Actinic energy ray-curable resin composition, cured product, and article

Abstract

Provided are a radiation curable resin composition, a cured product, and an article, which have high refractive index performance and the cured product has excellent abrasion resistance. The radiation curable resin composition is characterized in that the following components are used as essential raw materials: a compound (A) having at least 2 aromatic rings and at least 1 epoxy group in one molecule, a polyanhydride (B), and a (meth)acrylate compound (C) having an alkylene oxide chain and / or an ester chain, wherein the polyanhydride (B) is an alicyclic polyanhydride and / or an aromatic polyanhydride, and the repeating unit number of the alkylene oxide chain of the compound (C) is in the range of 2 to 20, and the number of carbon atoms of the ester chain is 5 or more.

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable resin composition having high refractive index performance and a cured product of the active energy ray-curable resin composition having excellent abrasion resistance, and an article. Background Art

[0002] In recent years, with the rapid development of display technologies such as liquid crystal display devices, the requirements for new functions and higher quality of sheet-like or film-like optical members used therein have been increasing. As such optical members, for example, brightness enhancement sheets such as prismatic sheets and microlens sheets used in the backlight of liquid crystal display devices can be cited. These brightness enhancement sheets are generally formed by laminating an optical functional layer having a fine concavo-convex structure on the surface of a substrate. By the fine concavo-convex structure on the surface, the backlight is refracted, whereby the brightness on the front surface of the display can be enhanced. For this brightness enhancement sheet, in order to maintain high brightness with a small amount of light, it is required that the material itself has high refractive index performance.

[0003] As a resin material for a brightness enhancement sheet known in the past, there is known a resin composition characterized by containing metal oxide nanoparticles, and in the particle size distribution of the metal oxide nanoparticles, there is the following distribution: the cumulative 10% particle size is 5 to 25 nm, the cumulative 50% particle size is 7 to 30 nm, the cumulative 90% particle size is 15 to 50 nm, and the cumulative 100% particle size is 50 to 250 nm. As a resin component, it contains a compound having two or more benzene skeletons (for example, refer to Patent Document 1). Such an inorganic fine particle compounding type resin material has high refractive index performance. On the other hand, there are problems such as insufficient abrasion resistance of the cured product.

[0004] Therefore, there is a demand for a material having high refractive index performance and a cured product having excellent abrasion resistance.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2013-249439 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] The problem to be solved by the present invention is to provide an active energy ray-curable resin composition, a cured product, and an article having high refractive index performance and a cured product having excellent abrasion resistance.

[0010] Solutions for Solving the Problems

[0011] In order to solve the above problems, the present inventors conducted in-depth research and found that the above problems can be solved by using an active energy ray-curable resin composition containing, as essential raw materials, a compound having at least 2 aromatic rings and at least 1 epoxy group in one molecule, a specific polyanhydride, and a specific (meth)acrylate compound, thereby completing the present invention.

[0012] That is, the present invention relates to an active energy ray-curable resin composition, a cured product formed from the above active energy ray-curable resin composition, and an article. The active energy ray-curable resin composition is characterized by containing the following components as essential raw materials: a compound (A) having at least 2 aromatic rings and at least 1 epoxy group in one molecule, a polyanhydride (B), and a (meth)acrylate compound (C) having an alkylene oxide chain and / or an ester chain. The above polyanhydride (B) is an alicyclic polyanhydride and / or an aromatic polyanhydride. The repeating unit number of the alkylene oxide chain of the above compound (C) is in the range of 2 to 20, and the number of carbon atoms of the ester chain is 5 or more.

[0013] Effects of the Invention

[0014] The active energy ray-curable resin composition of the present invention has a high refractive index property, and the cured product has excellent abrasion resistance. Therefore, it can be suitably used for optical members such as brightness enhancement sheets such as prism sheets and microlens sheets. Detailed Description

[0015] The active energy ray-curable resin composition of the present invention is characterized by containing, as essential raw materials, a compound (A) having at least 2 aromatic rings and at least 1 epoxy group in one molecule, a polyanhydride (B), and a (meth)acrylate compound (C) having an alkylene oxide chain and / or an ester chain.

[0016] It should be noted that in the present invention, “(meth)acrylate” means acrylate and / or methacrylate. In addition, “(meth)acryloyl” means acryloyl and / or methacryloyl. Furthermore, “(meth)acrylic acid” means acrylic acid and / or methacrylic acid.

