JP7635538B2 - lens - Google Patents

Description

The present invention relates to an active energy ray-curable resin composition for forming a resin layer of a laminate having a resin layer and an inorganic layer, a cured product of the active energy ray-curable resin composition, a laminate, and a lens made of the laminate.

In recent years, curable resin compositions, such as active energy ray curable resin compositions that can be cured by active energy rays such as ultraviolet rays, and thermosetting resin compositions that can be cured by heat, have been widely used in the fields of inks, paints, coatings, adhesives, optical components, and the like. In particular, in the field of optical components, they are preferably used as lens resins for smartphones and car-mounted cameras. As a molding method for the lens resins, a manufacturing process using optical imprinting has been actively studied because it leads to thinner lens modules and improved production efficiency. The optical imprinting method is a method in which uncured resin is applied to a substrate such as a wafer, and then the shape is transferred by sandwiching it between lens molds, and then photocuring is performed, making it possible to mold hundreds of wafer-level lenses at once.

As a resin used in the optical imprinting, a curable resin composition containing urethane (meth)acrylate is known (see, for example, Patent Document 1). However, when the upper layer of the lens is covered with an anti-reflection film after the lens is molded, problems such as the generation of cracks have been encountered.

Therefore, there was a need for a material for forming a resin layer that could suppress the occurrence of cracks in an inorganic layer after the formation of an inorganic layer such as an anti-reflective film.

International Publication No. 2019/142061

The problem that the present invention aims to solve is to provide an active energy ray-curable resin composition for forming a resin layer having excellent crack resistance capable of suppressing cracking in the inorganic layer in a laminate having a resin layer and an inorganic layer, a cured product of the active energy ray-curable resin composition, a laminate, and a lens made of the laminate.

As a result of intensive research into solving the above problems, the present inventors discovered that the above problems can be solved by using an active energy ray-curable resin composition containing a hyperbranched polymer compound (A) having a hyperbranched structure and six or more (meth)acryloyl groups in one molecule, and an aliphatic urethane (meth)acrylate (B), and thus completed the present invention.

That is, the present invention relates to an active energy ray curable resin composition for forming a resin layer of a laminate having a resin layer and an inorganic layer, the active energy ray curable resin composition containing a compound (A) having six or more (meth)acryloyl groups and a multi-branched structure in one molecule, and an aliphatic urethane (meth)acrylate (B), a cured product of the active energy ray curable resin composition, a laminate, and a lens made of the laminate.

The present invention provides an active energy ray-curable resin composition for forming a resin layer having excellent crack resistance capable of suppressing cracking in the inorganic layer in a laminate having a resin layer and an inorganic layer, a cured product of the active energy ray-curable resin composition, a laminate, and a lens made of the laminate.

The active energy ray-curable resin composition of the present invention can also suppress the occurrence of cracks in the inorganic layer in a laminate having a resin layer and an inorganic layer, and can therefore be suitably used in lens production by photoimprinting.

The active energy ray-curable resin composition of the present invention is characterized by containing a hyperbranched polymer compound (A) having a hyperbranched structure and six or more (meth)acryloyl groups in one molecule, and an aliphatic urethane (meth)acrylate (B).

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

Examples of the hyperbranched polymer compound (A) having a hyperbranched structure and six or more (meth)acryloyl groups in one molecule include compounds having a dendrimer structure (hereinafter sometimes referred to as "dendrimer"), compounds having a hyperbranched structure (hereinafter sometimes referred to as "hyperbranch" or "hyperbranched polymer"), compounds having a star structure, etc., and are not particularly limited as long as the effects of the present invention can be obtained.

Commercially available products of the compound having the dendrimer structure include, for example, "Viscoat #1000LT" manufactured by Osaka Organic Chemical Industry Co., Ltd. and "Miramer SP1106" manufactured by MIWON Corporation. These compounds having a dendrimer structure can be used alone or in combination of two or more kinds.

Commercially available compounds having the hyperbranched structure include, for example, "CN2302," "CN2303," and "CN2304" manufactured by Arkema, and "Photomer 5500" manufactured by IGM. These compounds having a hyperbranched structure can be used alone or in combination of two or more types.

The multi-branched polymer compound (A) contains a compound having 6 or more (meth)acryloyl groups in its structure. The average number of (meth)acryloyl groups contained per molecule of the multi-branched polymer compound is preferably in the range of 6 to 64, since an active energy ray-curable resin composition having excellent crack resistance capable of suppressing cracking in the inorganic layer can be obtained, and is particularly preferably in the range of 10 to 32, since the crack suppression effect is significant.

The weight average molecular weight (Mw) of the hyperbranched polymer compound (A) is preferably in the range of 500 to 30,000, since an active energy ray-curable resin composition having excellent crack resistance capable of suppressing cracking in the inorganic layer can be obtained, and more preferably in the range of 1,000 to 10,000, since the effect of suppressing cracking is significant. In the present invention, the weight average molecular weight (Mw) indicates a value measured by gel permeation chromatography (GPC).

The viscosity of the hyperbranched polymer compound (A) at 25°C is preferably in the range of 10 mPa·s to 1,500 mPa·s, and more preferably in the range of 100 mPa·s to 1,000 mPa·s. In the present invention, the viscosity is a value measured using an E-type viscometer.

The method for producing the multi-branched polymer compound (A) is not particularly limited, and the compound can be produced by any known method. For example, the divergent method, in which a branch is formed by bonding a molecule to a central core molecule for each generation, the convergent method, in which a branch portion synthesized in advance is bonded to a core molecule, and a method of synthesis in one step using a monomer ABx having a branch portion having two or more reaction points B and a linking portion having another reaction point A in one molecule are listed. Among these, the divergent method is preferred, and for example, the multi-branched polymer compound (A) is preferably produced by a method in which a polyhydric alcohol and a compound having one or more carboxyl groups and two or more hydroxyl groups are subjected to an esterification reaction to obtain a multi-branched polyester polyol, and then the terminal hydroxyl groups are reacted with (meth)acrylic acid.

