104831 A [Patent Document 2] JP 2015-183079 A Summary of the Invention [Problem to be solved by the invention]

[0010] The problem to be solved by the present invention is to provide an active energy ray-curable composition that has excellent curing and leveling properties and utilizes an organic wax component derived from a living organism, which imposes a small burden on the environment. [Means for solving the problem]

[0011] As a result of intensive research by the present inventors to solve the above problems, they have found that the above problems can be solved by the active energy ray-curable ink composition shown below, and have completed the present invention.

[0012] An active energy ray-curable composition comprising a biologically derived organic wax and a (meth)acrylate compound, The melting point of the biologically derived organic wax is 40°C or higher; The iodine value of the biologically derived organic wax is 1 or more; When the specific gravity of the (meth)acrylate compound is A and the specific gravity of the organic wax derived from living organisms is B, A B > 0.11 The present invention relates to an active energy ray-curable composition,

[0013] The present invention relates to the above active energy ray-curable composition, wherein the degree of dispersion of the active energy ray-curable composition is 25 μm or less.

[0014] The present invention relates to the above active energy ray-curable composition, wherein the content of the biologically derived organic wax is 0.1 to 10 mass % based on the total amount of the active energy ray-curable composition.

[0015] The present invention relates to the above active energy ray-curable composition, wherein the specific gravity of the organic wax derived from a living organism is 1.00 or less.

[0016] The present invention relates to the above active energy ray-curable composition, wherein the (meth)acrylate compound contains a compound having two or more (meth)acryloyl groups in the molecule.

[0017] The present invention relates to the above active energy ray-curable composition, which further contains a resin.

[0018] The present invention relates to a laminate having a substrate and a layer of the cured product of the active energy ray-curable composition. Effect of the Invention

[0019] The present invention has made it possible to provide an active energy ray-curable composition and a laminate that utilize an organic wax component of biological origin, which has excellent curability and leveling properties and imposes a small burden on the environment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] Hereinafter, the embodiments of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments, and can be modified in various ways within the scope of the present invention.

[0021] The terms used in this specification are explained below. "(Meth)acryloyl" means acryloyl and / or methacryloyl (methacryloyl), and "(meth)acrylate" means acrylate and / or methacrylate (methacrylate). "Active energy rays" means energy rays such as ultraviolet rays and electron beams that have the property of causing chemical changes such as chemical reactions in the irradiated object.

[0022] <Active energy ray curable composition> The active energy ray-curable composition of the present invention contains an organic wax derived from a living organism and a (meth)acrylate compound, The melting point of the biologically derived organic wax is 40°C or higher; The iodine value of the biologically derived organic wax is 1 or more; When the specific gravity of the (meth)acrylate compound is A and the specific gravity of the organic wax derived from living organisms is B, A B > 0.11 The active energy ray-curable composition is

[0023] <Organic wax derived from living organisms> The biologically derived organic wax in the present invention has a melting point of 40° C. or higher and an iodine value of 1 or higher; When the specific gravity of the (meth)acrylate compound is A and the specific gravity of the organic wax derived from living organisms is B, A B > 0.11 This is what happens. By using an organic wax derived from living organisms with an iodine value of 1 or more, some or all of the unsaturated bonds in the wax can form bonds with (meth)acrylate compounds upon hardening, thereby maintaining high abrasion resistance. In addition, since the melting point is 40° C. or higher, high blocking properties can be maintained. In addition, when the difference between the specific gravity of the (meth)acrylate compound and the specific gravity of the biologically derived organic wax falls within this range, the effect of the wax is prominently exhibited. This is thought to be because when the difference in specific gravity falls within this range, the wax component is oriented toward the surface side (the side opposite to the substrate) after printing of the composition.

[0024] Examples of organic waxes of biological origin in the present invention include rice wax, snow wax, Japan wax, urushi wax, sugar cane wax, beeswax, candelilla wax, wood wax, and montan wax. These waxes may be used alone or in combination. Among these, it is preferable to use one or more types of biologically derived organic wax selected from the group consisting of rice wax and snow wax, and it is more preferable to use rice wax, since this can provide a particularly high abrasion resistance effect.