[0017] As the aforementioned compound (A), a compound having at least 2 aromatic rings and at least 1 epoxy group in one molecule is used. Examples thereof include bisphenol type epoxy resins, phenylene ether type epoxy resins, naphthalene ether type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol novolac type epoxy resins, naphthol novolac type epoxy resins, naphthol-phenol co-novolac type epoxy resins, naphthol-cresol co-novolac type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, biphenyl aralkyl type epoxy resins, fluorene type epoxy resins, xanthene type epoxy resins, dihydroxybenzene type epoxy resins, trihydroxybenzene type epoxy resins, oxazolidone type epoxy resins, hydrogenated bisphenol type epoxy resins, biphenol type epoxy resins, hydrogenated biphenol type epoxy resins, etc.

[0018] As the aforementioned bisphenol type epoxy resins, examples thereof include bisphenol A type epoxy resins, bisphenol AP type epoxy resins, bisphenol B type epoxy resins, bisphenol BP type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, etc.

[0019] As the aforementioned hydrogenated bisphenol type epoxy resins, examples thereof include hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol B type epoxy resins, hydrogenated bisphenol E type epoxy resins, hydrogenated bisphenol F type epoxy resins, hydrogenated bisphenol S type epoxy resins, etc.

[0020] As the aforementioned biphenol type epoxy resins, examples thereof include 4,4'-biphenol type epoxy resins, 2,2'-biphenol type epoxy resins, tetramethyl-4,4'-biphenol type epoxy resins, tetramethyl-2,2'-biphenol type epoxy resins, etc.

[0021] As the aforementioned hydrogenated biphenol type epoxy resins, examples thereof include hydrogenated 4,4'-biphenol type epoxy resins, hydrogenated 2,2'-biphenol type epoxy resins, hydrogenated tetramethyl-4,4'-biphenol type epoxy resins, hydrogenated tetramethyl-2,2'-biphenol type epoxy resins, etc.

[0022] These compounds (A) can be used alone or in combination of two or more. In addition, among these, from the viewpoint of obtaining an active energy ray curable resin composition having high refractive index performance and capable of forming a cured product having excellent abrasion resistance, bisphenol A type epoxy resin is preferred.

[0023] As the aforementioned polyanhydride (B), an alicyclic polyanhydride and / or an aromatic polyanhydride is used.

[0024] As the aforementioned alicyclic polyanhydride, in the present invention, the alicyclic polyanhydride is formed by bonding an anhydride group to an alicyclic structure, and there is no limitation on whether there is an aromatic ring in other structural parts. As the aforementioned alicyclic polyanhydride, for example, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, the anhydride of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, etc. can be cited.

[0025] As the aforementioned aromatic polyanhydride, for example, phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, the anhydride of benzophenonetetracarboxylic acid, etc. can be cited.

[0026] These polyanhydrides (B) can be used alone or in combination of two or more.

[0027] In addition, as the aforementioned polyanhydride (B), if necessary, in addition to the aforementioned alicyclic polyanhydride and the aforementioned aromatic polyanhydride, an aliphatic polyanhydride can also be used in combination.

[0028] As the aforementioned aliphatic polyanhydride, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, pentenedioic acid, the anhydride of 1,2,3,4-butanetetracarboxylic acid, etc. can be cited. In addition, as the aforementioned aliphatic polyanhydride, the aliphatic hydrocarbon group can be either straight-chain or branched-chain, and an unsaturated bond can also be present in the structure.

[0029] As the aforementioned polyanhydride (B), from the aspect of obtaining an active energy ray-curable resin composition capable of forming a cured product having high refractive index performance and excellent abrasion resistance, it is preferable to use an aromatic polyanhydride. The content of the aforementioned aromatic polyanhydride in the aforementioned polyanhydride (B) is preferably in the range of 30 to 100% by mass, more preferably 100% by mass.

[0030] In addition, from the aspect of obtaining an active energy ray-curable resin composition having high refractive index performance and capable of forming a cured product having excellent abrasion resistance, the amount of the aforementioned polyanhydride (B) is preferably in the range of 30 to 300 parts by mass, more preferably in the range of 50 to 200 parts by mass, relative to 100 parts by mass of the aforementioned compound (A).

