JP7707537B2 - Active energy ray curable resin composition, cured product and article - Google Patents

Description

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

In recent years, with the rapid development of display technology such as liquid crystal display devices, there is an increasing demand for sheet-like or film-like optical components used therein that have new functions and are of higher quality. Examples of such optical components include brightness-enhancing sheets such as prism sheets and microlens sheets used in the backlights of liquid crystal display devices. These brightness-enhancing sheets are usually made by laminating an optical functional layer having a fine uneven structure on the surface of a substrate, and the fine uneven structure on the surface can refract backlight light to improve the brightness on the front of the display. In order to maintain high brightness with a small amount of light, the material itself of the brightness-enhancing sheet is required to have a high refractive index.

Conventionally known resin materials for brightness-enhancing sheets are resin compositions containing metal oxide nanoparticles, in which the metal oxide nanoparticles have a particle size distribution with a cumulative 10% particle diameter of 5-25 nm, a cumulative 50% particle diameter of 7-30 nm, a cumulative 90% particle diameter of 15-50 nm, and a cumulative 100% particle diameter of 50-250 nm, and the resin composition contains a compound having two or more benzene skeletons as a resin component (see, for example, Patent Document 1). However, while such resin materials containing inorganic fine particles have a high refractive index, they have problems such as insufficient abrasion resistance in the cured product.

Therefore, there was a demand for a material that had high refractive index performance and excellent abrasion resistance when cured.

JP 2013-249439 A

The problem that the present invention aims to solve is to provide an active energy ray-curable resin composition, a cured product, and an article that have high refractive index performance and excellent abrasion resistance in the cured product.

As a result of intensive research into solving the above problems, the present inventors discovered that the above problems could 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 thus completed the present invention.

That is, the present invention relates to an active energy ray curable resin composition comprising, 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 in the compound (C) is in the range of 2 to 20, and the number of carbon atoms in the ester chain is 5 or more, and the present invention also relates to a cured product and article made of the active energy ray curable resin composition.

The active energy ray-curable resin composition of the present invention has a high refractive index and excellent abrasion resistance in the cured product, and therefore can be suitably used for optical components such as brightness-enhancing sheets such as prism sheets and microlens sheets.

The active energy ray-curable resin composition of the present invention is characterized in that it comprises, 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.

In the present invention, "(meth)acrylate" means acrylate and/or methacrylate. Furthermore, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acrylic" means acrylic and/or methacrylic.

The compound (A) used has at least two aromatic rings and at least one epoxy group in one molecule. Examples include bisphenol type epoxy resins, phenylene ether type epoxy resins, naphthylene 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-condensed novolac type epoxy resins, naphthol-cresol co-condensed 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, etc.

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, etc.

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, and hydrogenated bisphenol S type epoxy resin.

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, and tetramethyl-2,2'-biphenol type epoxy resin.

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, and hydrogenated tetramethyl-2,2'-biphenol type epoxy resin.

These compounds (A) can be used alone or in combination of two or more. Among these, bisphenol A type epoxy resins are preferred because they give active energy ray-curable resin compositions capable of forming cured products having high refractive index performance and excellent abrasion resistance.

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

In the present invention, the alicyclic polybasic acid anhydride is one in which an acid anhydride group is bonded to an alicyclic structure, and the presence or absence of aromatic rings in other structural parts is not important. Examples of the alicyclic polybasic acid anhydride include 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, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid.

Examples of the aromatic polybasic acid anhydrides include anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylic acid.

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

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.

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

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

The amount of the polybasic acid anhydride (B) used is preferably in the range of 30 to 300 parts by mass, more preferably 50 to 200 parts by mass, per 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.

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 units of the alkylene oxide chain are in the range of 2 to 20, and the range of 4 to 15 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. When the compound (C) has an ester chain, the number of carbon atoms of the ester chain is 5 or more, and the range of 5 to 25 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.

Examples of the 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, polyethylene glycol mono(meth)acrylate is preferred because it can provide an active energy ray-curable resin composition that has high refractive index performance and can form a cured product with excellent abrasion resistance.

The amount of compound (C) used is preferably in the range of 70 to 650 parts by mass, more preferably 90 to 500 parts by mass, per 100 parts by mass of 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.