[0025] The content of the biologically derived organic wax in the present invention is preferably 0.1 to 10 mass% of the total amount of the active energy ray curable composition. By the content of the biologically derived organic wax being 0.1 to 10 mass% of the total amount of the composition, all of the abrasion resistance, gloss, and printability become good. The content of the biologically derived organic wax is more preferably 1.5 to 8 mass% of the total amount of the composition.

[0026] Furthermore, the biologically derived organic wax in the present invention is characterized by being easily dispersible in an active energy ray-curable composition, among other organic waxes.

[0027] <(Meth)acrylate compounds> The active energy ray-curable composition of the present invention contains a (meth)acrylate compound. The compound preferably used as the (meth)acrylate compound in the present invention may be any compound having at least one (meth)acryloyl group in the molecule, and includes those having chemical forms such as monomers, oligomers, polymers, etc. The (meth)acrylate compound may be used alone or in combination of two or more kinds.

[0028] From the viewpoint of curability, the (meth)acrylate compound in the present invention preferably contains a (meth)acrylate compound having two or more (meth)acryloyl groups in the molecule, more preferably contains a (meth)acrylate compound having three or more (meth)acryloyl groups in the molecule, and particularly preferably contains a (meth)acrylate compound having four or more (meth)acryloyl groups in the molecule.

[0029] The content of the (meth)acrylate compound in the present invention is preferably 10 to 95% by mass based on the total amount of the active energy ray-curable composition.

[0030] Specific examples of the (meth)acrylate compound in the present invention include 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, β-carboxyethyl (meth)acrylate, 4-tert-butylcyclohexanol (meth)acrylate, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, caprolactone (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isoamyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isodecyl (meth)acrylate, 3,3,5-trimethylcyclohexanol (meth)acrylate, cyclohexyl (meth)acrylate, and the like. (meth)acrylate compounds having one (meth)acryloyl group in the molecule, such as acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (oxyethyl) (meth)acrylate, 1,4-cyclohexanedimethanol (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, benzyl (meth)acrylate, EO-modified (2) nonylphenol acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, acryloylmorpholine, 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, Hydroxypivalic acid neopentyl glycol di(meth)acrylate, Dipropylene glycol di(meth)acrylate (1) 1,6-hexanediol di(meth)acrylate, PO-modified (2) neopentyl glycol di(meth)acrylate, (neopentyl glycol-modified) trimethylolpropane di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, EO-modified (3) 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, and other (meth)acrylate compounds having two (meth)acryloyl groups in the molecule; (meth)acrylate compounds having three (meth)acryloyl groups in the molecule, such as trimethylolpropane tri(meth)acrylate, EO-modified (3) trimethylolpropane tri(meth)acrylate, PO-modified (3) trimethylolpropane tri(meth)acrylate, ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate, ethoxylated isocyanuric acid tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; (meth)acrylate compounds having four (meth)acryloyl groups in the molecule, such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; (meth)acrylate compounds having five (meth)acryloyl groups in the molecule, such as dipentaerythritol penta(meth)acrylate; Examples of such compounds include (meth)acrylate compounds having six (meth)acryloyl groups in the molecule, such as dipentaerythritol hexa(meth)acrylate.

[0031] As the (meth)acrylate compound, urethane acrylates such as aliphatic urethane acrylates and aromatic urethane acrylates, polyester acrylates, polyether acrylates, epoxy acrylates, and the like can be used.

[0032] <Polymerization inhibitor> The active energy ray-curable composition of the present invention may contain a polymerization inhibitor, which can provide high storage stability. The polymerization inhibitor in the present invention is not particularly limited, and known ones can be used. Specific examples include hydroquinone, methylhydroquinone, methoxyhydroquinone, tert-butylhydroquinone, and N-nitrosophenylhydroxylamine. These polymerization inhibitors may be used alone or in combination. The content of these polymerization inhibitors is preferably 0.01 to 3 mass% of the total amount of the active energy ray curable composition. When the content of the polymerization inhibitor is within this range, the balance between storage stability and curability is good. The content of the polymerization inhibitor is preferably 0.03 to 2 mass%, and particularly preferably 0.05 to 1 mass%, of the total amount of the active energy ray curable composition.

