Active energy ray-curable resin composition, cured product, laminate, and article

Abstract

To provide an active energy ray-curable resin composition which has high refractive index performance and is excellent in hardness, scratch resistance, and moist heat resistance.SOLUTION: The active energy ray-curable resin composition is used which contains a urethane (meth)acrylate (A), a bisphenol A type epoxy (meth)acrylate (B), a compound (C) having at least three (meth)acryloyl groups, and a photopolymerization initiator (D). The urethane (meth)acrylate (A) uses a polyvalent isocyanate compound (a1) and a compound (a2) having at least one hydroxyl group and at least two (meth)acryloyl groups as essential raw materials.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an active energy ray curable resin composition, a cured product, a laminate, and an article.

Background Art

[0002] An optical laminate used on the surface or inside of an image display device typified by a liquid crystal display (LCD) is usually required to have hardness so as not to be damaged during handling. Therefore, a hard coat layer or the like is generally provided on a light transmissive substrate to impart hardness and an antireflection function (see, for example, Patent Document 1). Conventionally, as the light transmissive substrate, TAC (triacetyl cellulose film) has been used because it has excellent transparency and optical isotropy and has little retardation in the plane, so that it has little influence on the display quality of a liquid crystal display device. However, it has a problem that its moisture and heat resistance is not sufficient, and when it is used as a polarizing plate protective film in a high temperature and high humidity environment, the polarizing plate functions such as a polarizing function and a hue are deteriorated.

[0003] Therefore, the replacement with a polarizing plate protective film using a special PET substrate having excellent water resistance and durability has been promoted, and for the hard coat layer on the substrate, it has been studied to impart high hardness, mechanical properties such as refractive index, and excellent durability.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The problem to be solved by the present invention is to provide an active energy ray curable resin composition, a cured product, a laminate, and an article having high refractive index performance and excellent hardness, scratch resistance, and moisture and heat resistance.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that a specific urethane (meth)acrylate having a polyisocyanate compound having an acryloyl group concentration in a specific range and a polyfunctional (meth)acrylate having a hydroxyl group as essential raw materials, bisphenol A type epoxy (meth)acrylate, a compound having at least three (meth)acryloyl groups having an acryloyl group concentration in a specific range, and a photoinitiator are used, and the above problems can be solved, and the present invention has been completed.

[0007] That is, the present invention relates to an active energy ray-curable resin composition containing a urethane (meth)acrylate (A), a bisphenol A type epoxy (meth)acrylate (B), a compound (C) having at least three (meth)acryloyl groups, and a photoinitiator (D), wherein the urethane (meth)acrylate (A) is characterized in that it uses a polyisocyanate compound (a1) and a compound (a2) having at least one hydroxyl group and at least two (meth)acryloyl groups as essential raw materials, and relates to a cured product, a laminate, and an article.

Effects of the Invention

[0008] The active energy ray-curable resin composition of the present invention has high refractive index performance and is excellent in hardness, scratch resistance, and heat and humidity resistance, and thus can be suitably used as a coating agent or the like.

Modes for Carrying Out the Invention

[0009] The active energy ray-curable resin composition of the present invention is characterized by containing a urethane (meth)acrylate (A), a bisphenol A type epoxy (meth)acrylate (B), a compound (C) having at least three (meth)acryloyl groups, and a photoinitiator (D).

[0010] In the present invention, “(meth)acrylate” means acrylate and / or methacrylate. Further, “(meth)acryloyl” means acryloyl and / or methacryloyl. Furthermore, “(meth)acrylic” means acrylic and / or methacrylic.

[0011] As the urethane (meth)acrylate (A), those using a polyvalent isocyanate compound (a1) and a compound (a2) having at least one hydroxyl group and at least two (meth)acryloyl groups as essential raw materials are used.

[0012] Examples of the polyvalent isocyanate compound (a1) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylene diisocyanate, m-tetramethylxylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (1); isocyanurate-modified products, biuret-modified products, allophanate-modified products, etc. of these. Among these, xylene diisocyanate and m-tetramethylxylene diisocyanate are preferable because an active energy ray-curable resin composition having high refractive index performance and excellent hardness, scratch resistance, and heat and humidity resistance can be obtained. These polyvalent isocyanate compounds can be used alone or in combination of two or more.

