JP2023030833A - Active energy ray-curable resin composition, cured product, laminate, and article - Google Patents

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

Optical laminates used on the surface and inside of image display devices typified by liquid crystal displays (LCDs) are usually required to be hardened so as not to be scratched during handling. Hardness and antireflection function are generally imparted by providing a hard coat layer or the like on the surface (see, for example, Patent Document 1). In addition, as the light-transmitting substrate, conventionally, TAC is excellent in transparency and optical isotropy and has little effect on the display quality of the liquid crystal display device because it has almost no in-plane retardation. (triacetyl cellulose film) has been used, but its resistance to moisture and heat is not sufficient, and when used as a polarizing plate protective film in a hot and humid environment, there is a problem that the polarizing plate functions such as polarizing function and hue are deteriorated. rice field.

Therefore, the replacement of polarizing plate protective films using special PET substrates with excellent water resistance and durability is being promoted, and the hard coat layer on such substrates has high hardness, refractive index, and other properties. It is being studied to impart mechanical properties and excellent durability.

WO 97/040115

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 moist heat resistance. be.

As a result of intensive studies to solve the above problems, the present inventors have found that a specific urethane ( An active energy ray-curable resin containing a meth)acrylate, a bisphenol A type epoxy (meth)acrylate, a compound having at least three (meth)acryloyl groups having an acryloyl group concentration within a specific range, and a photopolymerization initiator. The inventors have found that the above problems can be solved by using the composition, and completed the present invention.

That is, the present invention comprises 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), wherein the urethane (meth)acrylate (A) comprises a polyvalent isocyanate compound (a1), at least one hydroxyl group and at least two (meth)acryloyl The present invention relates to an active energy ray-curable resin composition, a cured product, a laminate, and an article, characterized by comprising a compound (a2) having a group as an essential raw material.

INDUSTRIAL APPLICABILITY The active energy ray-curable resin composition of the present invention has high refractive index performance and is excellent in hardness, scratch resistance, and moist heat resistance, and thus can be suitably used for coating agents and the like.

The active energy ray-curable resin composition of the present invention comprises urethane (meth)acrylate (A), bisphenol A type epoxy (meth)acrylate (B), and a compound (C) having at least three (meth)acryloyl groups. , and a photopolymerization initiator (D).

In addition, in this invention, "(meth)acrylate" means an acrylate and/or a methacrylate. Moreover, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acryl" means acryl and/or methacryl.

As the urethane (meth)acrylate (A), one containing 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 is used.

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; norbornane diisocyanate , isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate and other alicyclic diisocyanate compounds; Aromatic diisocyanate compounds such as 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 thereof, biuret Modified products, allophanate modified products and the like can be mentioned. Among these, xylene diisocyanate and m-tetramethylxylene diisocyanate are preferred because they have high refractive index performance and yield an active energy ray-curable resin composition having excellent hardness, scratch resistance, and moist heat resistance. In addition, these polyvalent isocyanate compounds can be used alone or in combination of two or more.

［式（１）中、Ｒ^１はそれぞれ独立して、水素原子、または炭素原子数１～６の炭化水素基の何れかである。Ｒ^２はそれぞれ独立して、炭素原子数１～４のアルキル基であり、ｌは０または１～３の整数であり、ｍは１～１５の整数である。］

[In formula (1), each R ¹ is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Each 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. ]

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, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate ) acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and the like. In addition, (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are added to the molecular structures of the compounds having various hydroxyl groups and (meth)acryloyl groups. Introduced (poly)oxyalkylene modified products; lactone modified products obtained by introducing a (poly)lactone structure into the molecular structure of the various compounds having a hydroxyl group and a (meth)acryloyl group can also be used. Among these, pentaerythritol tri(meth)acrylate is preferable because it has a high refractive index performance and provides an active energy ray-curable resin composition excellent in hardness, scratch resistance, and moist heat resistance. In addition, these compounds can be used alone or in combination of two or more.

