Active energy ray-curable composition, cured product, lens, wafer-level lens, and camera module

Abstract

The present invention relates to an active energy ray-curable composition, a cured product, a lens, a wafer-level lens, and a camera module. The active energy ray-curable composition is characterized by comprising: a compound (A) having at least one structure selected from the group consisting of formula (1), formula (2), and formula (3) and two or more (meth)acryloyl groups in one molecule; and a polycarbonate diol di(meth)acrylate (B) represented by formula (4), wherein the component (A) (R) contains 1% by mass or more and less than 50% by mass of the component (A) relative to 100% by mass of the total mass of the compounds having (meth)acryloyl groups other than the component (A). 1 is a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a (meth)acryloyloxyalkyl group or a (meth)acryloyloxyalkyloxy group, X is a methylene group or an oxygen atom, R 2 is a hydrogen atom or a methyl group, R 3 is a hydrocarbon group, and n is an integer from 1 to 10). #imgabs0#

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable composition, a cured product, a lens, a wafer-level lens, and a camera module. Background Art

[0002] In recent years, the demand for small camera modules for electronic devices such as smartphones and mobile personal computers has been rapidly increasing, and development efforts aimed at improving the production efficiency of camera modules are underway. In addition, as electronic devices continue to become thinner, the demand for thinner camera modules has also become stricter. Previously, camera modules were produced by molding resin lenses using injection molds using thermoplastic resins such as cycloolefin polymers, and assembling lens units. However, existing methods have limitations in productivity and thinness. In response to this market trend, a method for producing camera modules that achieves both productivity and thinness by assembling lens units by overlapping wafer-level lenses formed using a replication method has been disclosed (Patent Document 1).

[0003] Generally speaking, a lens unit is a combination of multiple optical constants, mainly refractive index (n d ) and Abbe number (ν d ) different lenses to correct chromatic aberration, thereby achieving high pixelation. Furthermore, active energy ray-curable resin compositions are preferably used as materials for the wafer-level lenses from the perspectives of productivity, transparency, and heat resistance. In particular, a resin composition for a wafer-level lens is disclosed that uses polycarbonate diol (meth)acrylate having an aliphatic skeleton as a material having optical constants of a medium refractive index and a high Abbe number (Patent Document 2).

[0004] Since the wafer-level lens is assumed to be mounted directly on the substrate, heat resistance that can withstand reflow (170°C to 260°C) is required. In terms of improving heat resistance, a method of adding a thiol compound or an antioxidant is disclosed (Patent Document 3, Patent Document 4). In addition, depending on the usage, in order to confirm the reliability under high temperature and high humidity, heat resistance that can withstand a wet heat test (85°C-85%RH-1000h) is required. However, there is no report of a wafer-level lens with excellent heat resistance that does not cause substrate peeling or defects inside the lens under the harsh temperature and humidity test conditions of 85°C-85%RH. In particular, there is the following problem: the aliphatic skeleton showing optical constants with a medium refractive index and a high Abbe number is hydrophobic and is prone to abnormalities after the wet heat test.

[0005] Generally speaking, an anti-reflection layer is provided on the lens surface for the purpose of improving the contrast during video recording. In the case where the same anti-reflection layer is also provided for a wafer-level lens, there is a problem of cracks being generated in the anti-reflection layer through the reflow process after installation. A method for preparing a lens resin composition with excellent crack resistance by preparing silica particles as the anti-reflection layer in the reflow process has been disclosed (Patent Document 5, Patent Document 6). However, by using particles, the processing properties in the manufacturing process caused by the sedimentation or cohesion of the particles in the resin composition, the high viscosity of the resin composition, etc., have become a new problem. In addition, when the interlayer adhesion between the anti-reflection layer and the lens is low, peeling or cracks of the anti-reflection layer may be generated by a wet heat test.