[0013] [Chemical formula] [In formula (1), R1 is independently either a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R 2 is independently an alkyl group having 1 to 4 carbon atoms, l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15.]

[0014] As the compound (a2), a compound having at least one hydroxyl group and at least two (meth)acryloyl groups in one molecule is used. For example, trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and the like can be mentioned. Further, a (poly)oxyalkylene-modified product in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the compound having the various hydroxyl groups and (meth)acryloyl groups; a lactone-modified product in which a (poly)lactone structure is introduced into the molecular structure of the compound having the various hydroxyl groups and (meth)acryloyl groups can also be used. Among these, pentaerythritol tri(meth)acrylate is preferable because an active energy ray-curable resin composition having high refractive index performance and excellent hardness, scratch resistance, and heat and humidity resistance can be obtained. Further, these compounds can be used alone or in combination of two or more.

[0015] Since an active energy ray-curable resin composition having high refractive index performance and excellent hardness, scratch resistance, and heat and humidity resistance can be obtained, the hydroxyl value of the compound (a2) is preferably 90 to 170 mgKOH / g, and more preferably 90 to 120 mgKOH / g.

[0016] The production method of the urethane (meth) acrylate (A) is not particularly limited, and it may be produced by any method. For example, the polyisocyanate compound (a1) and the compound (a2) are used in a ratio such that the molar ratio [(NCO) / (OH)] of the isocyanate group of the polyisocyanate compound (a1) to the hydroxyl group of the compound (a2) is in the range of 1 / 1.01 to 1 / 1.1, and the reaction is carried out at a temperature in the range of 60 to 100 °C, and if necessary, using a urethanization catalyst. Further, the production of the urethane (meth) acrylate (A) may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.

[0017] Examples of the urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, and tin octylate, and organic zinc compounds such as zinc octylate.

[0018] Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more.

[0019] Examples of the basic catalyst include amine compounds such as N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide; quaternary ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxylpropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organometallic compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. In addition, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, etc. can also be used. These basic catalysts can be used alone or in combination of two or more.

[0020] In addition, as the raw material of the urethane (meth) acrylate (A), an alkylene oxide-modified bisphenol compound can also be used in addition to the polyvalent isocyanate compound (a1) and the compound (a2).

[0021] Examples of the alkylene oxide-modified bisphenol compound include compounds having a molecular structure represented by the following structural formula (2).

[0022] [Chemical formula] [In the formula, R 3 are each independently any one of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, an aryl group, and a halogenated aryl group. R 4 is any one of a halogen atom, an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, an aryl group, and a halogenated aryl group, and p is each an integer of 0 or 1 to 4. R 5 is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and q is each an integer of 1 or more. ]

[0023] In the structural formula (2), R 3 are each independently any one of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, an aryl group, and a halogenated aryl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. The aliphatic hydrocarbon group may be either linear or branched and may have an unsaturated bond in the structure. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, etc. are mentioned. Examples of the halogenated aliphatic hydrocarbon group include those in which one or all of the hydrogen atoms in the aliphatic hydrocarbon group are substituted with the halogen atom. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a structural moiety in which the aliphatic hydrocarbon group is substituted on these aromatic nuclei. Examples of the halogenated aryl group include those in which one or all of the hydrogen atoms in the aryl group are substituted with the halogen atom.

[0024] R in the structural formula (2) 4 is each independently any one of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, an aryl group, and a halogenated aryl group. Specific examples of each are the same as those of the above R 3 and the like can be mentioned.

[0025] R in the structural formula (2) 5 is an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Among them, since it becomes a urethane (meth) acrylate resin that is even more excellent in the balance between elongation and chemical resistance in the cured product, R 5 is preferably an ethylene group or a propylene group. q in the structural formula (2) is an integer of 1 or more. The alkylene oxide-modified bisphenol compound (B) may contain a plurality of components having different q values.

[0026] Moreover, as commercially available products of the alkylene oxide-modified bisphenol compound, for example, "Newpole BPE-20" manufactured by Sanyo Chemical Industries, Ltd. and the like can be mentioned.

[0027] The acryloyl group concentration of the urethane (meth) acrylate (A) is preferably 6 to 12 mmol / g, more preferably 7 to 10 mmol / g, because an active energy ray-curable resin composition having high refractive index performance and excellent hardness, scratch resistance, and heat and humidity resistance can be obtained.