The hydroxyl value of the compound (a2) is preferably 90 to 170 mgKOH/g because it has a high refractive index performance and provides an active energy ray-curable resin composition having excellent hardness, scratch resistance, and moisture and heat resistance. , 90 to 120 mg KOH/g is more preferred.

The method for producing the urethane (meth)acrylate (A) is not particularly limited, and any method may be used. For example, the polyvalent isocyanate compound (a1) and the compound (a2), the isocyanate group of the polyvalent isocyanate compound (a1), the molar ratio of the hydroxyl group of the compound (a2) [(NCO) / (OH)] is used at a ratio in the range of 1/1.01 to 1/1.1, and the temperature range is 60 to 100 ° C., and if necessary, a method of using a urethanization catalyst. mentioned. Moreover, the urethane (meth)acrylate (A) may be produced in an organic solvent, if necessary, or a basic catalyst may be used, if necessary.

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

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; toluene, xylene and solvent. Aromatic solvents such as naphtha; Alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene glycol monomethyl ether; Alkylene glycol monoalkyl ethers and dialkylene glycol monoalkyl ethers , dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like. These organic solvents can be used alone or in combination of two or more.

Examples of the basic catalyst include 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-methyl imidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2- Amine compounds such as aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide; quaternary ammonium compounds such as trioctylmethylammonium chloride and trioctylmethylammonium acetate Salts; Phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; Phosphonium salts such as triphenylphosphonium chloride and benzylphosphonium chloride; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, Organic tin compounds such as 1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; Organometallic compounds such as zinc octylate and bismuth octylate; Inorganic tin compounds such as tin octoate; mentioned. Alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides and the like can also be used. These basic catalysts can be used alone or in combination of two or more.

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

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

［式中Ｒ^３はそれぞれ独立して、水素原子、ハロゲン原子、脂肪族炭化水素基、ハロゲン化脂肪族炭化水素基、アリール基、ハロゲン化アリール基の何れかである。Ｒ^４はハロゲン原子、脂肪族炭化水素基、ハロゲン化脂肪族炭化水素基、アリール基、ハロゲン化アリール基の何れかであり、ｐはそれぞれ０又は１～４の整数である。Ｒ^５は炭素原子数１～６の脂肪族炭化水素基であり、ｑはそれぞれ１以上の整数である。］

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

Each ^R3 in the structural formula (2) is independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, an aryl group, or a halogenated aryl group. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and the like. The aliphatic hydrocarbon group may be linear or branched, and may have an unsaturated bond in its structure. Specific examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group and the like. 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 atoms. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and structural sites in which the aromatic nuclei of these groups are substituted with the aliphatic hydrocarbon group. 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 atoms.

Each R ⁴ in the structural formula (2) is independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, an aryl group, or a halogenated aryl group. Specific examples of each are the same as those for R ³ above.

R ⁵ in the structural formula (2) is an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Among these, ^R5 is preferably an ethylene group or a propylene group, since the urethane (meth)acrylate resin will have a better balance between elongation and chemical resistance in the cured product. 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 with different q values.

Examples of commercially available products of the alkylene oxide-modified bisphenol compound include "Newpol BPE-20" manufactured by Sanyo Chemical Industries, Ltd., and the like.

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

The content of the urethane (meth)acrylate (A) has a high refractive index performance, and an active energy ray-curable resin composition having excellent hardness, scratch resistance, and moist heat resistance is obtained. It 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 radiation-curable resin composition.

The bisphenol A type epoxy (meth)acrylate (B) is not particularly limited. The molar ratio [(glycidyl group) / (COOH)] with the carboxyl group of meth)acrylic acid is used at a rate in the range of 1/1.01 to 1/1.03, and the temperature range is 80 to 120 ° C. Among them, if necessary, those obtained by reacting with an epoxidation catalyst can be used.

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. , quaternary phosphonium salts, 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.