[0006] Therefore, there is a need for a lens material that can form a lens having a high Abbe number and transmittance, excellent heat resistance and heat and humidity resistance, and that can suppress cracking or peeling of inorganic layers such as antireflection layers laminated on the surface under thermal history or high temperature and high humidity.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 2009-251368

[0010] Patent Document 2: International Publication No. 2019 / 124156

[0011] Patent Document 3: Japanese Patent Application Laid-Open No. 2014-52424

[0012] Patent Document 4: International Publication No. 2018 / 030351

[0013] Patent Document 5: International Publication No. 2019 / 142601

[0014] Patent Document 6: International Publication No. 2019 / 167461 Summary of the Invention

[0015] Problems to be solved by the invention

[0016] The problem to be solved by the present invention is to provide an active energy ray-curable composition capable of forming a lens having a high Abbe number and transmittance, minimal transmittance change after reflow, excellent heat resistance and resistance to moist heat, crack resistance of an inorganic layer formed on the surface, and excellent adhesion to the inorganic layer formed on the surface.

[0017] Technical means to solve the problem

[0018] The present inventors have conducted intensive studies to solve the above-mentioned problems and have found that the above-mentioned problems can be solved by using an active energy ray-curable composition, thereby completing the present invention. The active energy ray-curable composition contains a compound having a (meth)acryloyl group, and the active energy ray-curable composition is characterized in that it contains: a compound (A) having at least one structure selected from the group consisting of the following general formulas (1), (2), and (3) and two or more (meth)acryloyl groups in one molecule; and a polycarbonate diol di(meth)acrylate (B) represented by the following general formula (4), wherein the component (A) is contained in an amount of 1% by mass or more and less than 50% by mass relative to 100% by mass of the total mass of the compounds having (meth)acryloyl groups excluding the component (A).

[0019] That is, the present invention relates to an active energy ray-curable composition, a cured product, a lens, a wafer-level lens, and a camera module, wherein the active energy ray-curable composition contains a compound having a (meth)acryloyl group, and the active energy ray-curable composition is characterized by containing: a compound (A) having, in one molecule, at least one structure selected from the group consisting of the following general formulas (1), (2), and (3) and two or more (meth)acryloyl groups; and a polycarbonate diol di(meth)acrylate (B) represented by the following general formula (4), wherein the component (A) is contained in an amount of 1% by mass or more and less than 50% by mass relative to 100% by mass of the total mass of the compounds having (meth)acryloyl groups excluding the component (A).

[0020]

[0021] (Where R 1 Each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a (meth)acryloyloxyalkyl group, or a (meth)acryloyloxyalkyloxy group; and X represents a methylene group or an oxygen atom.

[0022]

[0023] (Where R 2 Each independently represents a hydrogen atom or a methyl group, R 3 Each independently represents a hydrocarbon group having 1 to 10 carbon atoms; n is an integer of 1 to 10.

[0024] The cured product is a cured product of the active energy ray-curable composition.

[0025] The lens is characterized by comprising the aforementioned cured product; or comprising the aforementioned cured product with an inorganic compound layer provided on at least one surface thereof.

[0026] The wafer-level lens is characterized by comprising the aforementioned hardened material.

[0027] The camera module is characterized by having the aforementioned lens.

[0028] Effects of the Invention

[0029] According to the present invention, an active energy ray-curable composition can be provided that is capable of forming a lens having a high Abbe number and transmittance, minimal transmittance change after reflow, excellent heat resistance and resistance to moist heat, crack resistance of an inorganic layer formed on the surface, and excellent adhesion to the inorganic layer formed on the surface.

[0030] Furthermore, the active energy ray-curable composition of the present invention can be easily cured by irradiation with active energy rays and can be preferably used in lens production by photoimprinting.

[0031] In addition to the above, the lens formed from the active energy ray-curable composition of the present invention has a high Abbe number, which can reduce chromatic aberration. In addition, the lens has a small change in transmittance before and after reflow and has heat resistance, and can be preferably used as a wafer-level lens. Furthermore, since it has heat resistance that does not cause peeling or defects from the substrate even under high temperature and high humidity, it can be preferably used as a wafer-level lens with excellent long-term stability. In addition, since the inorganic layer formed on the lens surface can suppress the occurrence of cracks or peeling caused by thermal history or high temperature and high humidity, it can be preferably used as a wafer-level lens including an inorganic layer such as an anti-reflection layer. DETAILED DESCRIPTION

[0032] The active energy ray-curable composition of the present invention is an active energy ray-curable composition containing a compound having a (meth)acryloyl group, and the active energy ray-curable composition is characterized in that it contains: a compound (A) having at least one structure selected from the group consisting of the following general formula (1), general formula (2) and general formula (3) and two or more (meth)acryloyl groups in one molecule; and a polycarbonate diol di(meth)acrylate (B) represented by the following general formula (4), wherein the component (A) is contained in an amount of 1 mass % or more and less than 50 mass % relative to 100 mass % of the total mass of the compounds having (meth)acryloyl groups other than the component (A).