Examples of the polyhydric alcohol include glycerin, trimethylolpropane, ditrimethylolpropane, trimethylolethane, ditrimethylolethane, tris(2-hydroxyethyl)isocyanurate, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol, sorbitol, mannitol, and alkylene oxide adducts or caprolactone adducts thereof. These polyhydric alcohols can be used alone or in combination of two or more.

Examples of the compound having one or more carboxyl groups and two or more hydroxyl groups include 2,3-dihydroxypropionic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, tartaric acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 3,5-bis(2-hydroxyethoxy)benzoic acid, 2,6-dihydroxy-4-methylbenzoic acid, 3,5-dihydroxy-4-methylbenzoic acid, citrazinic acid, 2,3-dihydroxyphenylacetic acid, 2,4-dihydroxyphenylacetic acid, 2,5-dihydroxyphenylacetic acid, 2,6-dihydroxyphenylacetic acid, 3,4-dihydroxyphenylacetic acid, 3,5-dihydroxyphenylacetic acid, and derivatives thereof. These compounds can be used alone or in combination of two or more.

As described above, the hyperbranched polyester polyol can be obtained by an esterification reaction between a polyhydric alcohol and a compound having one or more carboxyl groups and two or more hydroxyl groups, or a commercially available product can be used.

Commercially available hyperbranched polyester polyols include, for example, Perstorp's "BOLTORN H20", "BOLTORN H30", "BOLTORN H40", "BOLTORN H311", "BOLTORN H2003", "BOLTORN H2004", "BOLTORN P500", "BOLTORN P501", and "BOLTORN P1000".

The urethane (meth)acrylate compound that can be used as the aliphatic urethane (meth)acrylate (B) is a compound having at least two (meth)acryloyloxy groups and at least two urethane structures represented by "-NH-C(=O)O-" in one molecule. Examples of the aliphatic urethane (meth)acrylate compound include EBECRYL (registered trademark) 4201, 8402, and 9270 (all manufactured by Daicel-Allnex Corporation), CN981NS, CN991NS, and CN996NS (all manufactured by Arkema), UA-TMC1, UA-TMC2, UA-TMC4, and UA-TMC5 (all manufactured by Kyoeisha Chemical Co., Ltd.), and NK Oligo UA-4200 and UA-4400 (all manufactured by Shin-Nakamura Chemical Co., Ltd.). By using these aliphatic urethane (meth)acrylates, it is possible to obtain a cured product that is resistant to heat yellowing. These aliphatic urethane (meth)acrylates can be used alone or in combination of two or more. "Aliphatic" refers to acyclic or cyclic, non-aromatic carbon compounds.

The active energy ray-curable resin composition of the present invention may also contain a photopolymerization initiator as necessary.

Examples of the 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-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 "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", Examples of photopolymerization initiators include Omnirad-81 (manufactured by IGM), Kayacure-DETX, Kayacure-MBP, Kayacure-DMBI, Kayacure-EPA, and Kayacure-OA (manufactured by Nippon Kayaku Co., Ltd.), Bikeure-10, Bikeure-55 (manufactured by Stouffer Chemical Co., Ltd.), Trigonal P1 (manufactured by Akzo Co., Ltd.), Sandray 1000 (manufactured by Sandoz Co., Ltd.), Deep (manufactured by Upjohn Co., Ltd.), Quantacure-PDO, Quantacure-ITX, and Quantacure-EPD (manufactured by Ward Blenkinsop Co., Ltd.), and Runtecure-1104 (manufactured by Runtec Co., Ltd.). These photopolymerization initiators can be used alone or in combination of two or more types.

The content of the photopolymerization initiator is, for example, preferably in the range of 0.05 to 10 mass % of the total components other than the solvent of the active energy ray-curable resin composition, and more preferably in the range of 0.1 to 5 mass %.

The photopolymerization initiator can also be used in combination with a photosensitizer.

Examples of the photosensitizer include amine compounds, urea compounds, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, and nitrile compounds.

The active energy ray-curable resin composition of the present invention may also contain, as necessary, a (meth)acrylic compound having a carbonate structure, a (meth)acrylic compound having a cyclic structure, or a (meth)acrylic compound having an alkylene glycol structure. By adding these compounds, the viscosity, refractive index, elastic modulus, etc. of the active energy ray-curable resin composition can be effectively adjusted.

Examples of the (meth)acrylic compound having a carbonate structure include those obtained by reacting polycarbonate polyol with (meth)acrylic acid and/or (meth)acrylic acid ester.

The polycarbonate polyol may be, for example, a reaction product of a compound having two or more hydroxyl groups with a carbonate ester.

Examples of compounds having two or more hydroxyl groups include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolpropane, trimethylolethane, glycerin, etc. These compounds can be used alone or in combination of two or more.

Examples of the carbonate ester include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. These compounds can be used alone or in combination of two or more.

Examples of the (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, octoxypolyethylene glycol Cholepolypropylene glycol mono(meth)acrylate, lauroxypolyethylene glycol mono(meth)acrylate, stearoxypolyethylene glycol mono(meth)acrylate, phenoxypolyethylene glycol mono(meth)acrylate, phenoxypolyethylene glycol-polypropylene glycol mono(meth)acrylate, nonylphenoxypolypropylene glycol mono(meth)acrylate, nonylphenoxypoly(ethylene glycol-propylene glycol) mono(meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, etc. can be used. These (meth)acrylic acid esters can be used alone or in combination of two or more.