The active energy ray-curable resin composition of the present invention is preferably represented by the following general formula (1), (2), (3) or (4) because it has high refractive index performance and can form a cured product with excellent abrasion resistance.

[In formulas (1) to (4), ring A is each independently an aromatic ring or a cyclo ring, R ¹ is each independently a hydrogen atom or a methyl group, R ² is each independently a hydrogen atom or a methyl group, and R ³ is each 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 each independently an integer of 3 to 8, s is each independently an integer of 1 to 5, and t is each independently an integer of 1 to 5.]

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

The method for producing the active energy ray-curable resin composition of the present invention is not particularly limited, and the composition can be produced by any known method. For example, the composition 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.

As a method for reacting the raw materials in sequence, for example, polybasic acid anhydride (B) and compound (C) are first reacted in the presence of triphenylphosphine at 100°C for 10 hours to obtain a reaction product, and then the obtained reaction product is reacted with compound (A) in the presence of triphenylphosphine at 105°C for 10 hours to produce the product.

Among these manufacturing methods, the method of reacting the raw materials sequentially is preferred because it produces an active energy ray-curable resin composition that can form a cured product with high refractive index performance and excellent abrasion resistance.

In addition, depending on the type of active energy rays used, it is preferable to use a photopolymerization initiator in the active energy ray-curable resin composition of the present invention. Examples of the photopolymerization initiator include photoradical polymerization initiators such as 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-diphenylethan-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, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone.

Examples of commercially available photopolymerization initiators 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" (IGM) Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (Nippon Kayaku Co., Ltd.); "Vicure 10", "Vicure 55" (Stoffa Chemical Co.); "Trigonal P1" (Akzo Nobel Co., Ltd.), "SANDORAY 1000" (SANDOZ Co., Ltd.); "DEAP" (Upjohn Chemical Co., Ltd.), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (Ward Blenkinsop Co., Ltd.); "Runtecure 1104" (manufactured by Runtec). These photopolymerization initiators can be used alone or in combination of two or more.

The photopolymerization initiator can also 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.

The amount of the photopolymerization initiator used is preferably in the range of 0.05 to 20 parts by mass, and more preferably in the range of 0.1 to 10 parts by mass, per 100 parts by mass of the nonvolatile content of the active energy ray-curable composition of the present invention.

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) as necessary. The content of the compound (A), the polybasic acid anhydride (B), and the compound (C) in the active energy ray curable resin composition is preferably in the range of 50 to 100 mass % in the non-volatile content of the active energy ray curable resin composition, and more preferably 100 mass %.

The other components include, for example, inorganic fine particles, silane coupling agents, phosphate ester compounds, solvents, UV absorbers, antioxidants, silicon-based additives, fluorine-based additives, antistatic agents, organic beads, quantum dots (QDs), rheology control agents, defoamers, antifogging agents, colorants, etc.

The 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 known and commonly used inorganic fine particles can be used. Examples of the inorganic fine particles include silica, alumina, zirconia, titania, barium titanate, and antimony trioxide. These inorganic fine particles can be used alone or in combination of two or more. Among these, silica particles, which are particularly versatile, come in various types such as fumed silica, precipitated silica, gel silica, and wet silica called sol-gel silica, and any of these may be used. 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 depending on the desired coating film performance, and the measured value by dynamic light scattering is preferably in the range of 10 to 250 nm. When inorganic fine particles are used, the amount of addition is preferably in the range of 0.1 to 60 parts by mass per 100 parts by mass of the nonvolatile content of the active energy ray curable resin composition.