[0033]

[0034] (Where R 1 (each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a (meth)acryloyloxyalkyl group, or a (meth)acryloyloxyalkyloxy group; X represents a methylene group or an oxygen atom)

[0035]

[0036] (Where R 2 Each independently represents a hydrogen atom or a methyl group, R 3 Each independently represents a hydrocarbon group having 1 to 10 carbon atoms; n is an integer of 1 to 10)

[0037] In the present invention, "(meth)acrylate" refers to acrylate and / or methacrylate. Furthermore, "(meth)acryloyl" refers to acryloyl and / or methacryloyl. Furthermore, "(meth)acrylic acid" refers to acrylic acid and / or methacrylic acid.

[0038] The compound (A) having at least one structure selected from the group consisting of general formula (1), general formula (2), and general formula (3) and two or more (meth)acryloyl groups in one molecule (hereinafter referred to as "component (A)") must have at least one structure selected from the group consisting of general formula (1), general formula (2), and general formula (3) and two or more (meth)acryloyl groups in one molecule. By using component (A), an active energy ray-curable composition can be obtained that can form a lens having a high Abbe number and excellent heat resistance and moisture-heat resistance, and an inorganic layer having excellent crack resistance and adhesion.

[0039] The component (A) has at least one structure selected from the group consisting of the general formula (1), the general formula (2) and the general formula (3), and thus includes an organic silane skeleton, a linear and cyclic siloxane skeleton, a random, ladder and cage silsesquioxane skeleton, and the like.

[0040] In addition, as R 1 , and examples thereof include, independently, a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a (meth)acryloyloxyalkyl group, and a (meth)acryloyloxyalkyloxy group.

[0041] Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, tert-pentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, neohexyl, cyclohexyl, heptyl, n-octyl, sec-octyl, isooctyl, tert-octyl, n-nonyl, and n-decyl.

[0042] Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyloxy group.

[0043] Specific examples of the (meth)acryloyloxyalkyl group include a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, a (meth)acryloyloxypropyl group, a (meth)acryloyloxybutyl group, a (meth)acryloyloxypentyl group, and a (meth)acryloyloxyhexyl group.

[0044] Specific examples of the (meth)acryloyloxyalkyloxy group include a (meth)acryloyloxymethyloxy group, a (meth)acryloyloxyethyloxy group, a (meth)acryloyloxypropyloxy group, a (meth)acryloyloxybutyloxy group, a (meth)acryloyloxypentyloxy group, and a (meth)acryloyloxyhexyloxy group.

[0045] The two or more (meth)acryloyl groups of the component (A) may also serve as the R 1 and are included in the general formula (1), general formula (2) and general formula (3) by being a partial skeleton. In addition, when the component (A) is a chain structure, it can be located at any position at the end of the main chain, inside the main chain skeleton, at the end of the branch chain, or inside the branch chain skeleton. In the case of a cyclic molecule, it can be directly bonded to the ring structure or bonded via a linking group. Examples of the chain structure include polyalkylene glycol, polyester, poly(meth)acrylate, polyurethane, polysiloxane, etc., which can be any of a straight chain structure and a branched chain structure. Examples of the linking group include alkanediol, caprolactone, alkylene isocyanate, etc.

[0046] Specific examples of the component (A) include (meth)acryloyl-modified organosilanes, (meth)acryloyl-modified siloxanes, (meth)acryloyl-modified polysiloxanes, (meth)acryloyl-modified silsesquioxanes, (meth)acryloyl-modified silicone oligomers, and (meth)acryloyl-modified silicone oils.