[0028] The content of the urethane (meth) acrylate (A) is preferably in the range of 40 to 80% by mass, more preferably in the range of 45 to 70% by mass, in the non-volatile content of the active energy ray-curable resin composition, because an active energy ray-curable resin composition having high refractive index performance and excellent hardness, scratch resistance, and heat and humidity resistance can be obtained.

[0029] The bisphenol A type epoxy (meth)acrylate (B) is not particularly limited. For example, a bisphenol A type epoxy resin and (meth)acrylic acid are used in a ratio such that the molar ratio [(glycidyl group) / (COOH)] of the glycidyl group of the bisphenol A type epoxy resin and the carboxyl group of the (meth)acrylic acid is in the range of 1 / 1.01 to 1 / 1.03, and the reaction is carried out at a temperature in the range of 80 to 120 °C, optionally using an epoxidation catalyst, and the resulting product can be used.

[0030] Examples of the epoxidation catalyst include amines such as triethylamine, dimethylbutylamine, and tri-n-butylamine; quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, and benzyltriethylammonium salt; or quaternary phosphonium salts, other phosphines such as triphenylphosphine, and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole. The amount of the epoxidation catalyst used is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 3 parts by mass, per 100 parts by mass of the reaction raw material mixture.

[0031] Examples of commercially available products of the bisphenol A type epoxy (meth)acrylate (B) include "LUXYDIR V-5500" manufactured by DIC Corporation.

[0032] These bisphenol A type epoxy (meth)acrylates can be used alone or in combination of two or more.

[0033] The number of (meth)acryloyl groups per molecule of the bisphenol A type epoxy (meth)acrylate (B) is preferably 2 or more, more preferably 2 to 4, because an active energy ray-curable resin composition excellent in hardness, scratch resistance, and heat and humidity resistance can be obtained. The liquid refractive index of the bisphenol A type epoxy (meth)acrylate (B) is preferably in the range of 1.51 to 1.56.

[0034] Since the content of the bisphenol A type epoxy (meth)acrylate (B) has high refractive index performance and an active energy ray-curable resin composition excellent in hardness, scratch resistance, and heat and humidity resistance can be obtained, the range of 5 to 50% by mass in the nonvolatile content of the active energy ray-curable resin composition is preferable, and the range of 10 to 40% by mass is more preferable.

[0035] As the compound (C), a compound having at least three (meth)acryloyl groups in one molecule is used. For example, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like can be mentioned. In addition, a (poly)oxyalkylene modified product in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the compound having various (meth)acryloyl groups; a lactone modified product in which a (poly)lactone structure is introduced into the molecular structure of the compound having various (meth)acryloyl groups can also be used. Among these, since an active energy ray-curable resin composition having high refractive index performance and excellent in hardness, scratch resistance, and heat and humidity resistance can be obtained, pentaerythritol tri(meth)acrylate is preferable. Further, these compounds can be used alone or in combination of two or more. The compound (C) can be used alone or in combination of two or more.

[0036] Since an active energy ray-curable resin composition excellent in hardness, scratch resistance, and heat and humidity resistance can be obtained, the acryloyl group concentration of the compound (C) is preferably in the range of 6 to 12 mmol / g, and more preferably in the range of 7 to 12 mmol / g.

[0037] Since the content of the compound (C) can provide an active energy ray-curable resin composition having high refractive index performance and excellent hardness, scratch resistance, and heat and humidity resistance, the content in the non-volatile matter of the active energy ray-curable resin composition is preferably in the range of 5 to 50% by mass, more preferably in the range of 10 to 40% by mass.

[0038] Examples of the photopolymerization initiator (D) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, and other radical photopolymerization initiators.

[0039] Examples of commercially available products of the photopolymerization initiator (D) include, for example, "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 907", "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad 754", "Omnirad 784", "Omnirad 500", "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure 10", "Vicure 55" (manufactured by Stoffa Chemical); "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ); "DEAP" (manufactured by Upjohn Chemical), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (manufactured by Ward Blenkinsop); "Runtecure 1104" (manufactured by Runtec), etc. These photopolymerization initiators can be used alone or in combination of two or more.

[0040] The addition amount of the photopolymerization initiator (D) is preferably in the range of 0.05 to 15% by mass, more preferably in the range of 0.1 to 10% by mass, for example, in the non-volatile content of the active energy ray curable resin composition.

