TW202130668A - Active energy ray-curable resin composition, cured product, multilayer body and lens - Google Patents

Abstract

The present invention addresses the problem of providing: an active energy ray-curable resin composition which enables a multilayer body having a resin layer and an inorganic layer to have excellent cracking resistance that is capable of suppressing the occurrence of a crack in the inorganic layer; a cured product of this active energy ray-curable resin composition; a multilayer body; and a lens which is formed of this multilayer body. The inventors have solved the above-described problem by using an active energy ray-curable resin composition for the formation of a resin layer of a multilayer body that has the resin layer and an inorganic layer, said active energy ray-curable resin composition being characterized by containing (A) a hyperbranched polymer compound that has a (meth)acryloyl group.

Description

Active energy ray curable resin composition, cured product, laminate and lens

The present invention relates to an active energy ray curable resin composition, cured product, laminated body and lens.

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 are widely used in inks, paints, and coatings. The fields of cloth agents, adhesives, optical components, etc. Among them, in the field of the optical member, it can be preferably used as a resin for lenses used in smart phones or in-vehicle cameras. As a molding method of the lens resin, since the thinning of the lens module and the improvement of production efficiency are considered, the manufacturing process using optical imprinting is actively studied. The photoimprint is to apply uncured resin to a substrate such as a wafer, and then to transfer the shape by sandwiching it with a lens mold. By performing photocuring, hundreds of crystals can be processed at a time. The method of round lens forming.

As the resin used for the photoimprint, a curable resin composition containing urethane (meth)acrylate is known (for example, refer to Patent Document 1). However, after the lens is formed, anti-reflection is used. When the film is used to cover the upper layer of the lens, there are problems such as cracks during heat treatment such as reflow.

Therefore, there is a need for a resin layer forming material that has excellent crack resistance that can suppress the generation of cracks in the inorganic layer during reflow treatment after forming an inorganic layer such as an anti-reflection film. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2008/149766

[The problem to be solved by the invention]

The problem to be solved by the present invention is to provide an active energy ray-curable resin composition for forming a resin layer having excellent crack resistance that can suppress the generation of cracks in the inorganic layer in a laminate comprising a resin layer and an inorganic layer. The cured product of the active energy ray-curable resin composition, a laminate, and a lens including the laminate. [Means to solve the problem]

The inventors of the present invention have made diligent studies to solve the above-mentioned problems. As a result, they have found that the use of an active energy ray-curable resin composition containing a multi-branched polymer compound having a (meth)acryloyl group can solve the above-mentioned problem. Problem, and completed the present invention.

That is, the present invention relates to an active energy ray-curable resin composition for forming a resin layer, a cured product of the active energy ray-curable resin composition, a laminate, and a lens including the laminate, the resin layer The active energy ray curable resin composition for forming is an active energy ray curable resin composition for forming a resin layer including a laminate of a resin layer and an inorganic layer, and is characterized in that the active energy ray curable resin composition contains (Meth)acrylic multi-branched polymer compound (A). [Effects of the invention]

The active energy ray-curable resin composition of the present invention can suppress the generation of cracks in the inorganic layer in a laminate including a resin layer and an inorganic layer, and therefore can be preferably used in the manufacture of lenses by light imprinting.

The active energy ray-curable resin composition of the present invention is characterized by containing a multi-branched polymer compound (A) having a (meth)acryloyl group.

In addition, in the present invention, "(meth)acryloyl group" means an allyl group and/or methacryloyl group. In addition, "(meth)acrylate" means acrylate and/or methacrylate. Furthermore, "(meth)acrylic acid" means acrylic acid and/or methacrylic acid.

Examples of the multi-branched polymer compound (A) having a (meth)acryloyl group include compounds having a dendrimer structure (dendrimer structure) (hereinafter sometimes referred to as "dendrimer"). "Hyperbranched polymer"), compounds with a hyperbranched structure (hyperbranched structure) (hereinafter sometimes referred to as "hyperbranched" or "hyperbranched polymer"), compounds with a star-shaped structure, etc. .

Commercial products of the compound having a dendrimer structure include, for example, "Viscoat #1000LT" manufactured by Osaka Organic Chemical Industry Co., Ltd., and "Milamo" manufactured by MIWON Co., Ltd. (Miramer) SP1106". These compounds having a dendrimer structure may be used alone, or two or more of them may be used in combination.

Commercial products of the compound having a hyperbranched structure include, for example, "CN2302", "CN2303", and "CN2304" manufactured by Arkema; and "Photomer 5500" manufactured by IGM. "Wait. These compounds having a hyperbranched structure may be used alone, or two or more of them may be used in combination.

In terms of obtaining an active energy ray-curable resin composition having excellent crack resistance capable of suppressing cracks in the inorganic layer, the average (meth)propylene per molecule of the multi-branched polymer compound (A) The base number is more preferably in the range of 6 to 64, and particularly preferably in the range of 10 to 32.

In order to obtain an active energy ray curable resin composition having excellent crack resistance capable of suppressing the generation of cracks in the inorganic layer, the weight average molecular weight (Mw) of the multi-branched polymer compound (A) is preferably 500 The range of ~30,000 is more preferably the range of 1,000 to 10,000. Furthermore, in the present invention, the weight average molecular weight (Mw) represents a value measured by a gel permeation chromatography (GPC) method.

The viscosity of the multi-branched 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 addition, in the present invention, viscosity means a value measured with an E-type viscometer.