[0033] <Photopolymerization initiator> In the active energy ray-curable composition of the present invention, a photopolymerization initiator can be used. The photopolymerization initiator used in the present invention may be a commercially available product, but it is particularly preferable to use at least one selected from the group consisting of acylphosphine oxide photopolymerization initiators, dialkoxyacetophenone photopolymerization initiators, benzophenone photopolymerization initiators, and α-hydroxyalkylphenone photopolymerization initiators. These photopolymerization initiators may be used alone or in combination.

[0034] Examples of the acylphosphine oxide photopolymerization initiator include diphenylacylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-bis(4-methylphenyl)phosphine oxide, and ethoxyphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.

[0035] Examples of the dialkoxyacetophenone photopolymerization initiator include 2,2-dimethoxy-2-phenylacetophenone, dimethoxyacetophenone, and diethoxyacetophenone.

[0036] Benzophenone-based photopolymerization initiators include benzophenone, 4-methylbenzophenone, and 4-phenylbenzophenone.

[0037] Examples of the α-hydroxyalkylphenone photopolymerization initiator 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.

[0038] In the present invention, the content of the photopolymerization initiator is preferably 2 to 15% by mass based on the total amount of the active energy ray-curable composition. When the content of the photopolymerization initiator is within this range, the curability and the abrasion resistance of the cured coating film become good. The content of the photopolymerization initiator is more preferably 5 to 15% by mass. However, when EB is used as the active energy ray, sufficient curability can be ensured even without using a photopolymerization initiator.

[0039] <Extender pigment> The active energy ray-curable composition of the present invention can use an extender pigment.

[0040] The extender pigment that can be used in the active energy ray-curable composition of the present invention is not particularly limited, and any known extender pigment can be used. Specific examples include calcium carbonate, magnesium carbonate, barium sulfate, silica, etc.

[0041] The content of the extender pigment is preferably 1 to 20% by mass based on the total amount of the active energy ray-curable composition. When the content of the extender pigment is within this range, the gloss and printability are good. The content of the extender pigment is more preferably 2 to 15% by mass.

[0042] <Coloring agent> The active energy ray-curable composition of the present invention may contain a colorant. The colorant that can be used in the active energy ray-curable composition of the present invention is not particularly limited, and any known pigment or dye can be used. As the pigment, both inorganic pigments and organic pigments can be used.

[0043] Examples of inorganic pigments include carbon blacks such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide.

[0044] Examples of organic pigments include soluble azo pigments such as β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid anilide, acetoacetate anilide, and pyrazolone; insoluble azo pigments such as β-naphthol, β-oxynaphthoic acid anilide, acetoacetate anilide monoazo, acetoacetate anilide disazo, and pyrazolone; phthalocyanine pigments such as copper phthalocyanine blue, halogenated (e.g., chlorinated, brominated, etc.) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, and metal-free phthalocyanine; polycyclic pigments and heterocyclic pigments such as quinacridone, dioxazine, threne (pyranthrone, anthanthrone, indanthrone, anthrapyrimidine, flavanthrone, thioindigo, anthraquinone, perinone, perylene, etc.), isoindolinone, metal complex, quinophthalone, and diketopyrrolopyrrole; and the like.

[0045] More specifically, in terms of the CI color index, black pigments include CI Pigment Black 1, 6, 7, 9, 10, 11, 28, 26, 31, and the like.

[0046] Examples of white pigments include CI Pigment White 5, 6, 7, 12, and 28.

[0047] Examples of yellow pigments include CI Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 18, 24, 73, 74, 75, 83, 93, 95, 97, 98, 100, 108, 109, 110, 114, 120, 128, 129, 138, 139, 174, 150, 151, 154, 155, 167, 180, 185, and 213.

