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

Abstract

To provide an active energy ray-curable resin composition which has high refractive index performance and gives a cured product having excellent abrasion resistance, a cured product and an article.SOLUTION: An active energy ray-curable resin composition contains a compound (A) having at least two aromatic rings and at least one epoxy group in one molecule, a polybasic acid anhydride (B) and a (meth)acrylate compound (C) having an alkylene oxide chain and / or an ester chain as essential raw materials, in which the polybasic acid anhydride (B) is an alicyclic polybasic acid anhydride and / or an aromatic polybasic acid anhydride; the number of repeating units of an alkylene oxide chain that the compound (C) has is within a range of 2-20; and the number of carbon atoms of the ester chain is 5 or more.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In recent years, with the rapid development of display technologies such as liquid crystal display devices, there has been an increasing demand for sheet-like or film-like optical members used therein that have new functions or higher quality. Examples of such optical members include brightness enhancement sheets such as prism sheets and microlens sheets used in the backlights of liquid crystal display devices. These brightness enhancement sheets are generally formed by laminating an optical functional layer having a fine concavo-convex structure on the surface on a substrate, and the fine concavo-convex structure on the surface can refract the backlight light to improve the brightness in the front of the display. The brightness enhancement sheet is required to have high refractive index performance by itself in order to maintain high brightness with a small amount of light.

[0003] Conventionally known resin materials for brightness enhancement sheets are resin compositions containing metal oxide nanoparticles. The metal oxide nanoparticles have a distribution in which the cumulative 10% particle diameter is 5 to 25 nm, the cumulative 50% particle diameter is 7 to 30 nm, the cumulative 90% particle diameter is 15 to 50 nm, and the cumulative 100% particle diameter is 50 to 250 nm, and contain a compound having two or more benzene skeletons as a resin component (for example, see Patent Document 1). However, such an inorganic fine particle-containing resin material has problems such as insufficient abrasion resistance in the cured product while having high refractive index performance.

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

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] The problem to be solved by the present invention is to provide an active energy ray-curable resin composition having high refractive index performance and excellent abrasion resistance in a cured product, a cured product, and an article.

Means for Solving the Problems

[0007] As a result of intensive studies to solve the above problems, the present inventors have 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 two aromatic rings and at least one epoxy group in one molecule, a specific polybasic acid anhydride, and a specific (meth)acrylate compound, and have completed the present invention.

[0008] That is, the present invention relates to an active energy ray-curable resin composition containing, as essential raw materials, a compound (A) having at least two aromatic rings and at least one epoxy group in one molecule, a polybasic acid anhydride (B), and a (meth)acrylate compound (C) having an alkylene oxide chain and / or an ester chain, wherein the polybasic acid anhydride (B) is an alicyclic polybasic acid anhydride and / or an aromatic polybasic acid anhydride, the number of repeating units 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, a cured product comprising the active energy ray-curable resin composition, and an article.

Effects of the Invention

[0009] The active energy ray-curable resin composition of the present invention has a high refractive index performance and excellent abrasion resistance in the cured product, and thus can be suitably used for optical members such as brightness improvement sheets such as prism sheets and microlens sheets.

Embodiments for Carrying Out the Invention

[0010] The active energy ray-curable resin composition of the present invention is characterized in that a compound (A) having at least two aromatic rings and at least one epoxy group in one molecule, a polybasic acid anhydride (B), and a (meth)acrylate compound (C) having an alkylene oxide chain and / or an ester chain are used as essential raw materials.

[0011] 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.

[0012] As the compound (A), those having at least two aromatic rings and at least one epoxy group in one molecule are used. For example, bisphenol type epoxy resins, phenylene ether type epoxy resins, naphthylene ether type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, bisphenol novolak type epoxy resins, naphthol novolak type epoxy resins, naphthol-phenol co-condensed novolak type epoxy resins, naphthol-cresol co-condensed novolak 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 and the like can be mentioned.

[0013] Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and the like.

[0014] Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol S type epoxy resin, and the like.

[0015] Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, tetramethyl-2,2'-biphenol type epoxy resin, and the like.

[0016] Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol type epoxy resin, hydrogenated tetramethyl-2,2'-biphenol type epoxy resin, and the like.