The method for producing the multi-branched polymer compound (A) is not particularly limited, and it can be produced by a suitably known method. For example, the divergent method in which the molecules are bonded to the central core molecule successively to form branches, the convergent method in which the pre-synthesized branch part is bonded to the core molecule, and the use of one molecule including two A method of synthesizing the branching part of more than one reaction point B and the monomer ABx having the connecting part of the other reaction point A in one stage. Among them, the divergence method is preferred. For example, it is preferred to manufacture by the following method of esterification of a polyol with a compound having one or more carboxyl groups and two or more hydroxyl groups to obtain a multi-branched poly The ester polyol then reacts the terminal hydroxyl group with (meth)acrylic acid.

When the entire active energy ray-curable resin composition for resin layer formation is 100 parts by mass, the multi-branched polymer compound in the active energy ray-curable resin composition for resin layer formation of the present invention ( The content of A) is preferably 1 part by mass to 80 parts by mass, and more preferably 5 parts by mass to 45 parts by mass in terms of improving crack resistance, and if it is 10 parts by mass to 35 parts by mass, the crack resistance is further improved , Therefore particularly good.

Examples of the polyol include glycerin, trimethylolpropane, ditrimethylolpropane, trimethylolethane, ditrimethylolethane, and tris(2-hydroxyethyl) Isocyanurate, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol, sorbitol, mannitol, and these alkylene oxide adducts or caprolactone adducts, etc. These polyols may be used alone, or two or more of them may be used in combination.

As the compound having one or more carboxyl groups and two or more hydroxyl groups, for example, 2,3-dihydroxypropionic acid, 2,2-dimethylolpropionic acid, and 2,2-dimethylolbutane may be mentioned. 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-methylbenzene Formic 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 their derivatives, etc. These compounds may be used singly, or two or more of them may be used in combination.

As the multi-branched polyester polyol, in addition to the esterification reaction of a polyol with a compound having one or more carboxyl groups and two or more hydroxyl groups as described above, commercially available products can also be used.

Examples of commercially available products of the multi-branched polyester polyol include: "BOLTORN H20", "BOLTORN H30", and "BOLTORN H20" manufactured by Perstorp. ) H40", "BOLTORN H311", "BOLTORN H2003", "BOLTORN H2004", "BOLTORN P500", "BOLTORN P501", " "BOLTORN P1000" and so on.

As the active energy ray-curable resin composition of the present invention, a photopolymerization initiator may be contained as necessary.

As the photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyl (Ethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-di Phenylethane-1-one, diphenyl (2,4,6-trimethoxybenzyl) phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide, bis (2,4,6-Trimethylbenzyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2- Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone and the like.

Examples of commercially available products of the other photopolymerization initiators include "Omnirad-1173", "Omnirad-184", and "Omnirad" -127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907" ", "Omnirad (Omnirad)-4265", "Omnirad (Omnirad)-1000", "Omnirad (Omnirad)-651", "Omnirad (Omnirad)-TPO", "Omnirad (Omnirad)-819", "Omnirad (Omnirad)-2022", "Omnirad (Omnirad)-2100", "Omnirad (Omnirad)-754", "O "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM); "Kayacure-DETX", "Kayacure-MBP", "Kayacure-DMBI", "Kayacure-EPA", "Kayacure-OA" (Nippon Kayaku Co., Ltd. Manufacturing); "Vicure-10", "Vicure-55" (manufactured by Stauffer Chemical); "Trigonal P1" (manufactured by Akzo) ); "SANDORAY 1000" (manufactured by SANDOZ); "DEAP" (manufactured by APJOHN); "Quantacure-PDO" , "Quantacure-ITX", "Quantacure-EPD" (manufactured by Ward Blenkinsop); "Runtecure-1104" (Hua Titanium (manufactured by Runtec), etc. These photopolymerization initiators may be used alone, or two or more of them may be used in combination.

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

In addition, the photopolymerization initiator may 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.

In addition, as the active energy ray-curable resin composition of the present invention, if necessary, it may contain a (meth)acrylic compound having a carbonate structure, a (meth)acrylic compound having a cyclic structure, or one or more compounds in one molecule. Two (meth)acrylic groups and a compound having an alkanediol structure in one molecule.

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

As the polycarbonate polyol, for example, a reaction product of a compound having two or more hydroxyl groups and a carbonate ester, and the like can be cited.

As the compound having two or more hydroxyl groups, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol can be used Alcohol, 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 -Propylene glycol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolpropane, trimethylolmethane Ethane, glycerin, etc. These compounds may be used singly, or two or more of them may be used in combination.

As said carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. are mentioned, for example. These compounds may be used singly, or two or more of them may be used in combination.

As the (meth)acrylate, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate can be used, for example Base) isobutyl acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, octyloxy polyacrylate Ethylene glycol-polypropylene glycol mono(meth)acrylate, lauryloxy polyethylene glycol mono(meth)acrylate, stearyloxypolyethylene glycol mono(meth)acrylate, phenoxy polyethylene Glycol mono(meth)acrylate, phenoxy polyethylene glycol-polypropylene glycol mono(meth)acrylate, nonylphenoxy polypropylene glycol mono(meth)acrylate, nonylphenoxy poly( Ethylene glycol-propylene glycol) mono(meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, etc. These (meth)acrylates may be used alone, or two or more of them may be used in combination.

In addition, as commercially available products of the (meth)acrylic compound having a carbonate structure, for example, "UH-100DA" and "UM-90(1/3)DA" manufactured by Ube Industries Co., Ltd. , "UM-90 (1/1) DA", "UM-90 (3/1) DA", "UH-100DM", "UM-90 (1/3) DM", "UM-90 (1/ 1) DM", "UM-90 (3/1) DM", etc.

As the (meth)acrylic compound having a cyclic structure, for example, a monocyclic alkane structure, a benzene ring, a tricyclodecane structure, a dicyclopentenyl structure, an isobornyl structure, and an oxygen atom as a heterocyclic structure can be used. (Meth)acrylic compounds such as heterocyclic structures of atoms. These compounds may be used singly, or two or more of them may be used in combination.