[0047] Examples of commercially available products of the component (A) include "X-12-1048", "X-12-1050", "X-12-2475", "X-12-2430C", "X-22-164", "X-22-164AS", "X-22-164A", "X-22-164B", "X-22-164C", "X-22-164E", "X-22-2445", "X-40-2475", "X-40-9296", "X-40-9308", "KP-410", "KP-411", "KP-412", "KP-413", "KP-414", "K BYK UV-3500, BYK UV-3530, BYK UV-3570, BYK UV-3575, BYK UV-3576 manufactured by BYK-Chemie, Silaplane FM-7711, Silaplane FM-7721, Silaplane FM-7725 manufactured by JNC Co., Ltd., AC-SQ TA-100, AC-SQ SI-20, MAC-SQ TM-100, MAC-SQ SI-20 manufactured by Toagosei Co., Ltd., etc.

[0048] The weight average molecular weight of the component (A) is not particularly limited within a range that exhibits the effects of the present invention. However, in order to facilitate compatibility with compounds having a (meth)acryloyl group other than the component (A) and to obtain a cured product with high transmittance, the weight average molecular weight is preferably in the range of 100 to 10,000, more preferably in the range of 200 to 5000, and particularly preferably in the range of 300 to 3000.

[0049] The content ratio of the component (A) is not particularly limited within the range that achieves the effects of the present invention. However, in order to obtain an active energy ray-curable composition capable of forming a lens having a high Abbe number, excellent heat resistance and moisture-heat resistance, and excellent crack resistance and adhesion of the inorganic layer, the content ratio of the component (A) is preferably 1% by mass or more and less than 50% by mass, more preferably 2.5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass, relative to the total mass (100% by mass) of the compounds having a (meth)acryloyl group excluding the component (A) in the active energy ray-curable composition.

[0050] The present invention may contain a compound having a (meth)acryloyl group other than component (A). There are no particular limitations on the compound having a (meth)acryloyl group other than component (A) as long as the effects of the present invention can be achieved. Compounds having a (meth)acryloyl group may be used as various components (B) to (D) described below, and compounds having a (meth)acryloyl group may be added and used as other additives.

[0051] The polycarbonate diol di(meth)acrylate (B) represented by the general formula (4) (hereinafter referred to as "component (B)") has a structure represented by the general formula (4). By using the component (B), an active energy ray-curable composition capable of forming a lens having a high Abbe number and excellent heat resistance can be obtained.

[0052] As the component (B), an active energy ray-curable composition capable of forming a lens having a further higher Abbe number and refractive index and further excellent transparency, flexibility and heat resistance can be obtained. In the general formula (4), R 2 Preferably, a hydrogen atom, R 3 Preferably, each is independently a linear hydrocarbon group having 5 to 6 carbon atoms or a cyclic hydrocarbon group having 6 to 10 carbon atoms, and n is preferably an integer of 4 to 10. In addition, in order to more easily prevent crystallization or subsequent warping of the lens, R 2 More preferably, each independently represents a linear hydrocarbon group having 5 to 6 carbon atoms, a cyclohexane structure, or an isosorbide structure, and n is more preferably an integer of 4 to 6.

[0053] Furthermore, in the general formula (4), R 3 When it represents a straight-chain hydrocarbon group having 5 to 6 carbon atoms and a cyclic hydrocarbon group having 6 to 10 carbon atoms, and n represents an integer of 4 to 6, the mass ratio of the straight-chain hydrocarbon group having 5 to 6 carbon atoms to the cyclic hydrocarbon group having 6 to 10 carbon atoms is preferably in the range of 10 / 90 to 90 / 10, more preferably in the range of 20 / 80 to 80 / 20, and particularly preferably in the range of 40 / 60 to 75 / 25, in terms of the ratio of straight-chain hydrocarbon group / cyclic hydrocarbon group.

[0054] Examples of the component (B) include reaction products of polycarbonate diol and (meth)acrylic acid and / or (meth)acrylate.

[0055] Examples of the polycarbonate diol include reaction products of a compound having two or more hydroxyl groups and a carbonate.

[0056] Examples of the compound having two or more hydroxyl groups include linear alkanediols, branched alkanediols, cyclic alkanediols, and heterocyclic diols. These compounds may be used alone or in combination of two or more.

[0057] Examples of the alkanediol having a linear structure include 1,2-ethanediol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol.

[0058] Examples of the alkanediol having a branched chain structure include 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-methyl-1,3-propylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,2-dimethyl-1,3-propylene 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, and 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.

[0059] Examples of the alkanediol having a cyclic structure include 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,3-adamantanediol, and 1-hydroxy-3-adamantylmethanol.