Examples of the silane coupling agent include (meth)acryloyloxy-based silane coupling agents such as [(meth)acryloyloxyalkyl]trialkylsilane, [(meth)acryloyloxyalkyl]dialkylalkoxysilane, [(meth)acryloyloxyalkyl]alkyldialkoxysilane, and [(meth)acryloyloxyalkyl]trialkoxysilane; vinyl-based silane coupling agents such as trialkylvinylsilane, dialkylalkoxyvinylsilane, alkyldialkoxyvinylsilane, trialkoxyvinylsilane, trialkylallylsilane, dialkylalkoxyallylsilane, alkyldialkoxyallylsilane, and trialkoxyallylsilane; styrene-based silane coupling agents such as styryltrialkyl, styryldialkylalkoxysilane, styrylalkyldialkoxysilane, and styryltrialkoxysilane; (glycidyloxyalkyl)trialkoxysilane; Examples of the silane coupling agents include epoxy-based silane coupling agents such as xylsilane, (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; and isocyanate-based silane coupling agents such as (isocyanate alkyl)trialkylsilane, (isocyanate alkyl)dialkylalkoxysilane, (isocyanate alkyl)alkyldialkoxysilane, and (isocyanate alkyl)trialkoxysilane. These silane coupling agents can be used alone or in combination of two or more.

Examples of the phosphate ester compound include commercially available products such as "Kayamar PM-2" and "Kayamar PM-21" manufactured by Nippon Kayaku Co., Ltd., which are phosphate ester compounds having a (meth)acryloyl group in the molecular structure, "Light Ester P-1M", "Light Ester P-2M", and "Light Acrylate P-1A(N)" manufactured by Kyoeisha Chemical Co., Ltd., "SIPOMER PAM 100", "SIPOMER PAM 200", "SIPOMER PAM 300", and "SIPOMER PAM 4000" manufactured by Solvay, "Viscoat #3PA" and "Viscoat #3PMA" manufactured by Osaka Organic Chemical Industry Co., Ltd., and "New Frontier S-23A" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and "SIPOMER PAM 5000" manufactured by Solvay, which is a phosphate ester compound having an allyl ether group in the molecular structure.

The solvent is added for the purpose of adjusting the coating viscosity of the active energy ray curable resin composition, and the type and amount of the solvent are appropriately adjusted according to the desired performance. In general, the solvent is used so that the non-volatile content of the active energy ray curable resin composition is in the range of 10 to 90 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.

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

Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate-based antioxidants. These antioxidants can be used alone or in combination of two or more.

Examples of the silicon-based additives 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 acrylic groups, and polydimethylsiloxanes having polyester-modified acrylic groups. These silicon additives can be used alone or in combination of two or more kinds.

The fluorine-based additives include, for example, the "Megaface" series from DIC Corporation. These fluorine-based additives can be used alone or in combination of two or more types.

Examples of the antistatic agent 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.

Examples of the organic beads include 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, polyethylene fluoride resin beads, polyethylene resin beads, etc. These organic beads can be used alone or in combination of two or more types. The average particle size of these organic beads is preferably in the range of 1 to 10 μm.

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, and 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; ZnSeS, ZnSeTe, ZnSTe, CdZnS, CdZnSe, CdZnTe, CdSeS, CdSeTe, CdSTe, CdHgS, CdHgSe, and Cd Ternary compounds such as HgTe, 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 B ₄ C ₃ , Al ₄ C ₃ , and Ga ₄ C ₃ . 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 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 , and InTe. Examples of the IV-VI group 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 I-III-VI group semiconductor compounds include CuInS ₂ , CuInSe ₂ , CuInTe ₂ , CuGaS ₂ , CuGaSe ₂ , CuGaSe ₂ , AgInS ₂ , AgInSe ₂ , AgInTe ₂ , AgGaSe ₂ , AgGaS ₂ , AgGaTe ₂ , etc. Examples of the IV group elements or compounds containing them include C, Si, Ge, SiC, SiGe, etc. The quantum dots may be made of a single semiconductor compound, or may have a core-shell structure made of multiple semiconductor compounds. In addition, the surface of the quantum dots may be modified with an organic compound.

These various additives can be added in any amount depending on the desired performance, but it is usually preferable to use them in the range of 0.01 to 40 parts by mass per 100 parts by mass of the non-volatile content of the active energy ray-curable resin composition.

The active energy ray-curable resin composition of the present invention is produced by mixing the above-mentioned components. The mixing method is not particularly limited, and a paint shaker, disperser, roll mill, bead mill, ball mill, attritor, sand mill, bead mill, etc. can be used.

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 radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out the curing reaction by ultraviolet rays.