[0041] In addition, the active energy ray curable resin composition of the present invention may contain various additives such as an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an inorganic filler, polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, a storage stabilizer, etc., if necessary.

[0042] Examples of the ultraviolet absorber include triazine derivatives such as 2-[4-{ (2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{ (2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; benzotriazoles such as 2-(2'-xanthene carboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole; benzophenones such as 2-xanthene carboxy-4-dodecyloxybenzophenone and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbers can be used alone or in combination of two or more kinds.

[0043] Examples of the polymerization inhibitor include phenol compounds such as p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecanedihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline; quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, diphenoquinone; and melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N-(1.(3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, the reaction product of styrenated diphenylamine and 2,4,4-trimethylpentene, amine compounds such as the reaction product of diphenylamine and 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl = bis[3-(dodecylthio)propionate], thioether compounds such as ditridecan-1-yl = 3,3'-sulfanediyl dipropanoate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitroso benzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc., N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrodimethylamine, p-nitro-N,N-diethylamine, N-nitrosoethanolamine, N-nitroso-di-n-butylamine, N-nitroso-N-n-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, dinitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N-n-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds, the ester of phosphoric acid and octadecan-1-ol, triphenyl phosphite, 3,9-dioctadecyl-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] Phosphite compounds such as undecane, tris(nonylphenyl) phosphite, phosphorous acid (1-methylethylidene)-di-4,1-phenylene tetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenylisodecyl phosphite, triisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, etc.; zinc compounds such as bis(dimethyldithiocarbamato-κ(2)S,S’)zinc, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, etc.; nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S’)nickel, etc.; 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, sulfur compounds such as distearyl 3,3’-thiodipropionate, etc. These polymerization inhibitors can be used alone or in combination of two or more kinds.

[0044] As the antioxidant, the same compounds as those exemplified for the polymerization inhibitor can be used, and the antioxidant can be used alone or in combination of two or more kinds.

[0045] Further, as commercially available products of the polymerization inhibitor and the antioxidant, for example, "Q-1300", "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., "Sumilizer BBM-S", "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd., etc. can be mentioned.

[0046] As the organic solvent, the same solvents as those exemplified as the above-mentioned organic solvents can be used, and the organic solvent can be used alone or in combination of two or more kinds.

[0047] As the inorganic filler, for example, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, etc. can be mentioned. These inorganic fillers can be used alone or in combination of two or more kinds.

[0048] As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0049] Examples of the inorganic pigment include white pigments, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, ultramarine blue, ultramarine, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more.

[0050] Examples of the white pigment include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, zinc sulfide, etc. These white pigments can be used alone or in combination of two or more.

[0051] Examples of the organic pigment include quinacridone pigment, quinacridone quinone pigment, dioxazine pigment, phthalocyanine pigment, anthrapyrimidine pigment, anthraquinone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, diketopyrrolopyrrole pigment, perinone pigment, quinophthalone pigment, anthraquinone pigment, thioindigo pigment, benzimidazolone pigment, azo pigment, etc. These organic pigments can be used alone or in combination of two or more.

[0052] Examples of the defoaming agent include silicone-based defoaming agents, polyether-based defoaming agents, fatty acid ester-based defoaming agents, etc. These defoaming agents can be used alone or in combination of two or more.

[0053] Examples of the viscosity modifier include acrylic polymers and synthetic rubber latexes that can be thickened by adjusting to an alkaline pH, urethane resins that can be thickened by molecular association, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, hydrogenated castor oil, amide wax, polyethylene oxide, metal soaps, dibenzylidene sorbitol, and the like. These viscosity modifiers can be used alone or in combination of two or more.

[0054] Examples of the leveling agent include silicone-based compounds, acetylene diol-based compounds, fluorine-based compounds, and the like. These leveling agents can be used alone or in combination of two or more.

[0055] Examples of the flame retardant include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic phosphorus compounds such as phosphoric acid amides; phosphorus ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic organic phosphorus compounds, and organic phosphorus compounds such as derivatives obtained by reacting them with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resin; inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low melting point glasses. These flame retardants can be used alone or in combination of two or more.