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

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

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

The content of the bisphenol A-type epoxy (meth)acrylate (B) has a high refractive index performance, and an active energy ray-curable resin composition having excellent hardness, scratch resistance, and moist heat resistance is obtained. It is preferably in the range of 5 to 50% by mass, more preferably in the range of 10 to 40% by mass, based on the non-volatile content of the active energy ray-curable resin composition.

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. In addition, a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, (poly)oxypropylene chain, or (poly)oxytetramethylene chain is introduced into the molecular structure of the compounds having various (meth)acryloyl groups. (Poly)oxyalkylene modified products; Lactone modified products obtained by introducing a (poly)lactone structure into the molecular structure of the various compounds having a (meth)acryloyl group can also be used. Among these, pentaerythritol tri(meth)acrylate is preferable because it has a high refractive index performance and provides an active energy ray-curable resin composition excellent in hardness, scratch resistance, and moist heat resistance. In addition, 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.

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

The content of the compound (C) has a high refractive index performance, and an active energy ray-curable resin composition having excellent hardness, scratch resistance, and moist heat resistance is obtained, so the active energy ray-curable resin It is preferably in the range of 5 to 50% by mass, more preferably in the range of 10 to 40% by mass, based on the non-volatile content of the composition.

Examples of the photopolymerization initiator (D) include 1-hydroxycyclohexylphenyl 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-diphenylethan-1-one, diphenyl (2,4,6-trimethoxy benzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone and other photoradical polymerization initiators.

Commercially available products of the photopolymerization initiator (D) include, for example, "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379" and "Omnirad 907". , “Omnirad 4265”, “Omnirad 1000”, “Omnirad 651”, “Omnirad TPO”, “Omnirad 819”, “Omnirad 2022”, “Omnirad 2100”, “Omnirad 754”, “Omnirad 784”, “Omnirad 500mni , "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). These photopolymerization initiators can be used alone or in combination of two or more.

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

In addition, the active energy ray-curable resin composition of the present invention may optionally contain an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an inorganic filler, a fine polymer particle, a pigment, an antifoaming agent, a viscosity Various additives such as regulators, leveling agents, flame retardants, and storage stabilizers can also be contained.

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

Examples of the polymerization inhibitor include 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)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine , 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and other phenolic compounds, hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy- quinone compounds such as 1,4-naphthoquinone, anthraquinone and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N.I. N'-diphenyl-p-phenylenediamine, Ni-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, styrenated diphenylamine and 2,4,4-trimethyl Amine compounds such as reaction products of pentene, reaction products of diphenylamine and 2,4,4-trimethylpentene, phenothiazine, distearylthiodipropionate, 2,2-bis({[3-(dodecylthio)propionyl]oxy } Methyl)-1,3-propanediyl = bis [3-(dodecylthio) propionate], ditridecan-1-yl = 3,3'-sulfanediyl dipropanoate and other thioether compounds, N-nitrosodiphenylamine, N- Nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc., N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N- Ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide , N-nitroso-N-ethylurethane, N-nitroso-Nn-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sulfone nitroso compounds such as sodium acid, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, phosphoric acid and octadecane- Ester of 1-ol, triphenylphosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosph aspiro[5.5]undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylene tetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, phosphite compounds such as diphenylisodecylphosphite, triisodecyl=phosphite, tris(2,4-di-tert-butylphenyl)phosphite, bis(dimethyldithiocarbamate-κ(2)S,S′) zinc, Zinc compounds such as zinc diethyldithiocarbamate and zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S') nickel, 1,3-dihydro-2H-benzimidazole-2 -thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octane-1-ylsulfanyl)methyl]phenol, dilaurylthiodipropionate, 3, Examples thereof include sulfur compounds such as distearyl 3'-thiodipropionate. These polymerization inhibitors can be used alone or in combination of two or more.

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

Further, commercial products of the polymerization inhibitor and the antioxidant include, for example, "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" manufactured by Sumitomo Chemical Co., Ltd. , “Sumilizer GA-80” and the like.

As the organic solvent, the same organic solvent as exemplified above can be used, and the organic solvent can be used alone or in combination of two or more.

Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. These inorganic fillers can be used alone or in combination of two or more.