As the (meth)acrylic compound having a cyclic structure, for example, a (meth)acrylic compound having a monocycloalkane structure, a benzene ring, a tricyclodecane structure, a dicyclopentenyl structure, an isobornyl structure, a heterocyclic structure having an oxygen atom as a hetero atom, etc. can be used. These compounds can be used alone or in combination of two or more kinds.

Examples of the (meth)acrylic compound having a monocycloalkane structure include cyclohexyl (meth)acrylate and 1,4-cyclohexanedimethanol monoacrylate. These compounds can be used alone or in combination of two or more.

Examples of the (meth)acrylic compound having a benzene ring include benzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, etc. These compounds can be used alone or in combination of two or more.

Examples of the (meth)acrylic compound having a tricyclodecane (dicyclopentanyl) structure include dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, tricyclodecane diol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, etc. These compounds can be used alone or in combination of two or more.

Examples of the (meth)acrylic compound having a dicyclopentenyl structure include dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, etc. These compounds can be used alone or in combination of two or more kinds.

Examples of the (meth)acrylic compound having an isobornyl structure include isobornyl (meth)acrylate, isobornyl di(meth)acrylate, etc. These compounds can be used alone or in combination of two or more kinds.

Examples of (meth)acrylic compounds having a heterocyclic ring structure with an oxygen atom as a hetero atom include cyclic trimethylolpropane formal acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and neopentyl glycol-modified trimethylolpropane di(meth)acrylate. These compounds can be used alone or in combination of two or more.

The (meth)acrylic compound having the alkylene glycol structure essentially has one or two (meth)acryloyl groups and an alkylene glycol structure in one molecule. Examples of the alkylene glycol structure include 1,2-ethanediol (ethylene glycol), 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,2-propanediol (propylene glycol), 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 3-methyl-1,3-butanediol, 2-methyl-1,3-butanediol, 1,2-hexanediol, ethanol, 1,5-hexanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,2-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 3,6-octanediol, 2,2,4-trimethyl 1,3-pentanediol, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1,3-hexanediol, 1,2-nonanediol, 1,8-nonanediol, 2,8-nonanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-decanediol, 2,2-diisobutyl-1,3-propanediol, etc. These alkylene glycol structures may be present in one molecule, or may have two or more types. Among these, ethylene glycol, propylene glycol, and neopentyl glycol are preferred, since they can provide an active energy ray-curable composition capable of forming a lens having excellent heat resistance. Furthermore, it is preferred that the number of repeating units of the alkylene glycol structure is 2 to 15, since they can provide an active energy ray-curable composition capable of forming a lens having even better heat resistance.

Commercially available (meth)acrylic compounds having an alkylene glycol structure include, for example, Miramer M170, Miramer M202, Miramer M210, Miramer M216, Miramer M220, Miramer M222, Miramer M232, Miramer M280, Miramer M282, Miramer M284, Miramer M286, Miramer M2040, Miramer M231, Miramer M233, Miramer M235, Miramer M281, and Miramer M283 manufactured by MIWON Corporation; and NK Ester manufactured by Shin-Nakamura Chemical Co., Ltd. A-30G", "NK Ester A-90G", "NK Ester A-130G", "NK Ester AM-30PG", "NK Ester A-200", "NK Ester A-400", "NK Ester A-600", "NK Ester APG-100", "NK Ester APG-200", "NK Ester APG-400", "NK Ester APG-700", "NK Ester A-PTMG-65", "NK Ester M-20G", "NK Ester M-30G", "NK Ester M-40G", "NK Ester M-90G", "NK Ester M-130G", "NK Ester M-30PG", "NK Ester EH-4E", "NK Ester B-20G", "NK Ester S-12E", "NK Ester 2G", "NK Ester 3G", "NK Ester 4G", "NK Ester 9G", "NK Ester 14G", "NK Ester 3PG", "NK Ester 9PG", Kyoeisha Chemical Co., Ltd.'s "Light Ester BC", "Light Ester 130MA", "Light Ester BC", "Light Ester 2EG", "Light Ester 3EG", "Light Ester 4EG", "Light Ester 9EG", "Light Ester 14EG", "Light Acrylate EC-A", "Light Acrylate MTG-A", "Light Acrylate EHDG-AT", "Light Acrylate 130A", "Light Acrylate DPM-A", "Light Acrylate P2H-A", "Light Acrylate P-200A", "Light Acrylate 3EG-A", "Light Acrylate 4EG-A", "Light Acrylate 9EG-A", "Light Acrylate 14EG-A", "Light Acrylate PTMGA-250", Hitachi Chemical Co., Ltd.'s "Fancryl FA-240A", "Fancryl FA-P240A", "Fancryl FA-P270A", "Fancryl FA-PTG9A", "Fancryl FA-400M (100)", "Fancryl FA-240M", "Fancryl FA-PTG9M", Daiichi Kogyo Seiyaku Co., Ltd.'s "New Frontier ME-3," "New Frontier ME-4S," "New Frontier MPE-600," "New Frontier PE-200," "New Frontier PE-300," "New Frontier PE-400," "New Frontier PE-600," "New Frontier MPEM-400," "New Frontier TEGDMA," "KAYARAD PEG400DA" and "KAYARAD PEG400DA" manufactured by Nippon Kayaku Co., Ltd., and "Viscoat #190," "Viscoat #MTG," "MPE400A," "MPE550A," and "Viscoat #310HP" manufactured by Osaka Organic Chemical Industry Co., Ltd. are examples of such products.

Furthermore, the active energy ray-curable resin composition of the present invention may contain, as necessary, urethane (meth)acrylate, epoxy (meth)acrylate, acrylic (meth)acrylate, etc., which are not included in the component (B).

In addition, the active energy ray-curable composition of the present invention may further contain other additives in addition to the components (A) and (B) as necessary.