[0060] Examples of the diol having a heterocyclic structure include 3,4-tetrahydrofurandiol, 1,4-dioxane-2,3-diol, 1,1-dicyclohexyl-4,4-diol, and hexahydrofluoro[3,2-b]furan-3,6-diol.

[0061] Examples of the carbonate ester include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate. These compounds may be used alone or in combination of two or more.

[0062] Examples of the (meth)acrylate 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, and n-octyl (meth)acrylate. These (meth)acrylates may be used alone or in combination of two or more.

[0063] In addition, commercially available products of the component (B) include, for example, "UH-100DA", "UM-90(1 / 3)DA", "UM-90(1 / 1)DA", "UM-90(3 / 1)DA", "UH-100DM", "UM-90(1 / 3)DM", "UM-90(1 / 1)DM", and "UM-90(3 / 1)DM" manufactured by Ube Industries, Ltd.

[0064] The content of the component (B) is preferably in the range of 5% by mass to 70% by mass, more preferably in the range of 10% by mass to 60% by mass, and particularly preferably in the range of 20% by mass to 50% by mass, in order to obtain an active energy ray-curable composition capable of forming a lens having a high Abbe number and excellent heat resistance and heat and humidity resistance.

[0065] In addition to the components (A) and (B), the active energy ray-curable composition of the present invention may also include a compound (C) having one or two (meth)acryloyl groups and an alkanediol structure in one molecule (hereinafter referred to as "component (C)") to further improve crack resistance. Component (C) in the present invention must have one or two (meth)acryloyl groups and an alkanediol structure in one molecule. The use of component (C) can produce an active energy ray-curable composition capable of forming a lens having a higher Abbe number, excellent heat resistance, and resistance to moist heat, and excellent crack resistance of the inorganic layer.

[0066] Examples of the alkanediol structure include 1,2-ethanediol (ethylene glycol), 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,2-propylene glycol (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, 1,5-hexanediol, and 1,10-decanediol. Alkyl alcohol, 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 alkanediol structures may be present in one molecule alone or in two or more kinds. Among these, ethylene glycol, propylene glycol, and neopentyl glycol are preferred for obtaining an active energy ray-curable composition capable of forming a lens having excellent heat resistance and resistance to heat and moisture. Furthermore, the number of repeating units of the alkanediol structure is preferably 2 to 15 for obtaining an active energy ray-curable composition capable of forming a lens having even better resistance to heat and moisture and crack resistance.

[0067] In addition, the component (C) may also have a cyclic structure, for example, a monocyclic structure such as a cyclopentane structure, a cyclohexane structure, a cyclooctane structure, a cyclodecane structure, a perhydroindene structure, a perhydroanthracene structure, a perhydrofluorene structure, a perhydrophenanthrene structure, a perhydroacenaphthene structure, a perhydrophenalene structure, a norbornane structure, an isobornane structure, an isobornyl structure, an adamantane structure, a bicyclo[3.3.0]octane structure, a tricyclo[5.2.1.0 2,6 ]Decane structure, tricyclic [6.2.1.0 2,7 ] undecane structure, dicyclopentane structure, dicyclopentenyl structure and other polycyclic structures, tetrahydrofuran structure, 1,3-dioxolane structure, 1,3-dioxane structure, 1,4-dioxane structure, hexahydrofluoro[3,2-b]furan structure and other heterocyclic structures, benzene structure, naphthalene structure, fluorene structure, acenaphthene structure, phenanthracene structure, anthracene structure, phenanthrene structure, tetracene structure, Aromatic ring structures such as pyrene structure, triphenylene structure, pentacene structure, benzopyrene structure, and perylene structure are preferred. These ring structures may be present alone or in combination. Among these, cyclohexane structure, tricyclo[5.2.1.0 2,6 ]Decane structure.

[0068] In the component (C), the cyclic structure and the (meth)acryloyl group may be bonded directly or through a linking group.

[0069] Examples of the linking group include oxygen atoms, linear and / or branched hydrocarbon groups having 1 to 10 carbon atoms, alkylene oxide groups having 1 to 10 repeating numbers, alkyl ester groups having 1 to 10 repeating numbers as ring-opening polymers of caprolactone, and amide groups.