[0017] These compounds (A) can be used alone or in combination of two or more. Among them, bisphenol A type epoxy resin is preferable because an active energy ray-curable resin composition having a high refractive index performance and capable of forming a cured product having excellent abrasion resistance can be obtained.

[0018] As the polybasic acid anhydride (B), an alicyclic polybasic acid anhydride and / or an aromatic polybasic acid anhydride is used.

[0019] In the present invention, as the alicyclic polybasic acid anhydride, those in which the acid anhydride group is bonded to an alicyclic structure are regarded as alicyclic polybasic acid anhydrides, regardless of the presence or absence of aromatic rings in other structural sites. Examples of the alicyclic polybasic acid anhydride include acid anhydrides of 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, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, and the like.

[0020] Examples of the aromatic polybasic acid anhydride include acid anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and the like.

[0021] These polybasic acid anhydrides (B) can be used alone or in combination of two or more.

[0022] In addition, as the polybasic acid anhydride (B), if necessary, an aliphatic polybasic acid anhydride can be used in combination with the alicyclic polybasic acid anhydride and the aromatic polybasic acid anhydride.

[0023] Examples of the aliphatic polybasic acid anhydride include acid anhydrides of 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, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, and the like. In addition, as the aliphatic polybasic acid anhydride, the aliphatic hydrocarbon group may be either linear or branched, and may have an unsaturated bond in the structure.

[0024] As the polybasic acid anhydride (B), since an active energy ray-curable resin composition capable of forming a cured product having high refractive index performance and excellent abrasion resistance can be obtained, it is preferable to use an aromatic polybasic acid anhydride as an essential component. The content of the aromatic polybasic acid anhydride is preferably in the range of 30 to 100% by mass, more preferably 100% by mass, in the polybasic acid anhydride (B).

[0025] In addition, the amount of the polybasic acid anhydride (B) used is preferably in the range of 30 to 300 parts by mass, more preferably in the range of 50 to 200 parts by mass, based on 100 parts by mass of the compound (A), since an active energy ray-curable resin composition capable of forming a cured product having high refractive index performance and excellent abrasion resistance can be obtained.

[0026] As the compound (C), a (meth)acrylate compound having an alkylene oxide chain and / or an ester chain is used. When the compound (C) has an alkylene oxide chain, the repeating unit of the alkylene oxide chain is in the range of 2 to 20, and preferably in the range of 4 to 15, since an active energy ray-curable resin composition capable of forming a cured product having high refractive index performance and excellent abrasion resistance can be obtained. When the compound (C) has an ester chain, the number of carbon atoms of the ester chain is 5 or more, and preferably in the range of 5 to 25, since an active energy ray-curable resin composition capable of forming a cured product having high refractive index performance and excellent abrasion resistance can be obtained.

[0027] Examples of the compound (C) include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol-propylene glycol-mono(meth)acrylate, unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone adduct, and the like. These compounds (C) can be used alone or in combination of two or more. Among these, polyethylene glycol mono(meth)acrylate is preferable since an active energy ray-curable resin composition capable of forming a cured product having high refractive index performance and excellent abrasion resistance can be obtained.

[0028] In addition, since the use amount of the compound (C) can provide an active energy ray-curable resin composition capable of forming a cured product having high refractive index performance and excellent abrasion resistance, the range of 70 to 650 parts by mass is preferable, and the range of 90 to 500 parts by mass is more preferable with respect to 100 parts by mass of the compound (A).

[0029] In addition, since the active energy ray-curable resin composition of the present invention can form a cured product having high refractive index performance and excellent abrasion resistance, it is preferably represented by the following general formula (1), (2), (3) or (4).

[0030] [Chemical formula]

[0031] [In formulas (1) to (4), ring A is independently an aromatic ring or a cyclo ring, R 1 is independently a hydrogen atom or a methyl group, R 2 is independently a hydrogen atom or a methyl group, R 3 is independently a hydrogen atom or a methyl group. X is -O-, -SO2-, 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. Also, 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.]

[0032] [Chemical formula] [In formula (5), R 4 , R 5 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.]

[0033] [Chemical formula]

[0034] The method for producing the active energy ray-curable resin composition of the present invention is not particularly limited and can be produced by a known method as appropriate. For example, it may be produced by a method in which all of the raw materials including the essential raw materials are reacted at once, or by a method in which the raw materials are reacted sequentially.