Examples of the other additives include additives such as polymerization inhibitors, surface conditioners, antistatic agents, defoamers, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, UV absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, silica beads, and organic beads; and inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, cerium oxide, and antimony oxide. These other additives can be used alone or in combination of two or more. Among these, it is preferable to add a heat stabilizer and an antioxidant, since they can improve heat resistance and moist heat resistance.

Examples of the heat resistance stabilizer include ethanethiol, 2-methylpropane-2-thiol, n-dodecanethiol, 2,3,3,4,4,5-hexamethylhexane-2-thiol, 2-mercaptoethanol, 4-mercapto-1-butanol, methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, 3-(trimethoxysilyl)propane-1-thiol, 3-(triethoxysilyl)propane-1-thiol, benzenethiol, benzylthiol, 3-methylbenzenethiol, 4-methylbenzenethiol, naphthalene-2-thiol, pyridine-2-thiol, and benzimidazole- 2-Thiol, benzothiazole-2-thiol, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, 2,3-dihydroxy-1,4-butanedithiol, 3,6-dioxa-1,8-octanedithiol 3,7-dithia-1,9-nonanedithiol, 1,4-bis(3-mercaptopropionyloxy)butane, 1,4-bis(3-mercaptobutyryloxy)butane, tetraethylene glycol bis(3-mercaptopropionate), 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 2,3-diamino-1,4-benzenedithiol, 4,5-dimethyl-O-xylylenedithiol, toluene-3,4-dithiol, 4,4'-biphenyldithiol, 1,5-naphthalenedithiol, 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol, 2-amino-1,3,5-triazine-4,6-dithiol, 6-anilino-1,3,5-triazine-2,4-dithiol, 6-(4'-anilinophenyl-isopropylamino) )-1,3,5-triazine-2,4-dithiol, 6-(3',5'-tert-butyl-4'-hydroxyanilino)-1,3,5-triazine-2,4-dithiol, quinoxaline-2,3-dithiol, purine-2,6-dithiol, 1,3,4-thiadiazole-2,5-dithiol, bis(2-mercaptoethyl)ether, trimethylolethane tris(3-mercaptopropione ester), trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), 1,3,5-benzenetrithiol, 1,3,5-triazine-2,4,6-trithiol, tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tris[2-(3-mercaptobutyryloxy)ethyl]isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptobutyrate), and other compounds having a mercapto group. These heat resistance stabilizers can be used alone or in combination of two or more.

Examples of commercially available heat stabilizers include "Chiokalcol 20" manufactured by Kao Corporation, "Karenz MT PE1", "Karenz MT BD1", "Karenz MT NR1", "TPMB", and "TEMB" manufactured by Showa Denko K.K., and "TMMP", "TEMPIC", "PEMP", "EGMP-4", "DPMP", "TMMP II-20P", and "PEMP II-20P" manufactured by SC Organic Chemical Co., Ltd.

From the viewpoint of obtaining sufficient heat resistance, the amount of the heat stabilizer used in the active energy ray-curable composition is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 5 parts by mass, and particularly preferably in the range of 0.5 to 3 parts by mass.

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

Examples of the phenol-based antioxidants include styrenated phenol, 2,6-ditertiary butyl-p-cresol, 2,5-ditertiary butyl hydroquinone, 2,5-ditertiary amyl hydroquinone, 3-(3,5-ditertiary butyl-4-hydroxyphenyl)octadecyl propionate, 2,4-bis(octylthiomethyl)-6-methylphenol, 2,2-methylenebis(6-tertiary butyl-p-cresol), 2,2-methylenebis(6-tertiary butyl-4-ethylphenol), 4,4-butylidenebis(6-tert-butyl-m-cresol), 4,4-thiobis(6-tert-butyl-m-cresol), 2,2-thiodiethylbis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate], bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate][ethylene bis(oxyethylene)], bis[3-[3 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl), N,N-bis[2-[2-(3,5-ditertiarybutyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxamide, N,N-(hexane-1,6-diyl)bis[3-(3,5-ditertiarybutyl-4-hydroxyphenyl)propanamide], 2,4,6-tris(3,5-ditertiarybutyl)-4-hydroxy-5-methylphenyl)propanoic acid], butyl-4-hydroxybenzyl) mesitylene, 1,3,5-tris(3,5-ditertiarybutyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris(2-methyl-4-hydroxy-5-tertiarybutylphenyl)butane, pentaerythritol tetrakis[3-(3,5-ditertiarybutyl-4-hydroxyphenyl)propionate], diethyl(3,5-ditertiarybutyl-4-hydroxybenzyl)phosphonate, etc.

Commercially available phenol-based antioxidants include, for example, "IRGANOX 1010", "IRGANOX 1010FF", "IRGANOX 1035", "IRGANOX 1035FF (W&C)", "IRGANOX 1076", "IRGANOX 1076FD", "IRGANOX 1098", "IRGANOX 1135", "IRGANOX 1330", "IRGANOX 1520L", "IRGANOX 245", "IRGANOX 245FF", "IRGANOX 259", and "IRGANOX 3114" manufactured by BASF Corporation; "ANTAGE BHT", "ANTAGE DAH", "ANTAGE DBH", and "ANTAGE 3114" manufactured by Kawaguchi Chemical Industry Co., Ltd. W-300", "ANTAGE W-400", "ANTAGE W-500", "ANTAGE Crystal", "ANTAGE SP", "ANTAGE HP-200", "ANTAGE HP-300", manufactured by ADEKA CORPORATION "ADK STAB AO-20", "ADK STAB AO-30", "ADK STAB AO-40", "ADK STAB AO-50", "ADK STAB AO-50F", "ADK STAB AO-50T", "ADK STAB AO-60", "ADK STAB AO-60G", "ADK STAB AO-80", "ADK STAB AO-330", manufactured by Sumitomo Chemical Co., Ltd. "SUMILIZER GA-80", "SUMILIZER GP", "SUMILIZER Examples include "MDP-S", "SUMILIZER WX-R", "SUMILIZER WX-RC", "Yoshinox BB" manufactured by Mitsubishi Chemical Corporation, and "JC-356" manufactured by Johoku Chemical Industry Co., Ltd.