[0048] Blue or cyan pigments include CI Pigment Blue 1, 2, 14, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and the like.

[0049] Red or crimson pigments include CI 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, 11 2, 114, 122, 144, 146, 148, 149, 150, 166, 168, 169, 170, 172, 173, 176, 177, 178, 184, 185, 187, 193, 202, 209, 214, 242, 254, 255, 264, 266, 269, CI Pigment Violet 19, etc.

[0050] Green pigments include CI Pigment Green 1, 2, 3, 4, 7, 8, 10, 15, 17, 26, 36, 45, 50, and the like.

[0051] Purple pigments include CI Pigment Violet 1, 2, 3, 4, 5:1, 12, 13, 15, 16, 17, 19, 23, 25, 29, 31, 32, 36, 37, 39, and 42.

[0052] Orange pigments include CI Pigment Orange 13, 16, 20, 34, 36, 38, 39, 43, 51, 61, 63, 64, 74, and the like.

[0053] In the present invention, the colorant may be used alone or in combination of two or more kinds. The amount of the colorant added is preferably 1 to 60% by mass based on the total amount of the active energy ray-curable composition.

[0054] <Resin> The active energy ray-curable composition of the present invention may contain a resin. Examples of resins contained in the active energy ray curable composition of the present invention include polyvinyl chloride, acrylic resins, epoxy resins, polyester resins, polyurethane resins, cellulose derivatives (e.g., ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride-vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, diallyl phthalate resins, alkyd resins, rosin-modified resins, petroleum resins, urea resins, and synthetic rubbers such as butadiene-acrylonitrile copolymers. Furthermore, these resins can also be modified for use. Specific examples include chlorination, bromination, amine modification, and carboxylic acid modification. The resins may be used alone or in combination of two or more.

[0055] As the resin contained in the active energy ray-curable composition of the present invention, it is particularly preferable to use a diallyl phthalate resin from the viewpoint of curability, and it is particularly preferable to contain a rosin-modified resin from the viewpoint of flowability.

[0056] <Diallyl phthalate resin> The diallyl phthalate resin in the present invention is a resin obtained by polymerizing a diallyl phthalate monomer. As the diallyl phthalate resin, a known one can be used, specifically, Daiso DAP series (Daiso DAP A, Daiso DAP K) manufactured by Osaka Soda Co., Ltd., etc. can be mentioned. By including the diallyl phthalate resin, the curing property is improved.

[0057] <Rosin modified resin> It is particularly preferred that the resin of the present invention contains a rosin-modified resin. The rosin-modified resin in the present invention is a resin that contains a skeleton derived from rosin in the resin skeleton. By containing the rosin-modified resin, the balance of fluidity is maintained and the ink emulsification rate is improved.

[0058] The rosin-modified resin in the present invention is preferably a rosin-modified resin obtained by reacting with a hydroxyl group of a compound obtained by the Diels-Alder reaction of an organic acid having a conjugated double bond contained in the rosin acids (a) with an α,β-unsaturated carboxylic acid or an acid anhydride thereof (b), an organic acid among the rosin acids (a) that does not have a conjugated double bond, or another organic acid, which forms an ester bond by reacting a carboxylic acid in each of these with a polyol (c) to form an ester bond.

[0059] <Rosin acids (a)> The rosin acids (a) used to obtain the rosin-modified resin in the present invention refer to monobasic acids having a cyclic diterpene skeleton. They represent rosin acid, disproportionated rosin acid, hydrogenated rosin acid, or alkali metal salts of the above compounds, and specifically include abietic acid having a conjugated double bond, and its conjugated compounds, such as neoabietic acid, palustric acid, and levopimaric acid, as well as pimaric acid, isopimaric acid, sandaracopimaric acid, and dehydroabietic acid, which do not have a conjugated double bond. Examples of natural resins containing these rosin acids (a) include gum rosin, wood rosin, and tall oil rosin.