As the (meth)acrylic compound having the monocycloalkane structure, for example, cyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol monoacrylate, and the like can be used. These compounds may be used singly, or two or more of them may be used in combination.

As the (meth)acrylic compound having a benzene ring, for example, benzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxy Base polyethylene glycol (meth)acrylate and the like. These compounds may be used singly, or two or more of them may be used in combination.

Examples of the (meth)acrylic compound having a tricyclodecane (dicyclopentyl) structure include dicyclopentyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, Dimethylol tricyclodecane di(meth)acrylate, tricyclodecanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, etc. These compounds may be used singly, or two or more of them may be used in combination.

Examples of the (meth)acrylic compound having a dicyclopentenyl structure include dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and the like. These compounds may be used singly, or two or more of them may be used in combination.

Examples of the (meth)acrylic compound having an isobornyl structure include isobornyl (meth)acrylate, isobornyl di(meth)acrylate, and the like. These compounds may be used singly, or two or more of them may be used in combination.

As the (meth)acrylic compound having a heterocyclic structure having an oxygen atom as a heteroatom, for example, cyclic trimethylolpropane formal acrylate, (meth)acrylic acid (2-methyl- 2-Ethyl-1,3-dioxol-4-yl) methyl ester, (3-ethyloxetan-3-yl) methyl (meth)acrylate, (methyl) Tetrahydrofurfuryl acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, etc. These compounds may be used singly, or two or more of them may be used in combination.

As the compound having one or two (meth)acrylic groups in one molecule and an alkanediol structure in one molecule, it must have one or two (meth)acrylic groups and an alkane in one molecule. Those with diol structure.

Examples of the alkanediol structure include: 1,2-ethylene glycol (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- Butylene glycol, 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, 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- Propylene glycol, 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-butane 2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-decanediol, 2,2-diisobutyl-1,3- Propylene glycol and so on. These alkanediol structures may have only one type in one molecule, or two or more types.

In addition, as a commercially available product of a compound having one or two (meth)acryloyl groups in one molecule and an alkanediol structure in one molecule, for example, "MIWON" manufactured by MIWON "Miramer M170", "Miramer M202", "Miramer M210", "Miramer M216", "Miramer M220", "Mi "Miramer M222", "Miramer M232", "Miramer M280", "Miramer M282", "Miramer M284", "Mi "Miramer M286", "Miramer M2040", "Miramer M231", "Miramer M233", "Miramer M235", "Miramer M235", "Miramer M281" and "Miramer M283"; "NK Ester A-30G" and "NK Ester A-90G" manufactured by Shinnakamura Chemical Industry Co., Ltd. , "NK Ester (NK Ester) A-130G", "NK Ester (NK Ester) AM-30PG", "NK Ester (NK Ester) A-200", "NK Ester (NK Ester) A-400", " "NK Ester (NK Ester) A-600", "NK Ester (NK Ester) APG-100", "NK Ester (NK Ester) APG-200", "NK Ester (NK Ester) APG-400", "NK Ester" (NK Ester) APG-700", "NK Ester (NK Ester) A-PTMG-65", "NK Ester (NK Ester) M-20G", "NK Ester (NK Ester) M-30G", "NK Ester" (NK Ester) M-40G", "NK Ester (NK Ester) M-90G", "NK Ester (NK Ester) M-130G", "NK Ester (NK Ester) M-30PG", "NK Ester (NK Ester) M-30PG", Ester EH-4E", "NK Ester (NK Ester) B-20G", "NK Ester (NK Ester) S-12E", "NK Ester (NK Ester) 2G", "NK Ester (NK Ester) 3G" , "NK Ester (NK Ester) 4G", "NK Ester (NK Ester) 9G", "NK Ester (NK Ester) 14G", "NK Ester (NK Ester) 3PG", "NK Ester (NK Ester) 9PG" ;Kyoeisha Chemical "Light Ester BC", "Light Ester (Light Ester) 130MA", "Light Ester BC", "Light Ester 2EG", "Light Ester" Ester 3EG", "Light Ester 4EG", "Light Ester 9EG", "Light Ester 14EG", "Light Acrylate EC-A", "Light Ester" Acrylate (Light Acrylate) MTG-A", "Light Acrylate (Light Acrylate) EHDG-AT", "Light Acrylate (Light Acrylate) 130A", "Light Acrylate (Light Acrylate) DPM-A", "Wright Acrylate (Light Acrylate) P2H-A", "Light Acrylate (Light Acrylate) P-200A", "Light Acrylate (Light Acrylate) 3EG-A", "Light Acrylate (Light Acrylate) 4EG-A", "Light Acrylate 9EG-A", "Light Acrylate 14EG-A", "Light Acrylate PTMGA-250"; "Fan Keli" manufactured by Hitachi Chemical Co., Ltd. (Fancryl) FA-240A", "Fancryl FA-P240A", "Fancryl FA-P270A", "Fancryl FA-PTG9A", "Fancryl ) FA-400M (100)", "Fancryl FA-240M", "Fancryl FA-PTG9M"; "New Frontier ME" manufactured by First Industrial Pharmaceutical Co., Ltd. -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"; Japaneseization "KAYA" manufactured by Pharmaceutical Co., Ltd. RAD) PEG400DA"; "Biske (Viscoat) #190", "Biske (Viscoat) #MTG", "MPE400A", "MPE550A", "Biske (Viscoat) #310HP" manufactured by Osaka Organic Chemical Industry Co., Ltd. "Wait.

Furthermore, as the active energy ray-curable resin composition of the present invention, urethane (meth)acrylate, epoxy (meth)acrylate, acrylic (meth)acrylate, etc. may be contained as necessary.