[0056] The cured product of the present invention can be obtained by irradiating the active energy ray-curable resin composition with active energy rays. Examples of the active energy rays include ionizing radiations such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. Further, when ultraviolet rays are used as the active energy rays, in order to efficiently perform the curing reaction by ultraviolet rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or irradiation may be performed in an air atmosphere.

[0057] As the ultraviolet ray light source, an ultraviolet lamp is generally used from the viewpoints of practicality and economy. Specifically, examples include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, an LED, and the like.

[0058] The integrated light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 and more preferably 0.5 to 10 kJ / m 2 This is because when the integrated light amount is within the above range, generation of uncured portions can be prevented or suppressed, which is preferable.

[0059] Note that the irradiation of the active energy rays may be performed in one step or may be performed in two or more steps.

[0060] The laminate of the present invention has a cured coating film of the active energy ray-curable resin composition on one side or both sides of a substrate, and can be obtained by applying the active energy ray-curable resin composition on the substrate and irradiating it with active energy rays to cure it.

[0061] Examples of the substrate include a polyethylene terephthalate substrate, a cyclic olefin-based substrate, a linear olefin-based substrate, an acrylic-based substrate, and the like. Further, the substrate may be in the form of a film.

[0062] As the polyethylene terephthalate substrate, for example, a super birefringent film (SRF) can also be used.

[0063] Examples of the method for forming the cured coating film include a coating method, a transfer method, a sheet adhesion method, etc.

[0064] The coating method is a method in which the paint is spray-coated or applied as a top coat to a molded article using printing equipment such as a curtain coater, a roll coater, or a gravure coater, and then irradiated with active energy rays to be cured.

[0065] The transfer method is a method in which a transfer material obtained by applying the above-mentioned active energy ray-curable resin composition on a substrate sheet having releasability is adhered to the surface of a molded article, then the substrate sheet is peeled off to transfer the top coat to the surface of the molded article, and then irradiated with active energy rays to be cured, or a method in which the transfer material is adhered to the surface of the molded article, irradiated with active energy rays to be cured, and then the substrate sheet is peeled off to transfer the top coat to the surface of the molded article.

[0066] The sheet adhesion method is a method of forming a protective layer on the surface of a molded article by adhering a protective sheet having a coating film made of the above-mentioned curable composition on a substrate sheet, or a protective sheet having a coating film made of a curable composition and a decorative layer on a substrate sheet to a plastic molded article.

[0067] Specifically, the sheet adhesion method includes a method (post-adhesion method) in which the substrate sheet of the protective layer forming sheet prepared in advance is adhered to the molded article and then heat-cured by heating to form a B-stage resin layer, and cross-linking and curing are performed, or a method in which the protective layer forming sheet is sandwiched in a molding die, resin is injected and filled into the cavity, and at the same time as obtaining a resin molded article, its surface is adhered to the protective layer forming sheet and then heat-cured by heating to perform cross-linking and curing of the resin layer (simultaneous molding and adhesion method), etc.

[0068] Here, when using a film-like polyethylene terephthalate substrate as the substrate, the coating amount when applying the active energy ray curable resin composition of the present invention onto the film-like polyethylene terephthalate substrate is preferably adjusted so that the film thickness after curing is in the range of 1 to 100 μm. Further, as the coating method at this time, for example, bar coater coating, die coating, spray coating, curtain coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing method, etc. can be mentioned. When the active energy ray curable resin composition of the present invention contains an organic solvent, after coating, it is preferably heated at 80 to 150 °C for several tens of seconds to several minutes to volatilize the organic solvent, and then irradiated with active energy rays to cure the active energy ray curable resin composition.

[0069] In addition to the cured coating film composed of the active energy ray curable resin composition, the laminate of the present invention may have other layer structures. The formation method of these various layer structures is not particularly limited. For example, it may be formed by directly applying a resin raw material, or a sheet-like material may be bonded with an adhesive.

[0070] The article of the present invention has the above laminate on its surface. Examples of the article include plastic molded products such as mobile phones, home appliances, interior and exterior automotive materials, and OA equipment.

Examples

[0071] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. It should be noted that the present invention is not limited to the following Examples.

[0072] In this Example, the weight average molecular weight (Mw) is a value measured under the following conditions using gel permeation chromatography (GPC).