[0035] As a method of reacting the raw materials sequentially, for example, first, a polybasic acid anhydride (B) and a 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 a compound (A) are reacted at 105 ° C. for 10 hours in the presence of triphenylphosphine.

[0036] Among these production methods, a method of sequentially reacting raw materials is preferable because an active energy ray-curable resin composition capable of forming a cured product having high refractive index performance and excellent abrasion resistance can be obtained.

[0037] In addition, depending on the type of active energy ray used, it is preferable to use a photoinitiator in the active energy ray-curable resin composition of the present invention. Examples of the photoinitiator 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 photo radical polymerization initiators.

[0038] Examples of commercially available products of the 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.

[0039] In addition, the photoinitiator can be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, or a nitrile compound.

[0040] The amount of the photoinitiator used is preferably 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 content of the active energy ray-curable composition of the present invention.

[0041] The active energy ray-curable resin composition used in the present invention may further contain other components other than the compound (A), the polybasic acid anhydride (B), and the compound (C), if necessary. The contents of the compound (A), the polybasic acid anhydride (B), and the compound (C) in the active energy ray-curable resin composition are preferably in the range of 50 to 100% by mass, more preferably 100% by mass, in the non-volatile matter of the active energy ray-curable resin composition.

[0042] Examples of the other components include inorganic fine particles, silane coupling agents, phosphate ester compounds, solvents, ultraviolet absorbers, antioxidants, silicone-based additives, fluorine-based additives, antistatic agents, organic beads, quantum dots (QD), rheology control agents, defoaming agents, antifogging agents, colorants, and the like.

[0043] The inorganic fine particles are added for the purpose of adjusting the hardness, refractive index, etc. in the cured coating film of the active energy ray-curable resin composition, and various known and commonly used inorganic fine particles can be used. Examples of the inorganic fine particles include silica, alumina, zirconia, titania, barium titanate, antimony trioxide, and the like. These inorganic fine particles can be used alone or in combination of two or more. Among these, silica particles with particularly high versatility include various types such as fumed silica, wet silica called precipitated silica, gel silica, sol-gel silica, etc., and any of them may be used. Further, the surface of the inorganic fine particles may be modified with a silane coupling agent or the like. The particle size of the inorganic fine particles is appropriately adjusted according to the desired coating film performance, etc., but the measured value by the dynamic light scattering method is preferably in the range of 10 to 250 nm. When using inorganic fine particles, the addition amount is preferably in the range of 0.1 to 60 parts by mass with respect to 100 parts by mass of the non-volatile matter of the active energy ray-curable resin composition.

[0044] Examples of the silane coupling agent include (meth)acryloyloxy-based silane coupling agents such as [(meth)acryloyloxyalkyl]trialkylsilane, [(meth)acryloyloxyalkyl]dialkylalkoxysilane, [(meth)acryloyloxyalkyl]alkyldialkoxysilane, [(meth)acryloyloxyalkyl]trialkoxysilane; vinyl-based silane coupling agents such as trialkylvinylsilane, dialkylalkoxyvinylsilane, alkyldialkoxyvinylsilane, trialkoxyvinylsilane, trialkylallylsilane, dialkylalkoxyallylsilane, alkyldialkoxyallylsilane, trialkoxyallylsilane; styrene-based silane coupling agents such as stryltrimethylsilane, stryldialkylalkoxysilane, strylalkyldialkoxysilane, stryltrimethoxysilane; epoxy-based silane coupling agents such as (glycidyloxyalkyl)trialkylsilane, (glycidyloxyalkyl)dialkylalkoxysilane, (glycidyloxyalkyl)alkyldialkoxysilane, (glycidyloxyalkyl)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; isocyanate-based silane coupling agents such as (isocyanatealkyl)trialkylsilane, (isocyanatealkyl)dialkylalkoxysilane, (isocyanatealkyl)alkyldialkoxysilane, (isocyanatealkyl)trialkoxysilane. These silane coupling agents can be used alone or in combination of two or more.

[0045] Examples of the phosphate ester compound 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, "Biscoat #3PA", "Biscoat #3PMA" manufactured by Osaka Organic Chemical Industry Co., Ltd., and "New Frontier S-23A" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., which are phosphate ester compounds having a (meth)acryloyl group in the molecular structure; and "SIPOMER PAM 5000" manufactured by SOLVAY, which is a phosphate ester compound having an allyl ether group in the molecular structure.