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

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

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, and zinc sulfide. etc. These white pigments can be used alone or in combination of two or more.

Examples of the organic pigments include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, Examples include quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments. These organic pigments can be used alone or in combination of two or more.

Examples of the antifoaming agent include silicone antifoaming agents, polyether antifoaming agents, and fatty acid ester antifoaming agents. These antifoaming agents can be used alone or in combination of two or more.

Examples of the viscosity modifier include acrylic polymers and synthetic rubber latex that can be thickened by alkalinity adjustment, urethane resins that can be thickened by molecular association, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, and polyvinyl alcohol. , hydrogenated castor oil, amide wax, polyethylene oxide, metal soap, dibenzylidene sorbitol and the like. These viscosity modifiers can be used alone or in combination of two or more.

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

Examples of the flame retardant include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate; inorganic phosphorus compounds such as phosphate amide; 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-dihydroxy Cyclic organic compounds such as phenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide Organic phosphorus compounds such as phosphorus compounds and derivatives obtained by reacting them with compounds such as epoxy resins and phenolic resins; triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, nitrogen-based flame retardants such as phenothiazine; silicone oils, silicone rubbers, silicone-based flame retardants such as silicone resins; inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass; These flame retardants can be used alone or in combination of two or more.

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

An ultraviolet lamp is generally used as a source of ultraviolet light from the viewpoint of practicality and economy. Specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

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

The irradiation with the active energy ray may be performed in one step, or may be performed in two or more steps.

The laminate of the present invention has a cured coating film of the active energy ray-curable resin composition on one or both sides of a substrate, and the active energy ray-curable resin composition is applied on the substrate. , can be obtained by curing by irradiating with an active energy ray.

Examples of the base material include polyethylene terephthalate base material, cyclic olefin base material, linear olefin base material, and acrylic base material. Moreover, the substrate may be in the form of a film.

As the polyethylene terephthalate base material, for example, a super-birefringent film (SRF) can also be used.

Examples of the method for forming the cured coating film include a coating method, a transfer method, and a sheet adhesion method.

The coating method is a method in which the coating material is spray-coated or coated as a top coat on a molded product using a printing device such as a curtain coater, a roll coater, or a gravure coater, and then cured by irradiation with an active energy ray. is.

In the transfer method, a transfer material obtained by applying the above active energy ray-curable resin composition to a base sheet having releasability is adhered to the surface of a molded product, and then the base sheet is peeled off to mold. A method in which the topcoat is transferred to the product surface and then cured by irradiation with active energy rays, or the transfer material is adhered to the surface of the molded product, cured by irradiation with active energy rays, and then the base sheet is peeled off. This is a method of transferring the top coat to the surface of the molded product by doing so.

The sheet adhesion method is a protective sheet having a coating film made of the curable composition on a base sheet, or a protective sheet having a coating film made of a curable composition and a decorative layer on a base sheet. This is a method of forming a protective layer on the surface of a molded product by adhering it to the molded plastic product.

Specifically, in the sheet bonding method, after bonding a prefabricated base sheet of a protective layer forming sheet to a molded product, the resin layer is formed into a B-stage by thermosetting by heating. A method of cross-linking and curing (post-adhesion method), a method of sandwiching the protective layer forming sheet in a molding die, injecting and filling a resin into a cavity, and simultaneously obtaining a resin molded product and forming a protective layer on its surface. A method in which a sheet is adhered and then thermally cured by heating to cross-link and cure the resin layer (molding-simultaneous adhesion method) can be used.

Here, when a film-like polyethylene terephthalate base material is used as the base material, the coating amount when applying the active energy ray-curable resin composition of the present invention onto the film-like polyethylene terephthalate base material is It is preferable to adjust the film thickness afterward to be in the range of 1 to 100 μm. Further, the coating method at this time includes, for example, bar coater coating, die coating, spray coating, curtain coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, Examples include offset printing, flexo printing, screen printing, and the like. When the active energy ray-curable resin composition of the present invention contains an organic solvent, it is heated under conditions of 80 to 150° C. after application for several tens of seconds to several minutes to volatilize the organic solvent, and then activated. It is preferable to irradiate an energy ray to cure the active energy ray-curable resin composition.