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. In addition, in the case of using ultraviolet rays as the active energy rays, the curing reaction by ultraviolet rays can be efficiently performed, and the irradiation can be carried out in an inert gas environment such as nitrogen, or in an air environment.

As a source of ultraviolet light, an ultraviolet lamp is generally used in consideration of practicality and economy. Specifically, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, light-emitting diodes (Light-Emitting Diode, LED), etc. can be cited.

The cumulative light quantity of the active energy rays is not particularly limited, and is preferably 100 mJ/cm ² to 10,000 mJ/cm ² , more preferably 300 mJ/cm ² to 8,000 mJ/cm ² . By setting the accumulated light intensity within the above-mentioned range, it is possible to suppress poor curing caused by insufficient light intensity and deterioration of the cured product caused by excessive light intensity.

Furthermore, the irradiation of the active energy ray may be performed in one stage, or may be performed in more than two stages.

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 55-60.

In addition, 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 and an inorganic layer including the cured product. In addition, if necessary, it may have a base material.

The inorganic layer refers to a layer containing an inorganic compound, and generally has functions such as anti-reflection and scratch resistance.

Examples of the inorganic compound include metal oxides, composite oxides, metal nitrides, metal fluorides, composite fluorides, silicon oxides, silicon nitrides, and mixtures of these.

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

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

As the inorganic compound used in the high refractive index layer, for example, lanthanum titanate (LaTiO ₃ ), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), niobium oxide ( Nb ₂ O ₅ ), hafnium oxide (HFO ₂ ), cerium oxide (CeO ₂ ), yttrium oxide (Y ₂ O ₃ ), and mixtures of these.

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 of these.

The inorganic layer is obtained by forming a film on the surface of the resin layer. The method for forming the inorganic layer is not particularly limited, and a known film forming method can be suitably used, but it is preferably by physical vapor deposition (physical vapor deposition (PVD)) or chemical vapor deposition (chemical vapor deposition). The film is formed by chemical vapor deposition (CVD).

From the viewpoint of consistency and simplification of the film formation step, the film formation method is more preferably to use the physical vapor deposition (PVD), for example, methods such as vacuum vapor deposition, ion plating, and sputtering can be cited.

As the vacuum vapor deposition, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method, etc. can be used.

The sputtering may be direct current (DC) sputtering or radio frequency (RF) sputtering, or magnetron sputtering or ion beam sputtering. In addition, it may be a parallel flat target method or an opposed target method. In addition, as the gas introduced into the vacuum chamber, for example, argon, krypton, oxygen, nitrogen, etc., may be used alone, or two or more of them may be mixed and used.

The film thickness of the inorganic layer can be appropriately adjusted according to the target function. In the case of an anti-reflection function, it is preferably in the range of 10 nm to 5,000 nm. From the viewpoint of the film strength and productivity of the inorganic layer, It is more preferably in the range of 100 nm to 2,000 nm, and particularly preferably in the range of 250 nm to 1,000 nm.

As the substrate, for example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polypropylene, polyethylene, and polymethyl Polyolefin resins such as pentene; cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, phthalate acetate Cellulose resins such as cellulose formate and nitrocellulose; acrylic resins such as polymethyl methacrylate; vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene monovinyl acetate copolymer ; Polystyrene; polyamide; polycarbonate; polysulfide; polyether sulfide; polyetheretherketone; polyimide resins such as polyimine and polyetherimine; norbornene resins "Zeonor" manufactured by Zeon Co., Ltd.), modified norbornene resins (such as "Arton" manufactured by JSR Co., Ltd.), cyclic olefin copolymers ( For example, "APEL" manufactured by Mitsui Chemicals Co., Ltd.) and other resin films; silicon, silicon carbide, silicon nitride, sapphire, aluminum nitride, gallium phosphide, gallium arsenide, indium phosphide, nitride Gallium and other semiconductor wafers; quartz glass, borosilicate glass, soda lime glass, silicate glass, optical glass (crown glass, flint glass) and other glasses.

As a method of applying the active energy ray-curable composition of the present invention to the film substrate, for example, die coating, micro-gravure coating, gravure coating, roll coating, chamfered wheel coating, and gas Knife coating, kiss coating, spray coating, dip coating, spin coating, brush coating, full-surface coating using screen, wire rod coating, flow coating, dispenser, inkjet printing, screen printing Printing, offset printing, etc.

The lens of the present invention includes the laminate.

As a manufacturing method of the lens, for example, coating an active energy ray curable resin composition on a wafer or a sensor substrate, using a mold or the like to irradiate the active energy ray to form a desired shape, and After the active energy ray curable resin composition is cured, the uncured part is washed 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. A method for cutting the obtained laminate into a desired shape, etc.

Examples of the organic solvent include ketone-based solvents such as methyl ethyl ketone, acetone, isobutyl ketone, cyclopentanone, and cyclohexanone; and cyclic ether-based solvents such as tetrahydrofuran, dioxolane, and dioxane. Solvents; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic hydrocarbon systems such as cyclohexane and methylcyclohexane Solvents; alcoholic solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether; alkanediol monoalkyl ether, dialkyldiol monoalkyl ether, dialkylene glycol mono Glycol ether solvents such as alkyl ether acetate, etc. These organic solvents may be used alone, or two or more of them may be used in combination. [Example]

Hereinafter, the present invention will be explained in detail with examples and comparative examples.