[0073] Measuring device: "HLC-8220" manufactured by Tosoh Corporation Column; "Guard Column H" manufactured by Tosoh Corporation XL -H + "TSKgel G5000HXL" manufactured by Tosoh Corporation + "TSKgel G4000HXL" manufactured by Tosoh Corporation + "TSKgel G3000HXL" manufactured by Tosoh Corporation + "TSKgel G2000HXL" manufactured by Tosoh Corporation Detector; RI (Differential Refractometer) Data Processing: "SC-8010" manufactured by Tosoh Corporation Measurement Conditions: Column Temperature 40°C Solvent: Tetrahydrofuran Flow Rate: 1.0 ml / min Standard; Polystyrene Sample; A 0.4 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

[0074] (Synthesis Example 1: Synthesis of Urethane Acrylate (A1)) Into a flask equipped with a stirring bar, a temperature sensor, and a water-cooled condenser, 1040.4 parts by mass of pentaerythritol (tri / tetra) acrylate ("Aronix M-305" manufactured by Toagosei Co., Ltd., hydroxyl value 110.0 mgKOH / g), 0.10 part by mass of methoquinone, and 0.10 part by mass of dibutyltin dilaurate were charged, mixed with a stirring blade, and heated to 60°C while blowing dry air. Next, 188 parts by mass of xylylene diisocyanate was added dropwise while paying attention to the exotherm to carry out a urethanization reaction. After the addition was completed, the temperature was raised to 80°C and the reaction was continued. After confirming that the isocyanate mass% had become 0.05 mass% or less, it was cooled, and methyl isobutyl ketone was added dropwise to obtain urethane acrylate (A1) with a resin solid content of 80 mass% and an acryloyl group concentration of 8.97 mmol / g.

[0075] (Synthesis Example 2: Synthesis of Urethane Acrylate (A2)) The synthesis was carried out in the same manner as in Synthesis Example 1, except that 188 parts by mass of the xylylene diisocyanate used in Synthesis Example 1 was changed to 244 parts by mass of m-tetramethylxylylene diisocyanate, to obtain a urethane acrylate (A2) having a resin solid content of 80% by mass and an acryloyl group concentration of 8.57 mmol / g.

[0076] (Synthesis Example 3: Synthesis of urethane acrylate (A3)) The synthesis was carried out in the same manner as in Synthesis Example 1, except that 1040.4 parts by mass of the pentaerythritol (tri / tetra) acrylate (manufactured by Toagosei Co., Ltd., "Aronix M-305", hydroxyl value 110.0 mgKOH / g) used in Synthesis Example 1 was changed to 715.3 parts by mass of the pentaerythritol (tri / tetra) acrylate (manufactured by Toagosei Co., Ltd., "Aronix M-306", hydroxyl value 160.0 mgKOH / g), to obtain a urethane acrylate (A3) having a resin solid content of 80% by mass and an acryloyl group concentration of 8.18 mmol / g.

[0077] (Synthesis Example 4: Synthesis of urethane acrylate (A4)) The synthesis was carried out in the same manner as in Synthesis Example 1, except that 188 parts by mass of the xylylene diisocyanate used in Synthesis Example 1 was changed to 222 parts by mass of isophorone diisocyanate, to obtain a urethane acrylate (A4) having a resin solid content of 80% by mass and an acryloyl group concentration of 8.72 mmol / g.

[0078] (Synthesis Example 5: Synthesis of polyfunctional urethane acrylate (A5)) The synthesis was carried out in the same manner as in Synthesis Example 1, except that 188 parts by mass of the xylylene diisocyanate used in Synthesis Example 1 was changed to 250 parts by mass of diphenylmethane diisocyanate ("Lupranate MI" manufactured by BASF INOAC Polyurethane Co., Ltd.), to obtain a urethane acrylate (A5) having a resin solid content of 80 parts by mass% and an acryloyl group concentration of 8.53 mmol / g.

[0079] (Synthesis Example 6: Synthesis of bisphenol A type epoxy acrylate (B1)) Into a flask equipped with a stirring rod, a temperature sensor, and a water-cooled condenser, 344.0 parts by mass of Epiklon 850CRP (bisphenol A type epoxy resin, epoxy equivalent 172.0, manufactured by DIC Corporation), 0.10 part by mass of methoquinone, and 0.50 part by mass of triphenylphosphine were charged, mixed with a stirring blade, and heated to 60 °C while blowing dry air. Next, 146.9 parts by mass of acrylic acid was added dropwise and charged in its entirety, and then, paying attention to heat generation, the temperature was raised to 105 °C, and the reaction was continued for 6 hours. After confirming that the epoxy equivalent exceeded 20,000, it was cooled, and methyl isobutyl ketone was added dropwise to obtain bisphenol A type epoxy acrylate (B1) having a resin solid content of 60% by mass and an acryloyl group concentration of 4.10 mmol / g.