As a source of ultraviolet light, ultraviolet lamps are generally used from the standpoint 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, LEDs, etc.

The cumulative 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 cumulative light amount is within the above range, it is preferable because the occurrence of uncured portions can be prevented or suppressed.

The irradiation of the active energy rays may be carried out in one step or in two or more steps.

Examples of the article of the present invention include optical components.

Examples of the optical components include plastic lenses, polarizing films, retardation films, anti-reflection films, brightness enhancement films (prism sheets, microlens sheets, etc.), light diffusion films, hard coat films, film-type liquid crystal elements, touch panels, etc.

The present invention will be specifically described below with reference to examples and comparative examples. Note that the present invention is not limited to the examples listed below.

( Reference Example 1 : Preparation of active energy ray curable resin composition ( r1 ))
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 unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone 2-mol adduct (Daicel Corporation "Placcel FA2D"), 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 system was controlled to 100 ° C. and stirred for 8 hours. Next, the temperature was lowered to 60 ° C., and then 186 parts by mass (0.50 mol) of bisphenol A type epoxy resin (DIC Corporation "Epicron 850-S") was added, and stirring was continued at 105 ° C. for 7 hours. The resulting reaction product was filtered and collected to obtain an active energy ray curable resin composition ( r1 ).

( Reference Example 2 : Preparation of active energy ray curable resin composition ( r2 ))
An active energy ray curable resin composition (r2) was obtained in the same manner as in Example 1, except that the 353 parts by mass of 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 unsaturated fatty acid hydroxyalkyl ester modified ε- caprolactone 1-mol adduct ("PLACCEL FA1DDM" manufactured by Daicel Corporation).

( Example 1 : Preparation of active energy ray curable resin composition ( 1 ))
An active energy ray curable resin composition (1) was obtained in the same manner as in Reference Example 1 , except that 353 parts by mass of the unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone 2-mol adduct (manufactured by Daicel Corporation, "Placcel FA2D") used in Reference Example 1 was changed to 359 parts by mass of polyethylene glycol monoacrylate (equivalent to 4.5 mol of EO chain) (manufactured by NOF Corporation, "Blenmar AE-200").

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

( Example 3 : Preparation of active energy ray curable resin composition ( 3 ))
An active energy ray curable resin composition (3) was obtained in the same manner as in Reference Example 1, except that the 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 the 353 parts by mass of the unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone 2-mol adduct (manufactured by Daicel Corporation, "Placcel FA2D") used in Reference Example 1 was changed to 540 parts by mass of polyethylene glycol monoacrylate (equivalent to 10 moles of EO chain) (manufactured by NOF Corporation, "Blenmar AE- 400 ").

( Example 4 : Preparation of active energy ray curable resin composition ( 4 ))
An active energy ray curable resin composition (4) was obtained in the same manner as in Reference Example 1 , except that the 186 parts by mass of the bisphenol A type epoxy resin ("Epicron 850-S" manufactured by DIC Corporation) used in Reference Example 1 was changed to 136 parts by mass of a naphthalene type epoxy resin ("HP-4032SS" manufactured by DIC Corporation), and the 353 parts by mass of the unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone 2-mol adduct ("PLAXEL 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).

(Comparative Example 1: Preparation of active energy ray curable resin composition (R1))
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 unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone 2-mol adduct (Daicel Corporation "Placcel FA2D"), 2 parts by mass of 2,6-di-tert-butyl-p-cresol, and 0.2 parts by mass of 4-methoxyphenol, and the system was controlled to 100 ° C. and stirred for 8 hours. Next, the temperature was lowered to 60 ° C., and then 108 parts by mass of an epoxy resin (ADEKA Corporation "ED-523T") mainly composed of neopentyl glycol diglycidyl ether was added, and stirring was continued for 7 hours at 105 ° C., and the resulting reaction product was collected by filtration to obtain an active energy ray curable resin composition (R1).

(Comparative Example 2: Preparation of active energy ray curable resin composition (R2))
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 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 system was controlled to 100 ° C. and stirred for 8 hours. Next, the temperature was lowered to 60 ° C., and then 186 parts by mass (0.50 mol) of bisphenol A type epoxy resin (DIC Corporation "Epicron 850-S") was added, and stirring was continued at 105 ° C. for 7 hours. The resulting reaction product was filtered and collected to obtain an active energy ray curable resin composition (R2).