[0031] As the aforementioned compound (C), a (meth)acrylate compound having an alkylene oxide chain and / or an ester chain is used. When the aforementioned compound (C) has an alkylene oxide chain, the repeating unit of the aforementioned alkylene oxide chain is in the range of 2 to 20, and from the viewpoint of obtaining an active energy ray-curable resin composition having high refractive index properties and capable of forming a cured product having excellent abrasion resistance, it is preferably in the range of 4 to 15. In addition, when the aforementioned compound (C) has an ester chain, the number of carbon atoms of the aforementioned ester chain is 5 or more, and from the viewpoint of obtaining an active energy ray-curable resin composition capable of forming a cured product having high refractive index properties and excellent abrasion resistance, it is preferably in the range of 5 to 25.

[0032] Examples of the aforementioned compound (C) include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol-propylene glycol-mono(meth)acrylate, and unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone adducts. These compounds (C) can be used alone or in combination of two or more. Among these, from the viewpoint of obtaining an active energy ray-curable resin composition having high refractive index properties and capable of forming a cured product having excellent abrasion resistance, polyethylene glycol mono(meth)acrylate is preferred.

[0033] In addition, from the viewpoint of obtaining an active energy ray-curable resin composition having high refractive index properties and capable of forming a cured product having excellent abrasion resistance, the amount of the aforementioned compound (C) is preferably in the range of 70 to 650 parts by mass, more preferably in the range of 90 to 500 parts by mass, relative to 100 parts by mass of the aforementioned compound (A).

[0034] In addition, from the viewpoint of having high refractive index properties and being capable of forming a cured product having excellent abrasion resistance, the active energy ray-curable resin composition of the present invention is preferably those represented by the following general formula (1), (2), (3), or (4).

[0035]

[0036] [In formulas (1) to (4), ring A is independently an aromatic ring or an aliphatic ring, and R 1 are independently a hydrogen atom or a methyl group, and R 2 are independently a hydrogen atom or a methyl group, and R 3 are independently a hydrogen atom or a methyl group. X is -O-, -SO 2 -, a structure represented by the following structural formula (5), or a structure represented by the following structural formula (6), m is 0 or an integer of 1 to 10, n is 0 or an integer of 1 to 10, and m + n is an integer of 2 to 20. In addition, r is independently an integer of 3 to 8, s is independently an integer of 1 to 5, and t is independently an integer of 1 to 5.]

[0037]

[0038] [In formula (5), R 4 and R 5 are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.]

[0039]

[0040] As a method for producing the active energy ray-curable resin composition of the present invention, there is no particular limitation, and it can be produced by using a suitably well-known method. For example, it can be produced by a method in which all raw materials including essential raw materials are reacted at once, or by a method in which the raw materials are reacted sequentially.

[0041] As a method in which the aforementioned raw materials are reacted sequentially, the following method can be cited, for example: First, polyanhydride (B) and compound (C) are reacted at 100 °C for 10 hours in the presence of triphenylphosphine to obtain a reaction product, and then the obtained reaction product and compound (A) are reacted at 105 °C for 10 hours in the presence of triphenylphosphine for production.

[0042] Among these production methods, from the viewpoint of obtaining an active energy ray-curable resin composition having high refractive index performance and capable of forming a cured product having excellent abrasion resistance, a method in which the raw materials are reacted sequentially is preferred.

[0043] In addition, in the active energy ray-curable resin composition of the present invention, a photopolymerization initiator is preferably used according to the type of active energy ray used. Examples of the aforementioned photopolymerization initiator 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-trimethylbenzoyl diphenylphosphine 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 free radical photopolymerization initiators.

[0044] Examples of commercially available products of the aforementioned other photoinitiators 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 photoinitiators can be used alone or in combination of two or more.

[0045] In addition, the aforementioned photoinitiators are also used in combination with photosensitizers such as amine compounds, urea compounds, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, and nitrile compounds.

[0046] Regarding the amount of the aforementioned photoinitiator, it is preferably used in the range of 0.05 to 20 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, based on 100 parts by mass of the non-volatile components of the active energy ray curable composition of the present invention.