The laminate of the present invention may have other layer structures in addition to the cured coating film made of the active energy ray-curable resin composition. The method of forming these various layer structures is not particularly limited, and for example, resin raw materials may be directly applied to form them, or sheets formed in advance may be pasted together with an adhesive.

The article of the present invention has the laminate on its surface. Examples of the articles include mobile phones, home electric appliances, automotive interior and exterior materials, plastic molded articles such as OA equipment, and the like.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples. It should be noted that the present invention is not limited to the examples given below.

In addition, in the present Examples, the weight average molecular weight (Mw) is a value measured under the following conditions using gel permeation chromatography (GPC).

Measuring device; "HLC-8220" manufactured by Tosoh Corporation
Column; "Guard Column H _XL -H" manufactured by Tosoh Corporation
+ "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 tetrahydrofuran solution of 0.4% by mass in terms of resin solid content filtered through a microfilter (100 μl)

(Synthesis Example 1: Synthesis of urethane acrylate (A1))
Pentaerythritol (tri/tetra) acrylate (manufactured by Toagosei Co., Ltd. "Aronix M-305", hydroxyl value 110.0 mg KOH / g) 1040.4 parts by mass, in a flask equipped with a stirring rod, a temperature sensor, and a water-cooled condenser, 0.10 parts by mass of methoquinone and 0.10 parts 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 xylene diisocyanate was added dropwise while paying attention to heat generation to carry out a urethanization reaction. After confirming that the isocyanate mass% is 0.05% by mass or less, cooling is performed, and methyl isobutyl ketone is added dropwise to obtain a urethane acrylate (A1 ).

(Synthesis Example 2: Synthesis of urethane acrylate (A2))
The procedure was carried out in the same manner as in Synthesis Example 1 except that 188 parts by mass of xylene diisocyanate used in Synthesis Example 1 was changed to 244 parts by mass of m-tetramethylxylene diisocyanate. g of urethane acrylate (A2) was obtained.

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

(Synthesis Example 4: Synthesis of urethane acrylate (A4))
In the same manner as in Synthesis Example 1 except that 188 parts by mass of xylene diisocyanate used in Synthesis Example 1 was changed to 222 parts by mass of isophorone diisocyanate, a urethane acrylate having a resin solid content of 80% by mass and an acryloyl group concentration of 8.72 mmol / g (A4) was obtained.

(Synthesis Example 5: Synthesis of polyfunctional urethane acrylate (A5))
Synthesis Example 1 except that 188 parts by mass of xylene 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.) was carried out in the same manner as in Synthesis Example 1, and the resin solid content was 80 parts by mass. % and an acryloyl group concentration of 8.53 mmol/g to obtain urethane acrylate (A5).

(Synthesis Example 6: Synthesis of bisphenol A type epoxy acrylate (B1))
Epiclon 850CRP (bisphenol A type epoxy resin, epoxy equivalent 172.0, manufactured by DIC Corporation) 344.0 parts by mass, methoquinone 0.10 parts by mass, triphenyl 0.50 part by mass of phosphine was 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 the entire amount was charged, then the temperature was raised to 105° C. while taking care of heat generation, and the reaction was continued for 6 hours. After confirming that the epoxy equivalent exceeds 20,000, it is cooled, and methyl isobutyl ketone is added dropwise to obtain a 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. got

(Example 1: Preparation of active energy ray-curable resin composition (1))
Each component was blended so as to have the following weight parts 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 epoxy acrylate (B1) obtained in Synthesis Example 6, pentaerythritol (tri/tetra) acrylate (Toagosei Co., Ltd.) as compound (C) Company "Aronix M-305", hydroxyl value 110.0 mgKOH / g) 20 parts by weight, photopolymerization initiator (D) (IGM RESINS B.V. "Omnirad TPO H) 2.0 parts by weight. , and methoxypropyl acetate to obtain an active energy ray-curable resin composition solution (1) having a nonvolatile content of 40% by mass.