[0046] The solvent is added for the purpose of adjusting the coating viscosity of the active energy ray curable resin composition, etc., and its type and addition amount are appropriately adjusted according to the desired performance. Generally, it is used so that the non-volatile content of the active energy ray curable resin composition is in the range of 10 to 90% by mass. Examples of the 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, isopropanol, butanol, and propylene glycol monomethyl ether; and 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.

[0047] The ultraviolet absorber is, for example, a triazine derivative such as 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)-1,3,5-triazine, 2-(2'-xanthene carboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthene carboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. These ultraviolet absorbers can be used alone or in combination of two or more kinds.

[0048] Examples of the antioxidant include hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, phosphate ester antioxidants, etc. These antioxidants can be used alone or in combination of two or more kinds.

[0049] Examples of the silicone-based additive include polyorganosiloxanes having an alkyl group or a phenyl group such as dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethylpolysiloxane copolymer, amino-modified dimethylpolysiloxane copolymer, etc., and polydimethylsiloxane having a polyether-modified acrylic group, polydimethylsiloxane having a polyester-modified acrylic group, etc. These silicone additives can be used alone or in combination of two or more kinds.

[0050] Examples of the fluorine-based additive include the "Megaface" series of DIC Corporation, etc. These fluorine-based additives can be used alone or in combination of two or more kinds.

[0051] The antistatic agent includes, for example, 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.

[0052] The organic beads include, for example, polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, polyester resin beads, polyamide resin beads, polyimide resin beads, polyvinylidene fluoride resin beads, polyethylene resin beads, etc. These organic beads can be used alone or in combination of two or more. The average particle size of these organic beads is preferably in the range of 1 to 10 μm.

[0053] Examples of the 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. Examples of the II-VI group semiconductor compounds include binary compounds such as ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, and HgTe; ternary compounds such as ZnSeS, ZnSeTe, ZnSTe, CdZnS, CdZnSe, CdZnTe, CdSeS, CdSeTe, CdSTe, CdHgS, CdHgSe, CdHgTe, HgSeS, HgSeTe, HgSTe, HgZnS, HgZnSe, and HgZnTe; and quaternary compounds such as CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, CdHgZnTe, HgZnSeS, HgZnSeTe, and HgZnSTe. Examples of the III-IV group semiconductor compounds include B4C3, Al4C3, and Ga4C3. Examples of the III-V group semiconductor compounds include binary compounds such as BP, BN, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb; ternary compounds such as GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, and GaAlNP; and quaternary compounds such as GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb. Examples of the III-VI group semiconductor compounds include Al2S3, Al2Se3, Al2Te3, Ga2S3, Ga2Se3, Ga2Te3, GaTe, In2S3, In2Se3, In2Te3, and InTe.Examples of the Group-IV to VI semiconductor compounds include binary compounds such as SnS, SnSe, SnTe, PbS, PbSe, and PbTe; ternary compounds such as SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, and SnPbTe; and quaternary compounds such as SnPbSSe, SnPbSeTe, and SnPbSTe. Examples of the Group-I to III-VI semiconductor compounds include CuInS2, CuInSe2, CuInTe2, CuGaS2, CuGaSe2, CuGaSe2, AgInS2, AgInSe2, AgInTe2, AgGaSe2, AgGaS2, and AgGaTe2. Examples of the Group-IV element or the compound containing the same include C, Si, Ge, SiC, and SiGe. The quantum dots may be composed of a single semiconductor compound or may have a core-shell structure composed of a plurality of semiconductor compounds. Further, the surface thereof may be modified with an organic compound.

[0054] These various additives can be added in an arbitrary amount according to desired performance and the like, but it is usually preferable to use them in the range of 0.01 to 40 parts by mass with respect to 100 parts by mass of the non-volatile content of the active energy ray curable resin composition.

[0055] 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 shaker, a disper, a roll mill, a bead mill, a ball mill, an attritor, a sand mill, a bead mill, etc. can be used.

[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, it may be irradiated in an inert gas atmosphere such as nitrogen gas or in an air atmosphere.