[0080] (Example 1: Preparation of Active Energy Ray-Curable Resin Composition (1)) The following components were blended so as to be the following parts by mass in terms of solid content. 50 parts by mass of urethane acrylate (A1) obtained in Synthesis Example 1, 30 parts by mass of bisphenol A type epoxy acrylate (B1) obtained in Synthesis Example 6, 20 parts by mass of pentaerythritol (tri / tetra) acrylate (manufactured by Toagosei Co., Ltd., "Aronix M-305", hydroxyl value 110.0 mgKOH / g) as compound (C), and 2.0 parts by mass of a photopolymerization initiator (D) ("Omnirad TPO H" manufactured by IGM RESINS B.V.) were blended, and prepared with methoxypropyl acetate to obtain an active energy ray-curable resin composition solution (1) having a nonvolatile content of 40% by mass.

[0081] (Examples 2 to 7: Preparation of Active Energy Ray-Curable Resin Compositions (2) to (7)) Active energy ray-curable resin compositions (2) to (7) were obtained in the same manner as in Example 1 at the blending ratios shown in Table 1.

[0082] (Comparative Examples 1 and 2: Preparation of Active Energy Ray-Curable Resin Compositions (R1) and (R2)) Active energy ray-curable resin compositions (R1) and (R2) were obtained in the same manner as in Example 1 at the blending ratios shown in Table 1.

[0083] Using the active energy ray-curable resin compositions (1) to (7), (R1), and (R2) obtained in the above Examples and Comparative Examples, the following evaluations were carried out.

[0084] [Preparation of laminate] The active energy ray-curable resin compositions obtained in the Examples and Comparative Examples were coated on a super birefringent film (SRF) ("Cosmo Shine SRF" manufactured by Toyobo Co., Ltd., film thickness 80 μm) with a bar coater and dried at 80°C for 40 seconds. Then, under a nitrogen atmosphere, ultraviolet rays were integrally irradiated with a high-pressure mercury lamp (lamp output 120 W / cm) so that the integrated irradiation amount was 1.5 kJ / m 2 to obtain a laminate having a cured coating film with a film thickness of 7 μm on the SRF substrate.

[0085] [Evaluation method for refractive index of cured film] For the above laminate, the refractive index was measured with an Abbe refractometer and evaluated according to the following criteria.

[0086] A: The refractive index was 1.53 or more. B: The refractive index was less than 1.53.

[0087] [Evaluation method for pencil hardness] For the above laminate, in accordance with JIS K5600-5-4 (1999), the pencil hardness of the coating film surface was measured under a load condition of 750 g. Five measurements were made for each hardness, and the hardness with four or more measurements without scratches was taken as the hardness of the cured coating film and evaluated according to the following criteria.

[0088] A: The pencil hardness was 2H or more. B: The pencil hardness was H or more and less than 2H. C: The pencil hardness was less than H.

[0089] [Evaluation method for abrasion resistance] Wrap a 2.4 - centimeter - diameter disc - shaped indenter with 0.5 g of steel wool (Bonsstar #0000 manufactured by Nippon Steel Wool Co., Ltd.), apply a load of 1 kg to the indenter, and conduct an abrasion test by reciprocating 10 times on the painted surface of the laminate. Measure the haze values of the laminate before and after the abrasion test using the "Haze Computer HZ - 2" manufactured by Suga Test Instruments Co., Ltd., and evaluate according to the following criteria using the difference value (dH) of these values. Note that the smaller the difference value (dH), the higher the resistance to scratches.

[0090] A: dH was 1.0 or less. B: dH was more than 1.0 and 3.0 or less. C: dH was more than 3.0.

[0091] The evaluation of the damp heat resistance was carried out by evaluating the substrate adhesion (initial) and the substrate adhesion (after the damp heat test).