In addition, in this example, the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8220 manufactured by Tosoh Co., Ltd. Column: Protection column H _XL- H manufactured by Tosoh Co., Ltd. + TSKgel G5000HXL manufactured by Tosoh Co., Ltd. + TSKgel G4000HXL manufactured by Tosoh Co., Ltd. +TSKgel G3000HXL manufactured by Tosoh Co., Ltd. +TSKgel G2000HXL manufactured by Tosoh Co., Ltd. Detector: RI (differential refractometer) Data processing: SC-8010 manufactured by Tosoh Co., Ltd. Measurement conditions: column temperature 40°C Solvent tetrahydrofuran flow rate 1.0 ml/min Standard: polystyrene sample: obtained by filtering 0.4% by mass of tetrahydrofuran solution in terms of resin solid content using a microfilter (100 μl)

(Synthesis example 1: Production of multi-branched polymer compound (A-1) having acrylic group) A reactor equipped with a partial condenser, a thermometer, and a stirring rod is charged with 134 parts by mass of trimethylolpropane, 2,500 parts by mass of dimethylolpropionic acid, and 15 parts by mass of p-toluenesulfonic acid at 100°C. Stir down to make a uniform liquid mixed melt. Then, 100 parts by mass of toluene was injected, and the temperature was raised to 140° C., while the toluene was refluxed, the generated water was distilled out of the system by azeotropic distillation. Then, after continuing the reaction at 140° C. for 3 hours, toluene was distilled off from the system to obtain a multi-branched polyester polyol (a). The weight average molecular weight of the multi-branched polyester polyol (a) is 1,800.

Then, 100 parts by mass of the multi-branched polyester polyol (a), 80 parts by mass of acrylic acid, 0.26 parts by mass of methoxyphenol, and 1.70 parts by mass of p-toluenesulfonic acid were charged into a reactor equipped with a partial condenser, a thermometer, and a stirring rod. , 120 parts by mass of toluene, while refluxing toluene at a reaction temperature of 110°C, the water was azeotropically removed to the outside of the system. Then, after continuing the reaction at 110° C. for 5 hours, the reaction mixture was neutralized with a 20% by mass aqueous sodium hydroxide solution, and washed with saline water three times. Finally, toluene was distilled under reduced pressure outside the system to obtain a multi-branched polymer compound (A-1) having an acrylic group. The weight average molecular weight of this multi-branched polymer compound (A-1) having an acrylic group was 2,600.

(Example 1: Preparation of active energy ray curable resin composition (1)) In a 200 mL brown bottle, 5 parts by mass of the acryl-based multi-branched polymer compound (A-1) obtained in Example 1 and polycarbonate diacrylate (manufactured by Ube Industries Co., Ltd. "UM -90 (1/3) DA") 85 parts by mass, tricyclodecane dimethanol dimethacrylate ("NK Ester (NK Ester) DCP" manufactured by Shinnakamura Chemical Industry Co., Ltd.) 10 parts by mass, light Polymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Company) 1 part by mass, heated at 60°C for 30 minutes to uniformly dissolve and defoam, thereby obtaining active energy rays Curable composition (1).

(Example 2: Preparation of active energy ray curable resin composition (2)) In a 200 mL brown bottle, 5 parts by mass of the acryl-based multi-branched polymer compound (A-1) obtained in Example 1 and polycarbonate diacrylate (manufactured by Ube Industries Co., Ltd. "UM -90 (1/3) DA") 80 parts by mass, tricyclodecane dimethanol dimethacrylate ("NK Ester (NK Ester) DCP" manufactured by Shinnakamura Chemical Industry Co., Ltd.) 15 parts by mass, light Polymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Company) 1 part by mass, heated at 60°C for 30 minutes to uniformly dissolve and defoam, thereby obtaining active energy rays Curable composition (2).

(Example 3: Preparation of active energy ray curable resin composition (3)) In a 200 mL brown bottle, 10 parts by mass of the acryl-based multi-branched polymer compound (A-1) obtained in Example 1 and polycarbonate diacrylate (manufactured by Ube Industries Co., Ltd. "UM -90 (1/3) DA") 75 parts by mass, tricyclodecane dimethanol dimethacrylate ("NK Ester (NK Ester) DCP" manufactured by Shinnakamura Chemical Industry Co., Ltd.) 15 parts by mass, light Polymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Company) 1 part by mass, heated at 60°C for 30 minutes to uniformly dissolve and defoam, thereby obtaining active energy rays Curable composition (1).

(Example 4: Preparation of active energy ray curable resin composition (4)) In a 200 mL brown bottle, 45 parts by mass of the acryl-based multi-branched polymer compound (A-1) obtained in Example 1 and polycarbonate diacrylate (manufactured by Ube Industries Co., Ltd. "UM -90 (1/3) DA") 55 parts by mass, and 1 part by mass of photopolymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Co., Ltd.), heated at 60°C It is uniformly dissolved and defoamed for 30 minutes, thereby obtaining the active energy ray curable composition (4).

(Example 5: Preparation of active energy ray curable resin composition (5)) In a 200 mL brown bottle, 70 parts by mass of the acryl-based multi-branched polymer compound (A-1) obtained in Example 1 and polycarbonate diacrylate (manufactured by Ube Industries Co., Ltd. "UM -90 (1/3) DA") 30 parts by mass, and 1 part by mass of photopolymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Co., Ltd.), heated at 60°C It is uniformly dissolved and defoamed for 30 minutes, thereby obtaining the active energy ray curable composition (5).

(Example 6: Preparation of active energy ray curable resin composition (6)) In a 200 mL brown bottle, 60 parts by mass of the acryl-based multi-branched polymer compound (A-1) obtained in Example 1 and polycarbonate diacrylate (manufactured by Ube Industries Co., Ltd. "UM -90 (1/3) DA") 40 parts by mass, and 1 part by mass of photopolymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Company), heated at 60°C It is uniformly dissolved and defoamed for 30 minutes, thereby obtaining an active energy ray curable composition (6).