[0057] As the ultraviolet 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 . When the integrated light amount is within the above range, it is preferable because the generation of uncured portions can be prevented or suppressed.

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

[0061] Examples of the optical member include a plastic lens, a polarizing film, a retardation film, an antireflection film, a brightness enhancement film (such as a prism sheet, a microlens sheet, etc.), a light diffusion film, a hard coat film, a film-type liquid crystal element, a touch panel, and the like.

Examples

[0062] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Note that the present invention is not limited to the Examples listed below.

[0063] ( Reference Example 1 : Preparation of active energy ray curable resin composition( r 1)) A flask equipped with a thermometer, a cooling tube, and a stirrer was charged with 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 part by mass of 4-methoxyphenol. 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 recovered by filtration to obtain an active energy ray-curable resin composition ( r 1).

[0064] ( Reference Example 2 : Preparation of active energy ray-curable resin composition ( r 2)) Except that 353 parts by mass of the unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone 2-mol 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-mol adduct (“Placcel FA1DDM” manufactured by Daicel Corporation), the same procedure as in Example 1 was carried out to obtain an active energy ray-curable resin composition ( r 2).

[0065] ( Example 1 : Preparation of active energy ray-curable resin composition ( 1 ) Reference Example 1 Except that 353 parts by mass of the unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone 2-mol adduct (“Placcel FA2D” manufactured by Daicel Corporation) used in Reference 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), the same procedure as 1 was carried out to obtain an active energy ray-curable resin composition (

[0066] ( Example 2: Preparation of an active energy ray-curable resin composition 2 ) Reference Example 1 Except that 353 parts by mass of the unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone 2 mol adduct ("Placcel FA2D" manufactured by Daicel Corporation) used in Reference Example 1 was changed to 540 parts by mass of polyethylene glycol monoacrylate (equivalent to 10 mol of EO chain) ("Blemmer AE-400" manufactured by NOF Corporation), an active energy ray-curable resin composition 2 ) was obtained in the same manner as

[0067] ( Example 3 : Preparation of an active energy ray-curable resin composition 3 ) Reference Example 1 Except that 148 parts by mass of phthalic anhydride used in Reference Example 1 was changed to 154 parts by mass of cis-cyclohexane-1,2-dicarboxylic anhydride, and 353 parts by mass of the unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone 2 mol adduct ("Placcel FA2D" manufactured by Daicel Corporation) used in Reference Example 1 was changed to 540 parts by mass of polyethylene glycol monoacrylate (equivalent to 10 mol of EO chain) ("Blemmer AE-400" manufactured by NOF Corporation), an active energy ray-curable resin composition 3 ) was obtained in the same manner as

[0068] ( Example 4 : Preparation of an active energy ray-curable resin composition 4 ) Reference Example 1 Except that 186 parts by mass of bisphenol A type epoxy resin ("Epiclon 850-S" manufactured by DIC Corporation) used in Reference Example 1 was changed to 136 parts by mass of naphthalene type epoxy resin ("HP-4032SS" manufactured by DIC Corporation), and 353 parts by mass of the unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone 2 mol adduct ("Placcel FA2D" manufactured by Daicel Corporation) used in Reference Example 1Similarly, an active energy ray-curable resin composition ( 4 ) was obtained.

[0069] (Comparative Example 1: Preparation of Active Energy Ray-Curable Resin Composition (R1)) Into 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 mol 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 system was controlled at 100 °C and stirred for 8 hours. Next, 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 recovered by filtration to obtain an active energy ray-curable resin composition (R1).

[0070] (Comparative Example 2: Preparation of Active Energy Ray-Curable Resin Composition (R2)) Into a flask equipped with a thermometer, a condenser, and a stirrer, 148 parts by mass (1.00 mol) of phthalic anhydride, 118 parts by mass of hydroxyethyl acrylate, 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 system was controlled at 100 °C and stirred for 8 hours. Next, 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 recovered by filtration to obtain an active energy ray-curable resin composition (R2).

[0071] Using the active energy ray-curable resin compositions obtained in the above Examples and Comparative Examples, the following measurements and evaluations were carried out.