(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 compounding ratios shown in Table 1.

(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 compounding ratios shown in Table 1.

The following evaluations were performed using the active energy ray-curable resin compositions (1) to (7), (R1) and (R2) obtained in the above examples and comparative examples.

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

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

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

[Method for evaluating pencil hardness]
With respect to the laminate, the pencil hardness of the coating film surface was measured under a load of 750 g according to JIS K5600-5-4 (1999). Each hardness was measured 5 times, and the hardness at which no scratch occurred 4 times or more was defined as the hardness of the cured coating film, and evaluated according to the following criteria.

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.

[Scratch resistance evaluation method]
A disk-shaped indenter with a diameter of 2.4 cm is wrapped with 0.5 g of steel wool (“Bonstar #0000” manufactured by Nippon Steel Wool Co., Ltd.), and a load of 1 kg is applied to the indenter to coat the surface of the laminate. A wear test was performed by reciprocating 10 times. The haze value of the laminate before and after the abrasion test was measured using a "Haze Computer HZ-2" manufactured by Suga Test Instruments Co., Ltd., and the difference (dH) was used for evaluation according to the following criteria. It should be noted that the smaller the value of the difference (dH), the higher the resistance to abrasion.

A: dH was 1.0 or less B: dH was more than 1.0 and 3.0 or less.
C: dH was greater than 3.0.

The wet heat resistance was evaluated by evaluating the substrate adhesion (initial stage) and the substrate adhesion (after the wet heat resistance test).

[Evaluation method for substrate adhesion (initial)]
Cut the surface of the cured coating film of the laminate with a cutter knife to create 100 grids of 1 mm × 1 mm. The number of cross-cuts remaining without any damage was counted and evaluated according to the following criteria.

A: The number of remaining grids was 80 or more.
B: Less than 80 grids remained.

[Evaluation method for substrate adhesion (after moist heat resistance test)]
The laminate was tested in a constant temperature and humidity environment tester (80° C., 95% RH) for 500 hours. After that, the same method as for the substrate adhesion (initial stage) described above was performed, and evaluation was performed according to the following criteria.

A: The number of remaining grids was 80 or more.
B: Less than 80 grids remained.

Compositions of active energy ray-curable resin compositions (1) to (7) prepared in Examples 1 to 7, and active energy ray-curable resin compositions (R1) and (R2) prepared in Comparative Examples 1 and 2 And the evaluation results are shown in Table 1.

In addition, description of the mass part in Table 1 is a solid content value.

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

"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).

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

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

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 a high refractive index performance, excellent hardness, scratch resistance, and moist heat resistance, and has a well-balanced combination of these performances.

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

Claims (9)

Urethane (meth)acrylate (A);
A bisphenol A type epoxy (meth)acrylate (B),
a compound (C) having at least three (meth)acryloyl groups;
An active energy ray-curable resin composition containing a photopolymerization initiator (D),
The urethane (meth)acrylate (A) comprises 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. An active energy ray-curable resin composition characterized by: 2. The active energy ray-curable resin composition according to claim 1, wherein the compound (a2) has a hydroxyl value of 90 to 170 mgKOH/g. 3. The active energy ray-curable resin composition according to claim 1, wherein the polyvalent isocyanate compound (a1) contains xylene diisocyanate and/or m-tetramethylxylene diisocyanate. 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 active energy ray-curable resin composition according to any one of claims 1 to 3. A cured product of the active energy ray-curable resin composition according to any one of claims 1 to 4. A laminate having a cured coating film of the active energy ray-curable resin composition according to any one of claims 1 to 4 on one or both sides of a substrate. 7. The laminate according to claim 6, wherein said substrate is a polyethylene terephthalate substrate. The laminate according to claim 6 or 7, wherein the substrate is film-like. An article having the laminate according to any one of claims 6 to 8 on its surface.