(Example 7: Preparation of active energy ray curable resin composition (7)) In a 200 mL brown bottle, 50 parts by mass of the acryl-based multi-branched polymer compound (A-1) obtained in Example 1 and polycarbonate diacrylate (manufactured by Ube Industries Co., Ltd. "UM -90 (1/3) DA") 50 parts by mass, and 1 part by mass of photopolymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Co., Ltd.), heated at 60°C It dissolves and defoams uniformly in 30 minutes, thereby obtaining the active energy ray curable composition (7).

(Example 8: Preparation of active energy ray curable resin composition (8)) In a 200 mL brown bottle, 35 parts by mass of the multi-branched polymer compound (A-1) having an acrylic group obtained in Example 1 and polycarbonate diacrylate (manufactured by Ube Industries Co., Ltd. "UM -90 (1/3) DA") 65 parts by mass, and 1 part by mass of photopolymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Company), heated at 60°C It is uniformly dissolved and defoamed for 30 minutes, thereby obtaining an active energy ray curable composition (8).

(Example 9: Preparation of active energy ray curable resin composition (9)) In a 200 mL brown bottle, 35 parts by mass of the multi-branched polymer compound (A-1) having an acrylic group obtained in Example 1 and polycarbonate diacrylate (manufactured by Ube Industries Co., Ltd. "UM -90 (1/3) DA") 45 parts by mass, polyethylene glycol diacrylate ("NK Ester (NK Ester) A-400" manufactured by Shinnakamura Chemical Industry Co., Ltd.) 20 parts by mass, photopolymerized Starter (Runtecure 1104 manufactured by Runtec Chemical) 1 part by mass, heated at 60°C for 30 minutes to uniformly dissolve and defoam, thereby obtaining active energy ray curability Composition (9).

(Example 10: Preparation of active energy ray curable resin composition (10)) In a 200 mL brown bottle, 35 parts by mass of a dendritic polymer compound having an acrylic group ("Viscoat (Viscoat) #1000LT" manufactured by Osaka Organic Chemical Industry Co., Ltd.), polycarbonate diacrylate ( "UM-90 (1/3) DA" manufactured by Ube Industries Co., Ltd.) 45 parts by mass, polyethylene glycol diacrylate ("NK Ester (NK Ester) A- manufactured by Shinnakamura Chemical Industry Co., Ltd.) 400") 20 parts by mass, 1 part by mass of the photopolymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Company), heated at 60°C for 30 minutes to uniformly dissolve and desorb Foam, thereby obtaining the active energy ray curable composition (10).

(Example 11: Preparation of active energy ray curable resin composition (11)) In a 200 mL brown bottle, 35 parts by mass of a hyperbranched polymer compound ("CN2302" manufactured by Arkema) and polycarbonate diacrylate (Ube Kosan Co., Ltd.) Manufactured "UM-90 (1/3) DA") 45 parts by mass, and polyethylene glycol diacrylate ("NK Ester (NK Ester) A-400" manufactured by Shinnakamura Chemical Industry Co., Ltd.) 20 parts by mass , 1 part by mass of photopolymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Company), heated at 60°C for 30 minutes to uniformly dissolve and defoam, thereby obtaining activity Energy ray curable composition (11).

(Example 12: Preparation of active energy ray curable resin composition (12)) In a 200 mL brown bottle, 35 parts by mass of a hyperbranched polymer compound ("CN2303" manufactured by Arkema), polycarbonate diacrylate (Ube Kosan Co., Ltd.) Manufactured "UM-90 (1/3) DA") 45 parts by mass, and polyethylene glycol diacrylate ("NK Ester (NK Ester) A-400" manufactured by Shinnakamura Chemical Industry Co., Ltd.) 20 parts by mass , 1 part by mass of photopolymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Company), heated at 60°C for 30 minutes to uniformly dissolve and defoam, thereby obtaining activity Energy ray curable composition (12).

(Example 13: Preparation of active energy ray curable resin composition (13)) In a 200 mL brown bottle, 35 parts by mass of a hyperbranched polymer compound having an acrylic group ("CN2304" manufactured by Arkema) and polycarbonate diacrylate (Ube Industries Co., Ltd.) were blended. Manufactured "UM-90 (1/3) DA") 45 parts by mass, and polyethylene glycol diacrylate ("NK Ester (NK Ester) A-400" manufactured by Shinnakamura Chemical Industry Co., Ltd.) 20 parts by mass , 1 part by mass of photopolymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Company), heated at 60°C for 30 minutes to uniformly dissolve and defoam, thereby obtaining activity Energy ray curable composition (13).

(Comparative example 1: Preparation of active energy ray curable resin composition (R1)) In a 200 mL brown bottle, 81 parts by mass of polycarbonate diacrylate ("UM-90 (1/3) DA" manufactured by Ube Industries Co., Ltd.), tricyclodecane dimethanol dimethacrylate ( "NK Ester DCP" manufactured by Shinnakamura Chemical Industry Co., Ltd.) 19 parts by mass, photopolymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Co., Ltd.) 1 Parts by mass, heated at 60° C. for 30 minutes to uniformly dissolve and defoam, thereby obtaining an active energy ray curable resin composition (R1).

(Comparative example 2: Preparation of active energy ray curable resin composition (R2)) In a 200 mL brown bottle, 35 parts by mass of dipentaerythritol hexaacrylate ("A-DPH6A" manufactured by Kyoeisha Chemical Co., Ltd.) and polycarbonate diacrylate ("UM-DPH6A" manufactured by Ube Industries Co., Ltd.) were blended. 90 (1/3) DA") 45 parts by mass, polyethylene glycol diacrylate ("NK Ester (NK Ester) A-400" manufactured by Shinnakamura Chemical Industry Co., Ltd.) 20 parts by mass, photopolymerization start (Runtecure 1104 manufactured by Runtec Chemical) 1 part by mass, heated at 60°C for 30 minutes to dissolve and defoam uniformly, thereby obtaining active energy ray curable resin Composition (R2).