Examples of the phosphite antioxidants include tris(2-ethylhexyl)phosphite, tridecyl phosphite, triisodecyl phosphite, trilauryl phosphite, tris(tridecyl)phosphite, tri(stearyl)phosphite, diphenyl mono(2-ethylhexyl)phosphite, diphenyl monodecyl phosphite, diphenyl isodecyl phosphite, diphenyl mono(tridecyl)phosphite, triphenyl phosphite, tricresyl phosphite, tris(2,4-ditertiary butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetraphenyl dipropylene glycol diphosphite, 4,4-butylidene bis(3-methyl-6-tertiary butylphenyl ditridecyl phosphite), tetra(C12 to C1 5 alkyl)-4,4-isopropylidenediphenyl diphosphite, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-ditertiarybutyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,4,8,10-tetrakis(1,1-dimethylethyl)-6-[(2-ethylhexyl)oxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, bis(decyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, etc.

Examples of commercially available phosphite antioxidants include "IRGAFOS 168" and "IRGAFOS 168FF" manufactured by BASF, and "ADK STAB PEP-8", "ADK STAB PEP-36", "ADK STAB HP-10", "ADK STAB 2112", "ADK STAB 2112RG", "ADK STAB 1178", "ADK STAB 1500", "ADK STAB C", "ADK STAB 135A", "ADK STAB 3010", and "ADK STAB 135A" manufactured by ADEKA CORPORATION. TPP" and Johoku Chemical Industry Co., Ltd.'s "JP-360", "JP-351", "JP-3CP", "JP-308E", "JPE-308E", "JP-310", "JP-312L", "JP-333E", "JPM-308", "JPM-311", "JPM-313", "JPP-100", "JA-805", "JPH-1200", "JPP-88", "JPE-10", "JPE-13R", "JP-318E", "JPP-2000PT", "JP-650", "JPH-3800", etc.

Examples of the sulfur-based antioxidant include didodecyl 3,3-thiodipropionate, ditridecyl 3,3-thiobispropionate, dioctadecyl 3,3-thiodipropionate, and pentaerythritol tetrakis[3-(dodecylthio)propionate].

Examples of commercially available sulfur-based antioxidants include "IRGANOX PS800FL" and "IRGANOX PS802FL" manufactured by BASF, "ADEKA STAB AO-412S" and "ADEKA STAB AO-503" manufactured by ADEKA CORPORATION, "KEMINOX PLS" manufactured by Chemipro Chemical Co., Ltd., and "SUMILIZER TP-D" manufactured by Sumitomo Chemical Co., Ltd.

The amount of the antioxidant used in the active energy ray-curable composition is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 5 parts by mass, and particularly preferably in the range of 0.5 to 3 parts by mass, from the viewpoint of obtaining sufficient heat resistance.

As the other additives, inorganic fillers are preferably used to adjust the refractive index and thermal expansion coefficient. Examples of the inorganic fillers include silica fine particles, zirconia fine particles, other fine particles, etc., and each of these can be used independently, or in combination of two or more. The particle size of the inorganic filler is preferably 1000 nm or less, more preferably 500 nm or less, and particularly preferably 100 nm or less.

Commercially available products of the silica fine particles include, for example, "Methanol Silica Sol", "MA-ST-M", "MA-ST-L", "IPA-ST", "IPA-ST-L", "IPA-ST-ZL", "IPA-ST-UP", "EG-ST", "NPC-ST-30", "PGM-ST", "DMAC-ST", "MEK-ST-40", "MEK-ST-L", "MEK-ST-ZL", "MEK-ST-UP", and MIBK-ST”, “MIBK-ST-L”, “CHO-ST-M”, “EAT-ST”, “PMA-ST”, “TOL-ST”, “MEK-AC-2140Z”, “MEK-AC-4130Y”, “MEK-AC -5140Z”, “MIBK-AC-2140Z”, “MIBK-SD-L”, “PGM-AC-2140Y”, “PGM-AC-4140Y”, “MEK-EC-2130Y”, “Seahoster” manufactured by Nippon Shokubai Co., Ltd. KE-E10", "SeaHoster KE-E30", "SeaHoster KE-E150", "SeaHoster KE-W10", "SeaHoster KE-W30", "SeaHoster KE-W50", "SeaHoster KE-P10", "SeaHoster KE-P30", "SeaHoster KE-P50", "SeaHoster KE-P100", "SeaHoster KE-P150", "SeaHoster KE-P250", "SeaHoster KE-S10", "SeaHoster KE-S30", "SeaHoster KE-S50", "SeaHoster KE-S100", "SeaHoster KE-S150", "SeaHoster Examples include "KE-S250" manufactured by Shin-Etsu Chemical Co., Ltd., "QSG-10", "QSG-30", "QSG-100", and "QSG-170" manufactured by Shin-Etsu Chemical Co., Ltd., "Admanano YA010C", "YA050C", and "YA100C" manufactured by Admatechs Co., Ltd., and "DLSB-001" and "DLSB-002" manufactured by Daiken Chemical Co., Ltd.

Examples of commercially available zirconia fine particles include "ZHR-101", "ZHR-103", and "ZHR-200" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "Zircostar ZP-153" and "Zircostar HR-101" manufactured by Nippon Shokubai Co., Ltd., "SZR-W", "SZR-M", "SZR-CW", "SZR-CM", "SZR-KM", and "SZR-K" manufactured by Sakai Chemical Industry Co., Ltd., "DLZ-001", "DLZ-007", "DLZ-003U", "DLM-001", and "DLM-002" manufactured by Daiken Chemical Industry Co., Ltd., "ZSL-10A", "ZSL-10T", "ZSL-20N", and "ZSL-00014" manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., "Zirconeo-Cw" and "Zirconeo-Ck" manufactured by ITEC Co., Ltd., and "TZP-103" manufactured by Taisei Kako Co., Ltd.