[0070] Specific examples of the component (C) having a cyclic structure include cyclopentyl alkylene oxide-modified (meth)acrylate, 1-methylcyclopentyl alkylene oxide-modified (meth)acrylate, 1-ethylcyclopentyl alkylene oxide-modified (meth)acrylate, cyclohexyl alkylene oxide-modified (meth)acrylate, 1-methylcyclohexyl alkylene oxide-modified (meth)acrylate, 1-ethylcyclohexyl alkylene oxide-modified (meth)acrylate, trimethylcyclohexyl alkylene oxide-modified (meth)acrylate, 4-tert-butylcyclohexyl alkylene oxide-modified (meth)acrylate, ) acrylate, 2-cyclohexyl chlorpyrifos alkylene oxide modified (meth) acrylate, hydrogenated bisphenol A alkylene oxide modified di(meth) acrylate, hydrogenated bisphenol F alkylene oxide modified di(meth) acrylate, benzyl alkylene oxide modified (meth) acrylate, phenyl alkylene oxide modified (meth) acrylate, nonylphenol alkylene oxide modified (meth) acrylate, phenoxybenzyl alkylene oxide modified (meth) acrylate, phenylbenzyl alkylene oxide modified (meth) acrylate, biphenyl alkylene oxide modified (meth) acrylate, bisphenol A alkylene oxide modified di(meth) Acrylates, bisphenol F alkylene oxide-modified di(meth)acrylates, fluorene alkylene oxide-modified di(meth)acrylates, isobornyl alkylene oxide-modified (meth)acrylates, isobornyl alkylene oxide-modified di(meth)acrylates, dicyclopentyl alkylene oxide-modified (meth)acrylates, dicyclopentenyl alkylene oxide-modified (meth)acrylates, tricyclodecanediol alkylene oxide-modified di(meth)acrylates, tricyclodecane dimethanol alkylene oxide-modified di(meth)acrylates, adamantyl alkylene oxide-modified (meth)acrylates, adamantyl alkylene oxide-modified Di(meth)acrylate, 2-methyladamantyl epoxy-modified (meth)acrylate, 2-ethyladamantyl epoxy-modified (meth)acrylate, 2-isopropyladamantyl epoxy-modified (meth)acrylate, (3-ethyloxetane-3-yl)methyl epoxy-modified (meth)acrylate, tetrahydrofurfuryl epoxy-modified (meth)acrylate, (2-oxo-1,3-dioxolane-4-yl)methyl epoxy-modified (meth)acrylate, isosorbide epoxy-modified di(meth)acrylate, etc. These compounds can be used alone or in combination of two or more. In addition, among these, hydrogenated bisphenol A epoxy-modified di(meth)acrylate and tricyclodecane dimethanol epoxy-modified di(meth)acrylate are preferred in terms of obtaining an active energy ray-curable composition that can form a lens with a high Abbe number and excellent heat resistance, heat and moisture resistance, and crack resistance.