(Comparative example 3: Preparation of active energy ray curable resin composition (R3)) In a 200 mL brown bottle, 35 parts by mass of polypentaerythritol polyacrylate ("Viscoat (Viscoat) #802" manufactured by Osaka Organic Chemical Industry Co., Ltd.), and polycarbonate diacrylate (manufactured by Ube Industries Co., Ltd.) were blended. "UM-90 (1/3) DA") 45 parts by mass, polyethylene glycol diacrylate ("NK Ester (NK Ester) A-400" manufactured by Shinnakamura Chemical Industry Co., Ltd.) 20 parts by mass, Photopolymerization initiator (Runtecure 1104 manufactured by Runtec Chemical) 1 part by mass, heated at 60°C for 30 minutes to uniformly dissolve and defoam, thereby obtaining active energy Linear curable resin composition (R3).

(Comparative example 4: Preparation of active energy ray curable resin composition (R4)) In a 200 mL brown bottle, 35 parts by mass of polypentaerythritol polyacrylate ("NK Ester (NK Ester) TPOA-30" manufactured by Shinnakamura Chemical Industry Co., Ltd.), polycarbonate diacrylate (Ube Industries Co., Ltd.) 45 parts by mass of "UM-90 (1/3) DA" manufactured by the company, and 20 parts by mass of polyethylene glycol diacrylate ("NK Ester (NK Ester) A-400" manufactured by Shinnakamura Chemical Industry Co., Ltd.) Parts, 1 part by mass of the photopolymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Company), heated at 60°C for 30 minutes to uniformly dissolve and defoam, thereby obtaining Active energy ray curable resin composition (R4).

Using the active energy ray-curable resin composition obtained in the above-mentioned Examples and Comparative Examples, the following evaluations were performed. The evaluation results are described in Table 1 and Table 2.

[Method for Measuring Refractive Index] The active energy ray curable composition obtained in the examples and comparative examples was poured into a triangular scallop mold (thickness 5 mm, one side length 10 mm), using EyeGraphics Co., Ltd. The company’s conveyor-type ultraviolet irradiation device (120 W metal halide lamp) irradiates 3,000 mJ/cm ² of ultraviolet rays to produce a triangular-shaped hardened product. The refractive index of the obtained cured product was measured using the Kalnew precision refractometer "KPR-3000" manufactured by Shimadzu Corporation. In addition, a matching liquid having a refractive index (nD) closest to the refractive index (nD) of the cured product is appropriately selected and used.

[Method for measuring Abbe number] The active energy ray curable composition obtained in the examples and comparative examples was poured into a triangular scallop mold (thickness 5 mm, length of one side 10 mm), using EyeGraphics Co., Ltd. The conveyor-type ultraviolet irradiation device (120 W metal halide lamp) manufactured by the Co., Ltd. irradiates 3,000 mJ/cm ² of ultraviolet rays to produce a hardened product in the shape of a triangle. The Abbe number of the obtained hardened product was measured using the Kalnew precision refractometer "KPR-3000" manufactured by Shimadzu Corporation. In addition, a matching liquid having a refractive index (nD) closest to the refractive index (nD) of the cured product is appropriately selected and used.

[Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Active energy ray curable resin composition (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) Multi-branched polymer compound with acrylic group (A-1) Composition (parts by mass) 5 5 10 45 50 60 70 35 35 Viscoat #1000LT 35 CN2302 35 CN2303 35 CN2304 35 Polycarbonate diacrylate 85 80 75 55 50 40 30 65 45 45 45 45 45 Tricyclodecane dimethanol diacrylate 10 15 15 A-400 20 20 20 20 20 Photopolymerization initiator 1 1 1 1 1 1 1 1 1 1 1 1 1 Refractive index (nD) 1.495 1.497 1.498 1.498 1.500 1.502 1.504 1.496 1.498 1.497 1.495 1.495 1.497 Abbe number (νD) 57.6 57.6 57.2 57.1 56.9 56.4 56.2 57.2 57.2 57.2 57.3 57.4 57.0

[Table 2] Table 2 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Active energy ray curable resin composition (R1) (R2) (R3) (R4) Multi-branched polymer compound with acrylic group (A-1) Composition (parts by mass) DPE-6A 35 Viscoat #802 35 TPOA-30 35 Polycarbonate diacrylate 81 45 45 45 Tricyclodecane dimethanol diacrylate 19 A-400 20 20 20 Photopolymerization initiator 1 1 1 1 Refractive index (nD) 1.496 1.504 1.505 1.503 Abbe number (νD) 56.9 56.2 56.0 55.8

(Example 14: Production of laminate (1)) Using a straw, the active energy ray-curable resin composition (1) obtained in Example 1 was added dropwise using a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-5103") is placed on a glass substrate that has been adhesively bonded and clamped in a mold. Using an LED light irradiation device ("LHPUV365" manufactured by Iwasaki Electric Co., Ltd.), the irradiation intensity is 50 mW/cm ² and the cumulative light intensity is 450 mJ/cm ² to make it semi-hardened and demold the mold. After rinsing the uncured resin composition on the obtained semi-cured product using cyclopentanone as a solvent, the LED irradiation device was used to completely cure it ^{at an irradiation intensity of 50 mW/cm 2} and a cumulative light amount of 7550 mJ/cm ^2. Then, the hardened product was put into an oven heated to 100°C, and an annealing treatment was performed for 90 minutes to obtain a hardened product. Using a magnetron sputtering device ("HSR-522" manufactured by Shimadzu Corporation), target: SiO ₂ , introduced gas: Ar, gas flow rate: 15 sccm, room temperature 25°C, sputtering time: 55 min The cured product obtained in this manner was sputtered under the conditions, and an SiO ₂ film was laminated on the surface of the cured product to a thickness of 0.6 μm to obtain a laminate (1).