Examples of commercially available products of the other fine particles include titania fine particles such as "TTP-113" and "TTP-1132" manufactured by Taisei Chemical Industry Co., Ltd., barium titanate fine particles such as "DLB-001", "DLB-002", and "DLB-003" manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., antimony tin oxide fine particles such as "DLAT-001" manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., and indium tin oxide fine particles such as "DLIT-001" manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.

The cured product of the present invention can be obtained, for example, 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 commonly 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 100 to 10,000 mJ/cm ² , and more preferably 300 to 8,000 mJ/cm ^2. By setting the cumulative light amount within the above range, poor curing due to insufficient light amount and deterioration of the cured product due to excessive light amount can be suppressed.

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

From the viewpoint of suppressing chromatic aberration, the Abbe number νD of the cured product is preferably 53 or more, and more preferably in the range of 55 to 60.

The refractive index nD of the cured product at a wavelength of 589 nm is preferably 1.48 or more, and more preferably in the range of 1.49 to 1.55.

The laminate of the present invention has a resin layer made of the cured product and an inorganic layer. If necessary, it may also have a substrate.

The inorganic layer is a layer made of an inorganic compound, and generally has functions such as anti-reflection and scratch resistance.

Examples of the inorganic compounds include metal oxides, complex oxides, metal nitrides, metal fluorides, complex fluorides, silicon oxides, silicon nitrides, and mixtures thereof.

Examples of the metals include lithium, sodium, magnesium, aluminum, titanium, yttrium, indium, tin, zirconium, niobium, cerium, hafnium, and tantalum.

When the inorganic layer is used as an anti-reflective coating layer, the anti-reflective coating layer may be a single layer, or may have a low refractive index layer and a high refractive index layer. In addition, each of the low refractive index layer and the high refractive index layer may be one layer or multiple layers. The stacking order of the low refractive index layer and the high refractive index layer is not particularly limited.

Examples of inorganic compounds used in the high refractive index layer include lanthanum titanate ( _LaTiO3 ), zirconium oxide ( _ZrO2 ), titanium oxide ( _TiO2 ), tantalum oxide ( _Ta2O5 ), niobium oxide ( _Nb2O5 ), hafnium oxide ( _HfO2 ), _cerium oxide ( _CeO2 ), _yttrium oxide ( _Y2O3 ), and mixtures thereof _.

Examples of the inorganic compound used in the low refractive index layer include magnesium fluoride (MgF ₂ ), silicon dioxide (SiO ₂ ), aluminum fluoride (AlF ₃ ), and mixtures thereof.

The inorganic layer may be formed by depositing a film on the surface of the resin layer. The method for depositing the inorganic layer is not particularly limited, and any known deposition method can be used as appropriate, but it is preferable to deposit the film by physical vapor deposition (PVD) or chemical vapor deposition (CVD).

From the viewpoint of consistency and simplification of the film formation process, it is more preferable to use physical vapor deposition (PVD), such as vacuum deposition, ion plating, and sputtering.

For example, the vacuum deposition can be performed using a resistance heating method, a high-frequency induction heating method, an electron beam heating method, etc.

The sputtering may be DC sputtering or RF sputtering, or may be magnetron sputtering or ion beam sputtering. In addition, it may be a parallel plate target system or a facing target system. In addition, examples of gases to be introduced into the vacuum chamber include argon, krypton, oxygen, nitrogen, etc., and each may be used alone or in a mixture of two or more types.

The thickness of the inorganic layer can be adjusted as appropriate depending on the intended function, but if the intended function is anti-reflection, a thickness in the range of 10 nm to 5,000 nm is preferred, and from the standpoint of the film strength of the inorganic layer and productivity, a thickness in the range of 100 nm to 2,000 nm is more preferred, and a thickness in the range of 250 nm to 1,000 nm is particularly preferred.

Examples of the substrate include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resins such as polypropylene, polyethylene, and polymethylpentene; cellulose resins such as cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, and cellulose nitrate; acrylic resins such as polymethyl methacrylate; vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl acetate copolymer; polystyrene; polyamide; polycarbonate nate; polysulfone; polyethersulfone; polyetheretherketone; polyimide-based resins such as polyimide and polyetherimide; resin films such as norbornene-based resins (e.g., "ZEONOR" manufactured by Nippon Zeon Co., Ltd.), modified norbornene-based resins (e.g., "ARTON" manufactured by JSR Corporation), and cyclic olefin copolymers (e.g., "Apel" manufactured by Mitsui Chemicals, Inc.); semiconductor wafers such as silicon, silicon carbide, silicon nitride, sapphire, aluminum nitride, gallium phosphide, gallium arsenide, indium phosphide, and gallium nitride; and glasses such as quartz glass, borosilicate glass, soda-lime glass, silicate glass, and optical glass (crown glass, flint glass).

Methods for applying the active energy ray-curable composition of the present invention to the film substrate include, for example, die coating, microgravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, dip coating, spinner coating, brush coating, solid coating using a silk screen, wire bar coating, flow coating, dispenser, inkjet printing, screen printing, offset printing, etc.

The lens of the present invention is made of the laminate.

Examples of the manufacturing method of the lens include a method in which an active energy ray-curable resin composition is applied onto a wafer or a sensor substrate, and the active energy ray-curable resin composition is cured by irradiating it with active energy rays using a mold or the like to form a desired shape, and then the uncured portions are washed away with an organic solvent, and an inorganic layer is formed on the surface of the cured product of the active energy ray-curable resin composition by physical vapor deposition or the like, and the resulting laminate is cut into the desired shape.