[0047] In the active energy ray-curable resin composition used in the present invention, other components may be contained as needed in addition to the aforementioned compound (A), the aforementioned polyacid anhydride (B), and the aforementioned compound (C). It should be noted that in the non-volatile components of the aforementioned active energy ray-curable resin composition, the contents of the aforementioned compound (A), the aforementioned polyacid anhydride (B), and the aforementioned compound (C) in the aforementioned active energy ray-curable resin composition are preferably in the range of 50 to 100% by mass, and more preferably 100% by mass.

[0048] Examples of the aforementioned other components include inorganic fine particles, silane coupling agents, phosphate compounds, solvents, ultraviolet absorbers, antioxidants, silicone-based additives, fluorine-based additives, antistatic agents, organic microbeads, quantum dots (QD), rheology control agents, defoaming agents, antifogging agents, colorants, and the like.

[0049] The aforementioned inorganic fine particles are added for the purpose of adjusting the hardness, refractive index, etc. of the cured coating film of the active energy ray-curable resin composition, and various publicly known and commonly used inorganic fine particles can be used. Examples of the aforementioned inorganic fine particles include silica, alumina, zirconia, titanium dioxide, barium titanate, antimony trioxide, and the like. These inorganic fine particles can be used alone or in combination of two or more. Among them, in particular, silica particles with high versatility include various types such as fumed silica, wet silica called precipitated silica, gel silica, sol-gel silica, etc., and all can be used. In addition, the surface of the inorganic fine particles can also be modified with a silane coupling agent or the like. The particle size of the inorganic fine particles can be appropriately adjusted according to the desired coating film properties, etc., and the measured value based on the dynamic light scattering method is preferably in the range of 10 to 250 nm. When using inorganic fine particles, the addition amount thereof is preferably in the range of 0.1 to 60 parts by mass with respect to 100 parts by mass of the non-volatile components of the active energy ray-curable resin composition.

[0050] As the aforementioned silane coupling agent, examples thereof include (meth)acryloyloxyalkyl]trialkylsilane, [(meth)acryloyloxyalkyl]dialkylalkoxysilane, [(meth)acryloyloxyalkyl]alkyldialkoxysilane, [(meth)acryloyloxyalkyl]trialkoxysilane and other (meth)acryloyloxy-based silane coupling agents; trialkylvinylsilane, dialkylalkoxyvinylsilane, alkyldialkoxyvinylsilane, trialkoxyvinylsilane, triallylalkylsilane, dialkylalkoxyallylsilane, alkyldialkoxyallylsilane, trialkoxyallylsilane and other vinyl-based silane coupling agents; styryl trialkylsilane, styryl dialkylalkoxysilane, styryl alkyldialkoxysilane, styryl trialkoxysilane and other styrene-based silane coupling agents; (glycidoxyalkyl)trialkylsilane, (glycidoxyalkyl)dialkylalkoxysilane, (glycidoxyalkyl)alkyldialkoxysilane, (glycidoxyalkyl)trialkoxysilane, [(3,4-epoxycyclohexyl)alkyl]trimethoxysilane, [(3,4-epoxycyclohexyl)alkyl]trialkylsilane, [(3,4-epoxycyclohexyl)alkyl]dialkylalkoxysilane, [(3,4-epoxycyclohexyl)alkyl]alkyldialkoxysilane, [(3,4-epoxycyclohexyl)alkyl]trialkoxysilane and other epoxy-based silane coupling agents; (isocyanatoalkyl)trialkylsilane, (isocyanatoalkyl)dialkylalkoxysilane, (isocyanatoalkyl)alkyldialkoxysilane, (isocyanatoalkyl)trialkoxysilane and other isocyanate-based silane coupling agents. These silane coupling agents can be used alone or in combination of two or more.

[0051] As the aforementioned phosphate compound, examples thereof include commercially available products such as "KAYAMER PM-2", "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd., "Light Ester P-1M", "Light Ester P-2M", "Light Acrylate P-1A(N)" manufactured by Kyoeisha Chemical Co., Ltd., "SIPOMER PAM 100", "SIPOMER PAM 200", "SIPOMER PAM 300", "SIPOMER PAM 4000" manufactured by SOLVAY, "Viscoat#3PA", "Viscoat#3PMA" manufactured by Osaka Organic Chemical Industry Co., Ltd., "NEWFRONTIER S-23A" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., which are phosphate compounds having a (meth)acryloyl group in the molecular structure; "SIPOMER PAM 5000" manufactured by SOLVAY, which is a phosphate compound having an allyl ether group in the molecular structure.