[0060] The amount of the rosin acids (a) used to obtain the rosin modified resin of the present invention is preferably 20 to 70 mass %, more preferably 30 to 60 mass %, based on the total amount of the resin raw materials. If the amount of the rosin acids (a) is 20 mass % or more, the gloss of the active energy ray curable coating varnish containing the resin will be good, and if the amount is 70 mass % or less, the abrasion resistance of the active energy ray curable coating varnish will be good.

[0061] <α,β-unsaturated carboxylic acid or its anhydride (b)> Examples of the α,β-unsaturated carboxylic acid or its acid anhydride (b) used to obtain the rosin-modified resin in the present invention include maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, isocrotonic acid, etc., and their acid anhydrides. In view of the reactivity with the rosin acids (a), maleic acid or its acid anhydride is preferred.

[0062] In the present invention, the amount of the α,β-unsaturated carboxylic acid or its anhydride (b) is preferably in the range of 60 to 200 mol %, more preferably in the range of 70 to 180 mol %, and particularly preferably in the range of 80 to 155 mol %, relative to the rosin acids (a). When the amount of the α,β-unsaturated carboxylic acid or its anhydride (b) is adjusted to within the above range, it is easy to obtain a rosin-modified resin having excellent friction resistance and adhesion.

[0063] <Carboxylic acids other than (a) and (b) (hereinafter also referred to as "other organic acids")> In order to obtain the rosin-modified resin of the present invention, in addition to the rosin acids (a) and the α,β-unsaturated carboxylic acid or its acid anhydride (b), other organic acids can also be used alone or in combination of two or more kinds. The blending amount of the other organic acids is preferably 0 to 30% by mass, and more preferably 0 to 20% by mass, based on the total blending amount of the resin raw material.

[0064] Specific examples of other organic acids include, but are not limited to, the following:

[0065] <Organic monobasic acid> Aromatic monobasic acids such as benzoic acid, methylbenzoic acid, tertiary butylbenzoic acid, naphthoic acid, and orthobenzoylbenzoic acid; Compounds that have conjugated double bonds but do not have a cyclic diterpene skeleton, such as conjugated linoleic acid, eleostearic acid, parinaric acid, and calendic acid etc.

[0066] <Alicyclic polybasic acid or its anhydride> Examples of the acid anhydride 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, and acid anhydrides thereof.

[0067] (Other organic polybasic acids or their anhydrides) Examples of the acid anhydride include alkenylsuccinic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, dodecenylsuccinic acid, and pentadecenylsuccinic acid, o-phthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid, and their acid anhydrides.

[0068] <Polyol (c)> Polyol (c) forms an ester bond by reaction with a compound obtained by Diels-Alder reaction between an organic acid having a conjugated double bond contained in rosin acids (a) and an α,β-unsaturated carboxylic acid or its acid anhydride (b), an organic acid having no conjugated double bond among rosin acids (a), or another organic acid, and a carboxylic acid in each of these. In order to obtain the rosin-modified resin of the present invention, the polyols described below can be used alone or in combination of two or more kinds. Specific examples of polyols include, but are not limited to, the following:

[0069] (Linear alkylene dihydric polyol) 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,16-hexadecanediol, 1,2-hexadecanediol, and the like.

[0070] <Branched alkylene dihydric polyol> 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, dimethylol octane, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, and the like.

[0071] <Cyclic dihydric polyol> Cyclic alkylene dihydric polyols such as 1,2-cycloheptanediol, tricyclodecane dimethanol, 1,2-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, hydrogenated catechol, hydrogenated resorcinol, and hydrogenated hydroquinone; aromatic dihydric polyols such as bisphenol A, bisphenol F, bisphenol S, catechol, resorcinol, and hydroquinone.

[0072] <Other dihydric polyols> Divalent polyether polyols such as polyethylene glycol (n=2 to 20), polypropylene glycol (n=2 to 20), and polytetramethylene glycol (n=2 to 20), and polyester polyols.

[0073] <Trivalent polyol> Glycerin, trimethylolpropane, 1,2,6-hexanetriol, 3-methylpentane-1,3,5-triol, hydroxymethylhexanediol, trimethylol octane, etc.