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

The present invention will be specifically explained below with examples and comparative examples.

In this example, the weight average molecular weight (Mw) was measured using gel permeation chromatography (GPC) under the following conditions:

Measuring device: Tosoh Corporation HLC-8220
Column: Tosoh Corporation guard column _HXL -H
+ Tosoh Corporation TSKgel G5000HXL
+ Tosoh Corporation TSKgel G4000HXL
+ Tosoh Corporation TSKgel G3000HXL
+ Tosoh Corporation TSKgel G2000HXL
Detector: RI (differential refractometer)
Data processing: Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40°C
Solvent Tetrahydrofuran
Flow rate: 1.0 ml/min. Standard: polystyrene Sample: 100 μl of a tetrahydrofuran solution containing 0.4% by mass of resin solids filtered through a microfilter

(Synthesis Example 1: Production of Hyperbranched Polymer Compound (A-1) Having Acryloyl Group)
In a reaction vessel equipped with a partial condenser, a thermometer, and a stirring rod, 134 parts by mass of trimethylolpropane, 2,500 parts by mass of dimethylolpropionic acid, and 15 parts by mass of paratoluenesulfonic acid were charged and stirred at 100°C to obtain a homogeneous liquid mixture melt. Then, 100 parts by mass of toluene was poured in, and the temperature was raised to 140°C, and water generated while refluxing toluene was distilled out of the system by azeotropy. Then, the reaction was continued for 3 hours at 140°C, and toluene was distilled out of the system to obtain a hyperbranched polyester polyol (a). The weight average molecular weight of the hyperbranched polyester polyol (a) was 1,800.

Next, 100 parts by mass of hyperbranched polyester polyol (a), 80 parts by mass of acrylic acid, 0.26 parts by mass of methoquinone, 1.70 parts by mass of paratoluenesulfonic acid, and 120 parts by mass of toluene were charged into a reaction kettle equipped with a partial condenser, a thermometer, and a stirring rod, and water was removed from the system by azeotropy while refluxing toluene at a reaction temperature of 110°C. Next, the reaction was continued at 110°C for 5 hours, after which the reaction mixture was neutralized with a 20% by mass aqueous solution of sodium hydroxide and washed three times with saline. Finally, toluene was distilled under reduced pressure to remove it from the system, and a hyperbranched polymer compound (A-1) having an acryloyl group was obtained. The weight average molecular weight of this hyperbranched polymer compound (A-1) having an acryloyl group was 2,600. In addition, the average number of functional groups was 18.

(Example 1: Preparation of active energy ray-curable resin composition (1))
Into a 200 mL brown bottle, 35 parts by mass of the hyperbranched polymer compound (A-1) having an acryloyl group obtained in Synthesis Example 1, 20 parts by mass of polyethylene glycol diacrylate ("A-400" manufactured by Shin-Nakamura Chemical Co., Ltd.), 45 parts by mass of an aliphatic urethane acrylate ("EB8402" manufactured by Daicel-Allnex Corporation), and 1 part by mass of a photopolymerization initiator ("Runtecure 1104" manufactured by Runtech Chemical Co., Ltd.) were blended, and the mixture was heated at 60° C. for 30 minutes to dissolve uniformly and degassed, thereby obtaining an active energy ray-curable composition (1).

(Example 2: Preparation of active energy ray-curable resin composition (2))
In a 200 mL brown bottle, 35 parts by mass of the hyperbranched polymer compound (A-1) having an acryloyl group obtained in Synthesis Example 1, 65 parts by mass of an aliphatic urethane acrylate ("UA-TMC4" manufactured by Kyoeisha Chemical Co., Ltd.), and 1 part by mass of a photopolymerization initiator ("Runtecure 1104" manufactured by Runtech Chemical Co., Ltd.) were blended, and the mixture was heated at 60° C. for 30 minutes to dissolve uniformly and degassed, thereby obtaining an active energy ray-curable composition (1).

(Example 3: Preparation of active energy ray-curable resin composition (3))
Into a 200 mL brown bottle, 35 parts by mass of the hyperbranched polymer compound (A-1) having an acryloyl group obtained in Synthesis Example 1, 65 parts by mass of an aliphatic urethane acrylate ("UA-TMC5" manufactured by Kyoeisha Chemical Co., Ltd.), and 1 part by mass of a photopolymerization initiator ("Runtecure 1104" manufactured by Runtech Chemical Co., Ltd.) were blended, and the mixture was heated at 60° C. for 30 minutes to dissolve uniformly and degassed, thereby obtaining an active energy ray-curable composition (1).

(Comparative Example 1: Preparation of active energy ray curable resin composition (4))
In a 200 mL brown bottle, 100 parts by mass of the hyperbranched polymer compound (A-1) having an acryloyl group obtained in Synthesis Example 1 and 1 part by mass of a photopolymerization initiator (Runtech Chemical Co., Ltd.'s "Runtecure 1104") were mixed and heated at 60°C for 30 minutes to dissolve uniformly, and then degassed, thereby obtaining an active energy ray-curable resin composition (4).

The following 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]
The active energy ray curable compositions obtained in the Examples and Comparative Examples were poured into a triangular prism mold (thickness 5 mm, length of one side 10 mm) and irradiated with 3,000 mJ/ ^cm2 of ultraviolet light using a belt conveyor type ultraviolet irradiation device (120 W metal halide lamp) manufactured by Eye Graphics Co., Ltd. to produce a triangular prism. The refractive indexes of the obtained triangular prisms at 25°C for the d-line, F-line, and C-line were measured using a Kalnew precision refractometer "KPR-3000" manufactured by Shimadzu Corporation. A matching liquid having a refractive index (n _d ) closest to the refractive index (n _d ) of the cured product was appropriately selected and used.