[0052] The aforementioned solvent is added for the purpose of adjusting the coating viscosity of the active energy ray-curable resin composition, and its type and addition amount can be appropriately adjusted according to the desired performance. Generally, it is used in such a manner that the nonvolatile component of the active energy ray-curable resin composition is in the range of 10 to 90% by mass. Examples of the aforementioned solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene and xylene; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropyl alcohol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monopropyl ether. These solvents can be used alone or in combination of two or more.

[0053] Examples of the aforementioned 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'-xanthone carboxyl-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole; benzophenones such as 2-xanthone carboxyl-4-dodecyloxydibenzophenone and 2-o-nitrobenzyloxy-4-dodecyloxydibenzophenone. These ultraviolet absorbers can be used alone or in combination of two or more.

[0054] Examples of the aforementioned antioxidant include hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, phosphate antioxidants, etc. These antioxidants can be used alone or in combination of two or more.

[0055] Examples of the aforementioned silicone-based additive include polyorganosiloxanes having alkyl or phenyl groups such as dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethylpolysiloxane copolymer, and amino-modified dimethylpolysiloxane copolymer; polydimethylsiloxanes having polyether-modified acryloyl groups; polydimethylsiloxanes having polyester-modified acryloyl groups. These silicone additives can be used alone or in combination of two or more.

[0056] Examples of the aforementioned fluorine-based additive include the "MEGAFACE" series of DIC Corporation. These fluorine-based additives can be used alone or in combination of two or more.

[0057] Examples of the aforementioned antistatic agents include pyridinium, imidazolium, phosphonium, ammonium, or lithium salts of bis(trifluoromethanesulfonyl)imide or bis(fluorosulfonyl)imide. These antistatic agents can be used alone or in combination of two or more.

[0058] Examples of the aforementioned organic microbeads include polymethyl methacrylate microbeads, polycarbonate microbeads, polystyrene microbeads, polyacrylic styrene microbeads, silicone microbeads, glass microbeads, acrylic microbeads, benzoguanamine resin microbeads, melamine resin microbeads, polyolefin resin microbeads, polyester resin microbeads, polyamide resin microbeads, polyimide resin microbeads, polyvinyl fluoride resin microbeads, polyethylene resin microbeads, etc. These organic microbeads can be used alone or in combination of two or more. The average particle size of these organic microbeads is preferably in the range of 1 to 10 μm.

[0059] Examples of the aforementioned quantum dots (QDs) include II-V group semiconductor compounds, II-VI group semiconductor compounds, III-IV group semiconductor compounds, III-V group semiconductor compounds, III-VI group semiconductor compounds, IV-VI group semiconductor compounds, I-III-VI group semiconductor compounds, II-IV-VI group semiconductor compounds, II-IV-V group semiconductor compounds, I-II-IV-VI group semiconductor compounds, group IV elements or compounds containing the same, etc. Examples of the aforementioned II-VI group semiconductor compounds include binary compounds such as ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe; ternary compounds such as ZnSeS, ZnSeTe, ZnSTe, CdZnS, CdZnSe, CdZnTe, CdSeS, CdSeTe, CdSTe, CdHgS, CdHgSe, CdHgTe, HgSeS, HgSeTe, HgSTe, HgZnS, HgZnSe, HgZnTe; quaternary compounds such as CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, CdHgZnTe, HgZnSeS, HgZnSeTe, HgZnSTe, etc. Examples of the aforementioned III-IV group semiconductor compounds include B 4 C 3 、Al 4 C 3 、Ga 4 C 3etc. As the aforementioned III-V semiconductor compounds, binary compounds such as BP, BN, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, etc. can be cited; ternary compounds such as GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, etc.; quaternary compounds such as GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, etc. As the aforementioned III-VI semiconductor compounds, for example, Al 2 S 3 、Al 2 Se 3 、Al 2 Te 3 、Ga 2 S 3 、Ga 2 Se 3 、Ga 2 Te 3 、GaTe、In 2 S 3 、In 2 Se 3 、In 2 Te 3 、InTe, etc. As the aforementioned IV-VI semiconductor compounds, binary compounds such as SnS, SnSe, SnTe, PbS, PbSe, PbTe, etc. can be cited; ternary compounds such as SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, etc.; quaternary compounds such as SnPbSSe, SnPbSeTe, SnPbSTe, etc. As the aforementioned I-III-VI semiconductor compounds, for example, CuInS 2 、CuInSe 2 、CuInTe 2 、CuGaS 2 、CuGaSe 2 、CuGaSe 2 、AgInS 2 、AgInSe 2 、AgInTe 2 、AgGaSe 2 、AgGaS2 , AgGaTe 2 etc. As the Group IV element or the compound containing the same, examples thereof include C, Si, Ge, SiC, SiGe, etc. The quantum dots may be formed of a single semiconductor compound, or may have a core-shell structure formed of a plurality of semiconductor compounds. Further, the surface thereof may be modified with an organic compound.