[0072] [Method for Measuring Refractive Index] On a glass plate, 3 parts by mass of a photopolymerization initiator ("Omnirad 184" manufactured by IGM Resins) was added to and mixed with 100 parts by mass of the active energy ray-curable resin composition obtained in the examples and comparative examples, and it was applied using an applicator so that the film thickness during curing would be 50 μm, and then irradiated with active energy rays to form a cured coating film of the active energy ray-curable resin composition on the surface of the substrate. The 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.).

[0073] [Method for Measuring Abrasion Resistance] 3 parts by mass of a photopolymerization initiator ("Omnirad 184" manufactured by IGM Resins) was added to and mixed with 100 parts by mass of the active energy ray-curable resin composition obtained in the examples and comparative examples, and after applying it to a suitable plastic film, it was irradiated with ultraviolet rays using an 80 W high-pressure mercury lamp to obtain a laminate having a cured coating film on the film. Next, a disc-shaped indenter with a diameter of 2.4 cm was wrapped with 0.5 g of steel wool ("Bonster #0000" manufactured by Nippon Steel Wool Co., Ltd.), a load of 500 g was applied to the indenter, and an abrasion test was performed by reciprocating 10 times on the coated surface of the laminate. The haze values of the laminated film before and after the abrasion test were measured using a haze computer ("HZ-2" manufactured by Suga Test Instruments Co., Ltd.), and evaluation was carried out according to the following criteria using the difference value (dH) between them. Note that the smaller the difference value (dH), the better the abrasion resistance.

[0074] A: dH was 2.0 or less B: dH was more than 2.0 and 5.0 or less. C: dH was more than 5.0 and 10.0 or less. D: dH was more than 10.0 and 15.0 or less. E: dH was more than 15.0

[0075] [Table 1] Note that the above Example 1 is Reference Example 1, the above Example 2 is Reference Example 2, and the above Examples 3 to 6 are Examples 1 to 4, respectively. Also, the above active energy ray curable resin composition (1) is active energy ray curable resin composition (r1), the above active energy ray curable resin composition (2) is active energy ray curable resin composition (r2), and the above active energy ray curable resin compositions (3) to (6) are active energy ray curable resin compositions (1) to (4), respectively.

[0076] The examples shown in Table 1 1~4This is an example using the active energy ray curable resin composition of the present invention. It has been confirmed that these active energy ray curable resin compositions have high refractive index performance and excellent abrasion resistance.

[0077] On the other hand, Comparative Example 1 is an example using an active energy ray curable resin composition that does not have a compound having at least two aromatic rings and at least one epoxy group in one molecule defined in the present invention. It has been confirmed that this active energy ray curable resin composition is excellent in abrasion resistance but insufficient in refractive index performance.

[0078] Comparative Example 2 is an example using an active energy ray curable resin composition that does not have Alkylene oxide chain It has been confirmed that this active energy ray curable resin composition has high refractive index performance but extremely poor abrasion resistance.

Claims

1. A compound (A) having at least two aromatic rings and at least one epoxy group in one molecule, a polybasic acid anhydride (B), a (meth)acrylate compound (C) having an alkylene oxide chain, which is an active energy ray-curable resin composition using the above as essential raw materials, wherein the polybasic acid anhydride (B) is an alicyclic polybasic acid anhydride and / or an aromatic polybasic acid anhydride, the number of repeating units of the alkylene oxide chain of the compound (C) is in the range of 4 to 10, the compound (C) is polyethylene glycol mono(meth)acrylate, the amount of the polybasic acid anhydride (B) used is in the range of 30 to 300 parts by mass with respect to 100 parts by mass of the compound (A), the amount of the compound (C) used is in the range of 70 to 650 parts by mass with respect to 100 parts by mass of the compound (A), and the active energy ray-curable resin composition is an active energy ray-curable resin composition represented by the following general formula (1) or (2). 【Chemical 1】 [In formulas (1) to (2), ring A is independently an aromatic ring or a cyclo ring, R1 is independently a hydrogen atom or a methyl group, R2 is a hydrogen atom, and R3 is a hydrogen atom. X is -O-, -SO2-, 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.] 【Chemical 2】 [In formula (5), R4 and R5 are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.] [Chemical Formula 3]

2. The active energy ray-curable resin composition according to claim 1, wherein the active energy ray-curable resin composition contains a reaction product of the polybasic acid anhydride (B) and the compound (C) and a reaction product of the compound (A).

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

4. An article having a cured coating film comprising the cured product according to claim 3.

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