[0074] <Quaternary or higher polyol> Linear, branched and cyclic polyols having 4 or more valences, such as pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, sorbitol, inositol and tripentaerythritol.

[0075] The rosin-modified resin in the present invention preferably has a weight-average molecular weight of 3,000 to 30,000, and more preferably 3,000 to 15,000. When the weight-average molecular weight is 3,000 to 30,000, good abrasion resistance and adhesion can be achieved.

[0076] In the present invention, Mw was measured by gel permeation chromatography (hereinafter referred to as "GPC"). The specific measurement method of GPC is as follows. HLC-8020 manufactured by Tosoh Corporation was used, and a calibration curve was prepared using a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M columns (manufactured by Tosoh Corporation) were used. 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.

[0077] The rosin-modified resin in the present invention preferably has an acid value of 20 to 80 mgKOH / g, more preferably 30 to 80 mgKOH / g, further preferably 40 to 80 mgKOH / g, and particularly preferably 50 to 80 mgKOH / g. When the acid value of the rosin-modified resin is within the above range, the adhesion of the active energy ray curable composition is good. The acid value is a value measured by neutralization titration. Specifically, first, 1 g of the rosin-modified resin was dissolved in 20 mL of a solvent mixed with xylene:ethanol=2:1 in a weight ratio. Next, 3 mL of a 3 wt % phenolphthalein solution was added as an indicator to the previously prepared rosin-modified resin solution, and then neutralization titration was performed with a 0.1 mol / L ethanolic potassium hydroxide solution.

[0078] The melting point of the rosin modified resin is preferably 50° C. or higher, and more preferably in the range of 60 to 100° C. The melting point can be measured using a Melting Point M-565 manufactured by BUCHI under conditions of a temperature rise rate of 0.5° C. / min.

[0079] <Other ingredients> In the present invention, the active energy ray-curable composition may contain, as necessary, a dispersant, a leveling agent, an antistatic agent, a surfactant, an antifoaming agent, an ultraviolet absorber, an antioxidant, and the like, within a range in which the effects of the present invention are not reduced.

[0080] <Dispersion> When the active energy ray curable composition is printed or coated, if coarse particles derived from the wax or aggregates due to mixing of the wax are generated, problems occur during printing or coating, etc., and problems occur in the surface state of the obtained cured product, etc. Therefore, the degree of dispersion of the active energy ray curable composition in the present invention is preferably 25 μm or less, and more preferably 12.5 μm or less. Note that the degree of dispersion in the present invention is a value obtained by measuring the active energy ray curable composition with a dispersed particle size measuring instrument (grind meter) according to JIS K5600-2-5.

[0081] <Laminate> The laminate of the present invention can be obtained by applying the active energy ray-curable composition of the present invention onto a substrate or onto the printed surface of a substrate having ink printed thereon, and curing the composition with active energy rays. The substrate is not particularly limited and may be any known substrate, specifically, coated paper such as art paper, coated paper, cast paper, etc., uncoated paper such as fine paper, medium-quality paper, newsprint, etc., synthetic paper such as Yupo paper, plastic films such as PET (polyethylene terephthalate), PP (polypropylene), OPP (biaxially oriented polypropylene), etc. As the ink used for the printed matter obtained by printing the ink on the substrate, any ink suitable for a known printing method such as offset printing, gravure printing, or flexographic printing can be used.

[0082] Methods for applying the active energy ray-curable composition of the present invention onto a substrate or onto the printed surface of a printed material formed by printing ink on a substrate include a roll coater, a gravure coater, a flexo coater, an air doctor coater, a blade coater, an air knife coater, a squeeze coater, an impregnation coater, a transfer roll coater, a kiss coater, a curtain coater, a cast coater, a spray coater, a die coater, 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.

[0083] In the present invention, the method for curing the active energy ray-curable composition is not particularly limited, and any known active energy ray source can be used, specifically, 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, gas / solid-state lasers, etc. EXAMPLES

[0084] The present invention will be described in detail below with reference to examples and comparative examples. The following examples are not intended to be limiting in any way. "Parts by mass" and "%" represent "parts by mass" and "% by mass", respectively.