[Calculation method of Abbe number]
The Abbe number (ν _d ) was calculated according to the following formula using the refractive indices of the d line, F line, and C line measured by the above-mentioned [Method of measuring refractive index].

[Method of measuring transmittance]
The active energy ray curable compositions obtained in the Examples and Comparative Examples were dropped onto a glass plate that had been subjected to a release treatment with octadecyltrichlorosilane, and 1 mm thick shim plates were placed on the left and right of the oil droplet as spacers, and the oil droplet was then sandwiched between two glass plates that had also been subjected to a release treatment with octadecyltrichlorosilane. The oil droplet of the active energy ray curable composition sandwiched between the two glass plates was irradiated with an irradiation intensity of 50 mW/cm ² and an accumulated light amount of 8000 mJ/cm ² using a UV-LED irradiation device "LHPUV365/2501" manufactured by Iwasaki Electric Co., Ltd., to obtain a coin-shaped cured product with a thickness of about 1 mm. The obtained coin-shaped cured product was heated in a blower oven at 100°C for 20 minutes, and then the initial transmittance at a wavelength of 410 nm was measured using a UV-visible near-infrared spectrophotometer "V-770" manufactured by JASCO Corporation.

[Method for measuring transmittance after heat resistance test]
The coin-shaped cured product measured by the transmittance measurement method described above was (1) heated at 175°C for 10 minutes in a fan oven, and then the transmittance at a wavelength of 410 nm was measured using a UV-Visible-Near-Infrared Spectrophotometer "V-770" manufactured by JASCO Corporation, with the transmittance set as transmittance after heat resistance test 1. The heating temperature was set to 175°C in accordance with the reflow process of low-temperature molten solder and normal molten solder.

[Method of evaluating cracks after reflow processing]
The active energy ray curable compositions obtained in the examples and comparative examples were dropped onto a cover glass that had been subjected to an adhesion treatment with a silane coupling agent "KBM-5103" manufactured by Shin-Etsu Chemical Co., Ltd., and shaped using a lens replica, and then provisionally cured by irradiation with an irradiation intensity of 50 mW/cm ² and an accumulated light quantity of 450 mJ/cm ² using a UV-LED irradiation device "LHPUV365/2501" manufactured by Iwasaki Electric Co., Ltd. After releasing the lens replica, a development treatment was performed using propylene glycol monomethyl ether to remove uncured resin composition. Furthermore, after main curing with an accumulated light quantity of 7,550 mJ/cm ² , a wafer-level lens was obtained by post-baking for 90 minutes at 100°C using a blower oven. The obtained wafer-level lens was sputtered using a three-target magnetron sputtering device "HSR-522" manufactured by Shimadzu Corporation under the conditions of target SiO ₂ , introduced gas as argon, gas flow rate of 15 sccm, room temperature of 25°C, and sputtering time of 40 min, to obtain a laminate in which a silicon oxide thin film having a thickness of 0.5 μm was laminated on the surface of the cured product. The surface of the laminate was observed with a microscope "VHX900" manufactured by Keyence Corporation, and the initial appearance of the laminate was evaluated according to the following criteria. Next, a heat treatment was performed at 175°C for 5 minutes using a blower oven, and the surface of the laminate was observed with a microscope "VHX900" manufactured by Keyence Corporation, and the appearance of the laminate after heat resistance was evaluated according to the following criteria.
◯: No cracks were observed in the sputtered film.
×: Cracks occurred in the sputtered film.

[Method for evaluating cracks after moist heat resistance test]
A wafer level lens was produced in the same manner as in the lens production procedure described in the evaluation method for cracks after reflow treatment, and a wafer level lens was obtained. The obtained wafer level lens was subjected to a moist heat resistance test for 200 hours at a temperature of 85°C and a relative humidity of 85% using an environmental tester (SH-222 manufactured by Espec). After the test, the lens was observed using a microscope "VHX900" manufactured by Keyence Corporation and a laser microscope "OLS5000" manufactured by Olympus Corporation, and evaluated according to the following criteria.

5: No cracks were observed in the sputtered film.
4: One crack occurred in the sputtered film.
3: 2 to 5 cracks occurred in the sputtered film.
2: 6 to 10 cracks occurred in the sputtered film.
1: 10 or more cracks occurred in the sputtered film.

The evaluation results in Table 1 reveal that the cured products formed from the active energy ray-curable compositions of the present invention in Examples 1 to 3 have a high Abbe number and high heat yellowing resistance, and are crack resistant even after reflow treatment and moist heat resistance tests. In addition, the lens samples of Examples 1 to 3 were free of warping, cracks, or cracks after curing, and had good appearances.

On the other hand, Comparative Example 1 is an example of an active energy ray-curable composition that does not contain the component (B) specified in the present invention, but cracks occurred after reflow treatment, confirming that the crack resistance is insufficient. Comparative Example 2 is an example of an active energy ray-curable composition that does not contain the component (A) specified in the present invention, but cracks occurred after reflow treatment, confirming that the crack resistance is insufficient.

Claims (4)

A lens comprising a laminate having an inorganic layer and a resin layer made of a cured product of an active energy ray-curable resin composition comprising: (A) a hyperbranched polymer compound having a hyperbranched structure and six or more (meth)acryloyl groups in one molecule; and (B) an aliphatic urethane (meth)acrylate . 2. The lens according to claim 1, wherein the hyperbranched polymer compound (A) is at least one selected from the group consisting of compounds having a dendrimer structure, compounds having a hyperbranched structure, and compounds having a star structure. 3. The lens according to claim 1, wherein the cured product has an Abbe number vD of 53 or more. 3. The lens according to claim 1, wherein the refractive index nD of the cured product at a wavelength of 589 nm is 1.48 or more.