The following measurements and evaluations were carried out using the active energy ray-curable resin compositions obtained in the above examples and comparative examples.

[Method of measuring refractive index]
On a glass plate, 100 parts by mass of the active energy ray curable resin composition obtained in the Examples and Comparative Examples was mixed with 3 parts by mass of a photopolymerization initiator (IGM Resins'"Omnirad184"), and the mixture was applied using an applicator so that the film thickness upon curing was 50 μm. The substrate was 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 (Atago Co., Ltd.'s "NAR-3T").

[Method of measuring abrasion resistance]
100 parts by mass of the active energy ray curable resin composition obtained in the examples and comparative examples were mixed with 3 parts by mass of a photopolymerization initiator (IGM Resins'"Omnirad184"), applied to a suitable plastic film, and then irradiated with ultraviolet light from an 80W high pressure mercury lamp to obtain a laminate having a cured coating film on the film. Next, a disc-shaped indenter having a diameter of 2.4 cm was wrapped with 0.5 g of steel wool (Japan Steel Wool Co., Ltd.'s "Bonstar #0000"), and a load of 500 g was applied to the indenter, and an abrasion test was performed in which the coated surface of the laminate was reciprocated 10 times. The haze value of the laminate film before and after the abrasion test was measured using Suga Test Instruments'"Haze Computer HZ-2", and the difference value (dH) was used to evaluate according to the following criteria. The smaller the difference value (dH), the better the abrasion resistance.

A: dH was 2.0 or less. B: dH was greater than 2.0 and 5.0 or less.
C: dH was greater than 5.0 and equal to or less than 10.0.
D: dH was greater than 10.0 and equal to or less than 15.0.
E: dH was greater than 15.0.

Incidentally, the above-mentioned Example 1 corresponds to Reference Example 1, the above-mentioned Example 2 corresponds to Reference Example 2, and the above-mentioned Examples 3 to 6 correspond to Examples 1 to 4, respectively. Moreover, the above-mentioned active energy ray-curable resin composition (1) corresponds to active energy ray-curable resin composition (r1), the above-mentioned active energy ray-curable resin composition (2) corresponds to active energy ray-curable resin composition (r2), and the above-mentioned active energy ray-curable resin compositions (3) to (6) correspond to active energy ray-curable resin compositions (1) to (4), respectively.

Examples 1 to 4 shown in Table 1 are examples in which the active energy ray-curable resin composition of the present invention was used. It was confirmed that these active energy ray-curable resin compositions had high refractive index performance and excellent abrasion resistance.

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

Comparative Example 2 is an example in which an active energy ray curable resin composition not having an alkylene oxide chain as defined in the present invention was used. It was confirmed that this active energy ray curable resin composition had a high refractive index performance, but was significantly insufficient in abrasion resistance.

Claims (4)

A compound (A) having at least two aromatic rings and at least one epoxy group in one molecule;
A polybasic acid anhydride (B),
(C) a (meth)acrylate compound having an alkylene oxide chain ;
An active energy ray-curable resin composition comprising the following as an essential raw material:
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 contained in 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 relative to 100 parts by mass of the compound (A);
An active energy ray-curable resin composition , wherein the amount of the compound (C) used is in the range of 70 to 650 parts by mass relative to 100 parts by mass of the compound (A) , and the active energy ray-curable resin composition is represented by the following general formula (1) or (2):
[In formulas (1) and (2), rings A are each independently an aromatic ring or a cyclo ring, R ¹ are each independently a hydrogen atom or a methyl group, R ² is a hydrogen atom, and 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 from 4 to 10, n is an integer from 4 to 10, and m+n is an integer from 8 to 20.]
[In formula (5), R ⁴ and R ⁵ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.]
The active energy ray curable resin composition according to claim 1, which contains a reaction product of the polybasic acid anhydride (B) and the compound (C) with the compound (A). A cured product of the active energy ray-curable resin composition according to claim 1 or 2. An article having a cured coating film comprising the cured product according to claim 3 .