[0085] [Production of active energy ray-curable composition] Example 1 15.0 parts of pigment, 40.0 parts of rosin modified resin, 39.5 parts of TMPTA (EO), 0.5 parts of rice wax, 2.0 parts of 379, 1.5 parts of DETX, 1.0 parts of 184, and 0.5 parts of Q-1301 were measured out and stirred at 60°C. After confirming that the mixture was homogenous, the mixture was dispersed using a three-roll mill and filtered to obtain an active energy ray curable composition.

[0086] Examples 2 to 18, Comparative Examples 1 to 6 Examples 2 to 18 and Comparative Examples 1 to 6 were obtained in the same manner as Example 1, except that the types and amounts of raw materials were used as shown in Table 1. Unless otherwise specified, the numerical values ​​indicate "parts by mass", and blank spaces indicate that no compound was added.

[0087] [Table 1]

[0088] [Table 1]

[0089] Table 2 shows the specific gravity of the (meth)acrylate compound, and Table 3 shows the melting point, iodine value, and specific gravity of the wax.

[0090] [Table 2]

[0091] [Table 3]

[0092] Details of the raw materials listed in Tables 1 to 3 are as follows. [resin] Rosin-modified resin: Resin 4 described in paragraph 0076 of WO 2017 / 164246 was used. Diallyl phthalate resin: Osaka Soda Co., Ltd., Daiso DAP A [(Meth)acrylate compounds] TMPTA (EO): BASF, LAROMER LR8863, trimethylolpropane ethylene oxide modified triacrylate DiTMPTA: Daicel-Allnex, EBECRYL1142, ditrimethylolpropane tetraacrylate DPHA: MIWON, MIRAMER M600, dipentaerythritol hexaacrylate DDDA: MIWON, MIRAMER M2010, 1,10-decanediol diacrylate Soybean oil acrylate: DKSH Japan Co., Ltd., PHOTOMER 3005, Epoxidized soybean oil acrylate [Pigment] ·Permanent Yellow BHS: Manufactured by Clariant, Permanent Yellow BHS (CIPigment Yellow 174) ·Permanent Rubine L5B-01: Manufactured by Clariant, Permanent Rubine L5B-01 (CIPigment Red 57:1) ·HELIOGEN BLUE D7088: Manufactured by BASF, HELIOGEN BLUE D7088(CIPigment Blue 15:3) ·Raven 1080 Ultra: Made by Bilra Carbon, Raven 1080 Ultra Powder (CIPigment Black 7) [Photopolymerization initiator] 379: IGM RESINS, Omnirad379, 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone DETX: Chemark Chemical Company, CHEMARK DETX, 2,4-diethylthioxanthone 184: IGM RESINS, Omnirad 184, 1-hydroxy-cyclohexyl phenyl ketone [Photopolymerization inhibitor] Q-1301: Fujifilm Wako Pure Chemical Industries, Ltd., nitroso-based compound, N-nitrosophenylhydroxylamine aluminum salt [wax] Rice wax: Rice wax manufactured by Nippon Seiro Co., Ltd. Snow wax: Snow wax made by Cerarica NODA Co., Ltd. Carnauba wax: Carnauba wax made by Cerarica NODA Co., Ltd. Polyethylene wax: Sanyo Chemical Industries Sanwax 161P polyethylene resin Liquid polyethylene wax: SHAMROCK VARSAFLOW EV polyethylene resin Polytetrafluoroethylene: SHAMROCK SST-3T1 RC Polytetrafluoroethylene

[0093] [How to create a laminate] A solid image was printed on an OK topcoat (paper substrate) in a volume of 0.25 ml using an RI tester (manufactured by Tester Sangyo Co., Ltd.) with the active energy ray curable compositions obtained in Examples 1 to 11, 13 to 18 and Comparative Examples 1 to 6. Thereafter, the active energy ray curable compositions were cured with a conveyor speed of 60 m / min and a high pressure mercury lamp (manufactured by Eye Graphics Co., Ltd., irradiation distance 10 mm, output 160 W / cm) to produce a laminate. In addition, a solid image was printed on the OK topcoat with a deposit of 0.25 ml of the active energy ray curable composition obtained in Example 12 using an RI tester (manufactured by Tester Sangyo Co., Ltd.). Thereafter, the active energy ray curable composition was cured using an electron beam irradiator EC250 / 15 / 180L manufactured by Iwasaki Electric Co., Ltd. under conditions of an acceleration voltage of 110 kV and an electron beam dose of 30 kGy to produce a laminate.