[0092] [Evaluation method of substrate adhesion (initial)] Make cuts on the cured coating film surface of the laminate with a cutter knife to create 100 squares of 1 mm×1 mm, stick cellophane adhesive tape on it, and then perform an operation of quickly peeling it off. Count the number of squares remaining without peeling, and evaluate according to the following criteria.

[0093] A: The remaining number of squares was 80 or more. B: The remaining number of squares was less than 80.

[0094] [Evaluation method of substrate adhesion (after the damp heat test)] Test the laminate in a thermo - hygrostat (80°C, 95%RH) for 500 hours. Then, perform the same method as the above - mentioned substrate adhesion (initial), and evaluate according to the following criteria.

[0095] A: The remaining number of squares was 80 or more. B: The remaining number of squares was less than 80.

[0096] Table 1 shows the compositions and evaluation results of the active energy ray-curable resin compositions (1) to (7) prepared in Examples 1 to 7 and the active energy ray-curable resin compositions (R1) and (R2) prepared in Comparative Examples 1 and 2.

[0097]

Table 1

[0098] Note that the parts by mass described in Table 1 are solid content values.

[0099] "Aronix M-305" in Table 1 indicates "Aronix M-305" manufactured by Toagosei Co., Ltd.; pentaerythritol (tri / tetra) acrylate (acryloyl group concentration: 10.59 mmol / g).

[0100] "Aronix M-920" in Table 1 indicates "Aronix M-920" manufactured by Toagosei Co., Ltd.; glycidyl (di / tri) acrylate (acryloyl group concentration: 8.88 mmol / g).

[0101] "Miramer M-240" in Table 1 indicates "Miramer M-240" manufactured by MIWON; bisphenol AEO-modified diacrylate (acryloyl group concentration: 3.91 mmol / g).

[0102] "Viscote #230" in Table 1 indicates "Viscote #230" manufactured by Osaka Organic Chemical Industry Co., Ltd.; 1,6-hexanediol diacrylate (acryloyl group concentration: 8.85 mmol / g).

[0103] Examples 1 to 7 shown in Table 1 are examples of the active energy ray-curable resin composition of the present invention. It was confirmed that this active energy ray-curable resin composition has high refractive index performance and excellent hardness, scratch resistance, and heat and humidity resistance, and has a well-balanced combination of each performance.

[0104] On the other hand, Comparative Examples 1 and 2 are examples of an active energy ray-curable resin composition that does not use a compound (C) having at least three (meth)acryloyl groups. It was confirmed that this active energy ray-curable resin composition does not have both high refractive index performance, hardness, scratch resistance, and wet heat resistance.

Claims

1. A urethane (meth)acrylate (A), a bisphenol A type epoxy (meth)acrylate (B), a compound (C) having at least three (meth)acryloyl groups (excluding the compound corresponding to the urethane (meth)acrylate (A)), and a photoinitiator (D), and is an active energy ray curable resin composition, wherein the content of the urethane (meth)acrylate (A) is 40 to 80% by mass in the total mass of the urethane (meth)acrylate (A), the epoxy (meth)acrylate (B), and the compound (C), the content of the bisphenol A type epoxy (meth)acrylate (B) is 5 to 50% by mass in the non-volatile content of the active energy ray curable resin composition, the content of the compound (C) is 5 to 40% by mass in the non-volatile content of the active energy ray curable resin composition, the urethane (meth)acrylate (A) is made from a polyisocyanate compound (a1) and a compound (a2) having at least one hydroxyl group and at least two (meth)acryloyl groups as essential raw materials, and the polyisocyanate compound (a1) contains xylylene diisocyanate and / or m-tetramethylxylylene diisocyanate, and is an active energy ray curable resin composition.

2. The active energy ray curable resin composition according to Claim 1, wherein the hydroxyl value of the compound (a2) is 90 to 170 mgKOH / g.

3. A cured product of the active energy ray curable resin composition according to Claim 1 or 2.

4. A laminate characterized by having a cured coating film of the active energy ray curable resin composition according to Claim 1 or 2 on one or both sides of a substrate.

5. The laminate according to Claim 4, wherein the substrate is a polyethylene terephthalate substrate.

6. The laminate according to Claim 4 or 5, wherein the substrate is in the form of a film.

7. An article characterized by having the laminate according to any one of Claims 4 to 6 on its surface.

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