[0060] Regarding these various additives, any amount may be added according to desired properties and the like. Generally, it is preferably used in the range of 0.01 to 40 parts by mass with respect to 100 parts by mass of the non-volatile components of the active energy ray-curable resin composition.

[0061] The active energy ray-curable resin composition of the present invention is produced by mixing the above-mentioned respective compounding components. The mixing method is not particularly limited, and a paint stirrer, a disperser, a roll mill, a bead mill, a ball mill, a grinder, a sand mill, etc. may be used.

[0062] The cured product of the present invention can be obtained by irradiating the above-mentioned active energy ray-curable resin composition with active energy rays. Examples of the active energy rays include ionizing radiation rays 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 carry out the curing reaction based on ultraviolet rays, irradiation may be carried out in an inert gas atmosphere such as nitrogen, or may be carried out in an air atmosphere.

[0063] As the ultraviolet ray source, from the viewpoints of practicality and economy, an ultraviolet lamp is generally used. Specifically, examples thereof 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, etc.

[0064] The cumulative light amount of the above-mentioned active energy rays is not particularly limited, and is preferably 0.1 to 50 kJ / m 2 , more preferably 0.5 to 10 kJ / m 2 . When the cumulative light amount is in the above range, generation of uncured portions can be prevented or suppressed, and thus it is preferred.

[0065] It should be noted that the irradiation of the above-mentioned active energy rays may be carried out in one stage, or may be carried out in two or more stages.

[0066] Examples of the article of the present invention include optical members and the like.

[0067] Examples of the optical member include a plastic lens, a polarizing film, a retardation film, an antireflection film, a brightness enhancement film (a prism sheet, a microlens sheet, etc.), a light diffusion film, a hard coat film, a thin film type liquid crystal element, a touch panel, etc.

[0068] Examples

[0069] Hereinafter, the present invention will be specifically described through Examples and Comparative Examples. It should be noted that the present invention is not limited to the Examples given below.

[0070] (Example 1: Preparation of Actinic Energy Ray-Curable Resin Composition (1))

[0071] In a flask equipped with a thermometer, a condenser, and a stirrer, 148 parts by mass (1.00 mol) of phthalic anhydride, 353 parts by mass (1.02 mol) of an unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone 2-molar adduct (“PLACCEL FA2D” manufactured by DAICEL CORPORATION), 2 parts by mass of 2,6-di-tert-butyl-p-cresol, and 0.2 part by mass of 4-methoxyphenol were charged, and the inside of the system was controlled at 100° C. and stirred for 8 hours. Then, after the temperature was lowered to 60° C., 186 parts by mass (0.50 mol) of a bisphenol A-type epoxy resin (“EPICLON 850-S” manufactured by DIC CORPORATION) was added, and stirring was continued at 105° C. for 7 hours. The resulting reaction product was filtered and recovered to obtain an actinic energy ray-curable resin composition (1).

[0072] (Example 2: Preparation of Actinic Energy Ray-Curable Resin Composition (2))

[0073] 353 parts by mass of the unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone 2-molar adduct (“PLACCEL FA2D” manufactured by DAICEL CORPORATION) used in Example 1 was changed to 231 parts by mass of an unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone 1-molar adduct (“PLACCEL FA1DDM” manufactured by DAICEL CORPORATION). Otherwise, an actinic energy ray-curable resin composition (2) was obtained in the same manner as in Example 1.

[0074] (Example 3: Preparation of Actinic Energy Ray-Curable Resin Composition (3))

[0075] 353 parts by mass of the unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone 2-molar adduct (“PLACCEL FA2D” manufactured by DAICEL CORPORATION) used in Example 1 was changed to 359 parts by mass of polyethylene glycol monoacrylate (equivalent to 4.5 mol of EO chain) (“BLEMMER AE-200” manufactured by NOF CORPORATION). Otherwise, an actinic energy ray-curable resin composition (3) was obtained in the same manner as in Example 1.