[0094] [Abrasion resistance] The laminate prepared by the above method was subjected to a rub resistance test using a Gakushin type rub fastness tester (load 500g, 200 times, paper: high-quality paper) manufactured by Tester Sangyo Co., Ltd., and the scratches on the laminate were evaluated. A rating of 3 or more is considered to be at a level that is acceptable for practical use. 5: No scratches at all 4: The damaged area is less than 5% 3: The damaged area is 5% or more but less than 10% 2: The damaged area is 10% or more but less than 20% 1: The damaged area is 20% or more

[0095] [Blocking properties] Two sheets of the laminate prepared by the above method were placed on top of each other, with the substrate surface of one laminate and the surface of the cured product of the active energy ray-curable composition of the other laminate, and a weight (1 m 2 The laminate was then placed under pressure (1 kg per unit area) and placed in a thermo-hygrostat (temperature 60°C, humidity 80% RH) and left for 24 hours. After removal, the laminate was peeled off and the condition of the peeled surface was evaluated. A rating of 3 or higher was considered to be at a level that is acceptable for practical use. 5: There is absolutely no peeling of the laminate. 4: The peeled area of ​​the laminate is less than 5%. 3: The peeled area of ​​the laminate is 5% or more but less than 10%. 2: The peeled area of ​​the laminate is 10% or more but less than 20%. 1: The peeled area of ​​the laminate is 20% or more.

[0096] [Leveling ability] Using the test pieces prepared by the above method, the gloss value (based on JIS Z 8741) of the surface of the cured product of the active energy ray curable composition at a reflection angle of 60° was measured using a gloss meter GM62D manufactured by Murakami Color Laboratory. ◯ and △ are evaluated as levels that are acceptable for practical use. ○ Gloss value is 40 or more △: Gloss value is 34 or more and less than 40 × Gloss value is less than 34

[0097] [Dispersion degree] The degree of dispersion of the obtained active energy ray-curable composition was measured using a dispersed particle size measuring device (grind meter) in accordance with JIS K5600-2-5. ◯ and △ are evaluated as being at a level that presents no practical problems. ○: Dispersed particle size is less than 12.5 μm △: Dispersed particle size is 12.5μm or more and 25μm or less ×: Dispersed particle size exceeds 25 μm

Claims

1. An active energy ray-curable composition comprising an organic wax derived from a living organism and a (meth)acrylate compound, The melting point of the biologically derived organic wax is 40° C. or higher; The iodine value of the biologically derived organic wax is 1 or more; When the specific gravity of the (meth)acrylate compound is A and the specific gravity of the organic wax derived from living organisms is B, A-B>0.11 The active energy ray-curable composition according to claim 1,

2. 2. The active energy ray-curable composition according to claim 1, wherein the degree of dispersion of the active energy ray-curable composition is 25 μm or less.

3. 2. The active energy ray-curable composition according to claim 1, wherein the content of the biologically derived organic wax is 0.1 to 10 mass % of the total amount of the active energy ray-curable composition.

4. 2. The active energy ray-curable composition according to claim 1, wherein the specific gravity of the biologically derived organic wax is 1.00 or less.

5. The active energy ray-curable composition according to claim 1 , wherein the (meth)acrylate compound comprises a compound having two or more (meth)acryloyl groups in the molecule.

6. The active energy ray-curable composition according to claim 1 , further comprising a resin.

7. A laminate comprising a substrate and a layer of a cured product of the active energy ray-curable composition according to any one of claims 1 to 6.

Images