(Example 15: Production of laminate (2)) Except that the active energy ray curable resin composition (2) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (2) was obtained in the same manner as in Example 14 .

(Example 16: Production of laminate (3)) Except that the active energy ray curable resin composition (3) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (3) was obtained in the same manner as in Example 14 .

(Example 17: Production of laminate (4)) Except that the active energy ray curable resin composition (4) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (4) was obtained in the same manner as in Example 14 .

(Example 18: Production of laminate (5)) Except that the active energy ray curable resin composition (5) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (5) was obtained in the same manner as in Example 14 .

(Example 19: Production of laminate (6)) Except that the active energy ray curable resin composition (6) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (6) was obtained in the same manner as in Example 14 .

(Example 20: Production of laminate (7)) Except that the active energy ray curable resin composition (7) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (7) was obtained in the same manner as in Example 14 .

(Example 21: Production of laminate (8)) Except that the active energy ray curable resin composition (8) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (8) was obtained in the same manner as in Example 14 .

(Example 22: Production of laminate (9)) Except that the active energy ray curable resin composition (9) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (9) was obtained in the same manner as in Example 14 .

(Example 23: Production of laminate (10)) Except that the active energy ray curable resin composition (10) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (10) was obtained in the same manner as in Example 14 .

(Example 24: Production of laminate (11)) Except that the active energy ray curable resin composition (11) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (11) was obtained in the same manner as in Example 14 .

(Example 25: Production of laminate (12)) Except that the active energy ray curable resin composition (12) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (11) was obtained in the same manner as in Example 14 .

(Example 26: Production of laminate (13)) Except that the active energy ray curable resin composition (13) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (13) was obtained in the same manner as in Example 14 .

(Comparative example 5: Production of laminate (R1)) Except that the active energy ray curable resin composition (R1) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (R1) was obtained in the same manner as in Example 14 .

(Comparative example 6: Production of laminate (R2)) Except that the active energy ray-curable resin composition (R2) was used instead of the active energy ray-curable resin composition (1) used in Example 14, a laminate (R2) was obtained in the same manner as in Example 14 .

(Comparative example 7: Production of laminate (R3)) Except that the active energy ray curable resin composition (R3) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (R3) was obtained in the same manner as in Example 11 .

(Comparative Example 8: Production of laminated body (R4)) Except that the active energy ray curable resin composition (R4) was used instead of the active energy ray curable resin composition (1) used in Example 14, a laminate (R4) was obtained in the same manner as in Example 14 .

The following evaluations were performed using the laminates obtained in the above-mentioned Examples and Comparative Examples.

[Evaluation method of crack resistance] The laminated body (1) to the laminated body (10) obtained in Example 11 to Example 20, and the laminated body (R1) to the laminated body (R7) obtained in Comparative Example 8 to Comparative Example 14 were placed and heated to After performing a heat treatment for 5 minutes in an oven at 175°C, the surface of the laminate (inorganic layer) was observed with a microscope ("VHX900" manufactured by Keyence Co., Ltd.), and evaluated according to the following criteria. ○: No cracks occurred on the surface of the laminate. △: One to three cracks occurred on the surface of the laminate. ×: Four or more cracks occurred on the surface of the laminate.

The evaluation results of the laminate (1) to the laminate (10) obtained in Example 11 to Example 20, and the laminate (R1) to the laminate (R7) obtained in Comparative Example 8 to Comparative Example 14 are shown in In Table 3 and Table 4.

[table 3] table 3 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Layered body (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) Crack resistance ○ ○ ○ ○ △ △ △ ○ ○ ○ ○ ○ ○

[Table 4] Table 4 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8 Layered body (R1) (R2) (R3) (R4) Crack resistance X X X X

Examples 1 to 26 shown in Table 1 and Table 3 are examples of active energy ray-curable resin compositions containing a multi-branched polymer compound (A) having a (meth)acryloyl group. It was confirmed that the laminate having the resin layer containing the active energy ray-curable resin composition suppresses the occurrence of cracks in the inorganic layer formed on the resin layer and has excellent crack resistance.

On the other hand, Comparative Examples 1 to 8 are examples of active energy ray-curable resin compositions that do not contain a multi-branched polymer compound (A) having a (meth)acryloyl group. A laminate having a resin layer containing the active energy ray-curable resin composition was heat-treated at 175°C for 5 minutes, and 4 or more cracks were generated on the surface. Therefore, it was confirmed that the film formation on the resin layer was suppressed. The crack resistance for the occurrence of cracks in the inorganic layer is clearly insufficient.

without

without

Claims (7)

An active energy ray curable resin composition for forming a resin layer, which is an active energy ray curable resin composition for forming a resin layer including a laminate of a resin layer and an inorganic layer, characterized in that the active energy ray curable The resin composition contains a multi-branched polymer compound (A) having a (meth)acryloyl group. The active energy ray-curable resin composition for forming a resin layer according to claim 1, wherein the multi-branched polymer compound (A) is selected from compounds having a dendritic polymer structure and those having a hyperbranched structure One or more compounds in the group consisting of compounds and compounds with star-shaped structures. A cured product which is a cured product of the active energy ray-curable resin composition described in claim 1 or 2. The hardened product according to claim 3, wherein the Abbe number νD is 53 or more. The cured product according to claim 3, wherein the refractive index nD at a wavelength of 589 nm is 1.48 or more. A laminated body characterized by comprising: a resin layer including the hardened product according to any one of claims 3 to 5; and an inorganic layer. A lens characterized by comprising the laminated body according to claim 6.