[0076] (Example 4: Preparation of Actinic Energy Ray-Curable Resin Composition (4))

[0077] The 353 parts by mass of the unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone 2-molar adduct (“PLACCEL FA2D” manufactured by DAICEL CORPORATION) used in Example 1 was changed to 540 parts by mass of polyethylene glycol monoacrylate (equivalent to 10 moles of EO chain) (“BLEMMER AE-400” manufactured by NOF CORPORATION). Except for this, an active energy ray-curable resin composition (4) was obtained in the same manner as in Example 1.

[0078] (Example 5: Preparation of active energy ray-curable resin composition (5))

[0079] The 148 parts by mass of phthalic anhydride used in Example 1 was changed to 154 parts by mass of cis-cyclohexane-1,2-dicarboxylic anhydride, and the 353 parts by mass of the unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone 2-molar adduct (“PLACCEL FA2D” manufactured by DAICEL CORPORATION) used in Example 1 was changed to 540 parts by mass of polyethylene glycol monoacrylate (equivalent to 10 moles of EO chain) (“BLEMMER AE-400” manufactured by NOF CORPORATION). Except for this, an active energy ray-curable resin composition (5) was obtained in the same manner as in Example 1.

[0080] (Example 6: Preparation of active energy ray-curable resin composition (6))

[0081] The 186 parts by mass of bisphenol A type epoxy resin (“EPICLON 850-S” manufactured by DIC CORPORATION) used in Example 1 was changed to 136 parts by mass of naphthalene type epoxy resin (DIC CORPORATION “HP-4032SS”), and the 353 parts by mass of the unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone 2-molar adduct (“PLACCEL FA2D” manufactured by DAICEL CORPORATION) used in Example 1 was changed to 359 parts by mass of polyethylene glycol monoacrylate (equivalent to 4.5 moles of EO chain) (“BLEMMER AE-200” manufactured by NOF CORPORATION). Except for this, an active energy ray-curable resin composition (6) was obtained in the same manner as in Example 1.

[0082] (Comparative Example 1: Preparation of active energy ray-curable resin composition (R1))

[0083] In a flask equipped with a thermometer, a cooling tube, and a stirrer, 148 parts by mass (1.00 mol) of phthalic anhydride, 353 parts by mass (1.02 mol) of an unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone 2-mol adduct ("PLACCEL FA2D" manufactured by Daicel Corporation), 2 parts by mass of 2,6-di-tert-butyl-p-cresol, and 0.2 parts by mass of 4-methoxyphenol were charged, and the inside of the system was controlled to 100 °C and stirred for 8 hours. Then, after the temperature was lowered to 60 °C, 108 parts by mass of an epoxy resin mainly composed of neopentyl glycol diglycidyl ether ("ED-523T" manufactured by ADEKA Corporation) was added, and stirring was continued at 105 °C for 7 hours. The resulting reaction product was filtered and recovered to obtain a radiation-curable resin composition (R1).

[0084] (Comparative Example 2: Preparation of Radiation-Curable Resin Composition (R2))

[0085] In a flask equipped with a thermometer, a cooling tube, and a stirrer, 148 parts by mass (1.00 mol) of phthalic anhydride, 118 parts by mass of 2-hydroxyethyl acrylate, 2 parts by mass of 2,6-di-tert-butyl-p-cresol, and 0.2 parts by mass of 4-methoxyphenol were charged, and the inside of the system was controlled to 100 °C and stirred for 8 hours. Then, after the temperature was lowered to 60 °C, 186 parts by mass (0.50 mol) of a bisphenol A-type epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation) was added, and stirring was continued at 105 °C for 7 hours. The resulting reaction product was filtered and recovered to obtain a radiation-curable resin composition (R2).

[0086] Using the radiation-curable resin compositions obtained in the above Examples and Comparative Examples, the following measurements and evaluations were carried out.

[0087] [Method for Measuring Refractive Index]

[0088] On a glass plate, 3 parts by mass of a photopolymerization initiator ("Omnirad 184" manufactured by IGM Resins) was added to 100 parts by mass of the radiation-curable resin composition obtained in the Examples and Comparative Examples and mixed. Using a spreader, it was coated so that the film thickness at the time of curing became 50 μm, irradiated with active energy rays, and a cured coating film of the radiation-curable resin composition was formed on the surface of the aforementioned substrate. The aforementioned cured coating film was peeled off from the glass substrate, and its refractive index was measured using an Abbe refractometer ("NAR-3T" manufactured by Atago Co., Ltd.).

[0089] [Method for Measuring Abrasion Resistance]

[0090] To 100 parts by mass of the active energy ray-curable resin composition obtained in the examples and comparative examples, 3 parts by mass of a photopolymerization initiator ("Omnirad 184" manufactured by IGM Resins) was added and mixed. After coating on a suitable plastic film, ultraviolet irradiation was performed using an 80 W high-pressure mercury lamp, whereby a laminate having a cured coating film on the film was obtained. Then, a 2.4 cm diameter disc-shaped indenter was wrapped with 0.5 g of steel wool ("BONSTAR #0000" manufactured by NIPPON STEEL WOOL CO., LTD.), a load of 500 g was applied to the indenter, and it was reciprocated 10 times on the coated surface of the laminate, thereby performing a wear test. The haze value of the laminated film before and after the wear test was measured using "Haze computer HZ-2" manufactured by Suga Test Instruments Co., Ltd., and using their difference (dH), evaluation was performed according to the following criteria. It should be noted that the smaller the difference (dH), the more excellent the abrasion resistance.

[0091] A: dH is 2.0 or less

[0092] B: dH is greater than 2.0 and 5.0 or less.

[0093] C: dH is greater than 5.0 and 10.0 or less.

[0094] D: dH is greater than 10.0 and 15.0 or less.

[0095] E: dH is greater than 15.0.

[0096] [Table 1]

[0097]

[0098] Examples 1 to 6 shown in Table 1 are examples of using the active energy ray-curable resin composition of the present invention. It can be confirmed that these active energy ray-curable resin compositions have high refractive index performance and excellent abrasion resistance.

[0099] On the other hand, Comparative Example 1 is an example of using an active energy ray-curable resin composition that does not have a compound having at least 2 aromatic rings and at least 1 epoxy group in one molecule as defined in the present invention. It can be confirmed that although the active energy ray-curable resin composition has excellent abrasion resistance, its refractive index performance is insufficient.

[0100] Comparative Example 2 is an example of using an active energy ray-curable resin composition that does not have a (meth)acrylate compound having an alkylene oxide chain and / or an ester chain as defined in the present invention. It can be confirmed that although the active energy ray-curable resin composition has high refractive index performance, its abrasion resistance is significantly insufficient.

Claims

1. A radiation curable resin composition, characterized in that, the following components are used as essential raw materials: a compound (A) having at least 2 aromatic rings and at least 1 epoxy group in one molecule, a polyanhydride (B), and an (meth)acrylate compound (C) having an alkylene oxide chain, the polyanhydride (B) is an alicyclic polyanhydride and / or an aromatic polyanhydride, the alkylene oxide chain of the compound (C) has a repeating unit number in the range of 4 to 10, and the compound (C) is polyethylene glycol mono(meth)acrylate, with respect to 100 parts by mass of the compound (A), the amount of the polyanhydride (B) is in the range of 30 to 300 parts by mass, and the amount of the compound (C) is in the range of 70 to 650 parts by mass, the radiation curable resin composition is represented by the following general formula (1) or (2), In Formulas (1) to (2), ring A is independently an aromatic ring or an aliphatic ring, and R 1 is independently a hydrogen atom or a methyl group, and R 2 is a hydrogen atom, R 3 is a hydrogen atom, X is -O-, -SO 2 -, a structure represented by the following Structural Formula (5), or a structure represented by the following Structural Formula (6), m is an integer of 4 to 10, n is an integer of 4 to 10, and m + n is an integer of 8 to 20. In formula (5), R 4 , R 5 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, 2. The radiation curable resin composition according to claim 1, wherein, the radiation curable resin composition contains: the reaction product of the polyanhydride (B) and the compound (C) and the reaction product of the compound (A).

3. A cured product which is a cured product of the radiation curable resin composition according to claim 1 or 2.

4. An article, characterized in that, it has a cured coating film formed from the cured product according to claim 3.

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