[0071] Examples of commercially available products of the component (C) include "Miramer M2040," "Miramer M231," "Miramer M233," "Miramer M235," "Miramer M281," "Miramer M283," "Miramer M1142," and "Miramer M1143" manufactured by MIWON. r)M140", "Miramer M141", "Miramer M142", "Miramer M144", "Miramer M164", "Miramer M166", "Miramer M1602", "Miramer M170", "Miramer M202", "Miramer M210", "Miramer Miramer M2100", "Miramer M2101", "Miramer M216", "Miramer M220", "Miramer M2200", "Miramer M222", "Miramer M2300", "Miramer M2301", "Miramer M232", "Miramer M2300", "Miramer M2301", "Miramer M2302", "Miramer M2303", "Miramer M2303", "Miramer M2304", "Miramer M2305", "Miramer M2306", "Miramer M2307", "Miramer M2308", "Miramer M2309", "Miramer M2310", "Miramer M2311", "Miramer M2312", "Miramer M2313", "Miramer M2314", "Miramer M2315", "Miramer M2316", "Miramer M2317", "Miramer M2318", "Miramer M2319", "Miramer M2320", "Miramer M2321", "Miramer M2322" er) M240", "Miramer M241", "Miramer M244", "Miramer M245", "Miramer M280", "Miramer M282", "Miramer M284", "Miramer M286", "Miramer M290", "NK ester (NK)" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. ESTER) A-30G", "NK Ester (NK ESTER) A-90G", "NK Ester (NK ESTER) A-130G", "NK Ester (NK ESTER) A-200", "NK Ester (NK ESTER) A-400", "NK Ester (NK ESTER) A-600", "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 (NKESTER) M-30PG", "NK Ester (NK 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", "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) AM-30PG", "NK Ester (NK ESTER) AMP-10G", "NK Ester (NK ESTER) AMP-20GY", "NK Ester (NK ESTER) ESTER)702A", "NK Ester (NK ESTER) A-LEN-10", "NK Ester (NK ESTER) 401P", "NK Ester (NK ESTER) A-BPEF", "NK Ester (NK ESTER) A-BPE-2", "NK Ester (NK ESTER) ABE-300", "NK Ester (NK ESTER) A-BPE-4", "NK Ester (NK ESTER) A-BPE-10", "NK Ester (NK ESTER) A-BPE-20", "NK Ester (NK ESTER) A-BPE-30", "NK Ester (NK ESTER) A-BPP-3", "NK Ester (NK ESTER) A-B1206PE", "NK Ester (NK ESTER) PHE-1G", "NK Ester (NK ESTER) PHE-2G", "NK Ester (NK ESTER) BPE-80N", "NK Ester (NK ESTER) BPE-100", "NK Ester (NK ESTER) NKESTER BPE-200", "NKESTER BPE-300", "NKESTER BPE-500", "NKESTER BPE-900", "NKESTER BPE-1300N", "Light Ester BC", "Light Ester 130MA", "Light Ester BC", "Light Ester 2EG", "Light Ester 3EG", "Light Ester" manufactured by Kyoeisha Chemical Co., Ltd.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 "Light Acrylate 14EG-A", "Light Acrylate PTMGA-250", "Viscoat #190", "Viscoat #MTG", "MPE400A", "MPE550A", "Viscoat #310HP", "Viscoat #192", "Viscoat #700HV", "Viscoat #540" manufactured by Osaka Organic Chemical Industry Co., Ltd., "Light Ester PO", "Light Ester BP-2EMK", "Light Acrylate PO-A", "Light Acrylate P2H-A", "Light Acrylate P-200A", "Epoxy Ester" manufactured by Kyoeisha Chemical Co., Ltd. Ester M-600A", "Light Acrylate BP-4PA", "KAYARAD PEG400DA", "KAYARAD R-128H", "KAYARAD R-551", "KAYARAD R-712" manufactured by Nippon Kayaku Co., Ltd., "New Frontier ME-3", "New Frontier ME-4S", "New Frontier MPE-600", "New Frontier" manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.New Frontier PE-200", "New Frontier PE-300", "New Frontier PE-400", "New Frontier PE-600", "New Frontier MPEM-400", "New Frontier TEGDMA", "New Frontier PHE", "New Frontier PHE-2", "New Frontier PHE-2D", "New Frontier NP-1", "New Frontier NP-4", "New Frontier N-177E", "New Frontier N-PGA", "New Frontier OPPE", "New Frontier BPE-4", "New Frontier BPE-10", "New Frontier BPE-20", "New Frontier BPEM-4", "New Frontier BPEM-10", "New Frontier Frontier) HBPE-4", "New Frontier (New Frontier) HBPEM-10", "Fancryl (Fancryl) FA-240A", "Fancryl (Fancryl) FA-P240A", "Fancryl (Fancryl) FA-P270A", "Fancryl (Fancryl) FA-PTG9A", "Fancryl (Fancryl) FA-400M (100)", "Fancryl (Fancryl) FA-240M", "Fancryl (Fancryl) FA-PTG9 ...PTG9M", "Fancryl (Fancryl) FA-PTG9A", "Fancryl (Fancryl) FA-PTG9M", "Fancryl (Fancryl) FA-PTG9A", "Fancryl (Fancryl) FA-PTG9M", "Fancryl (Fancryl) FA-PTG9A", "Fancryl (Fancryl) FA-PTG9A", "Fancryl (Fancryl) FA-PTG9M", "Fancryl (Fancryl) FA-PTG9A", "Fancryl (Fancryl) FA-PTG9A", "Fancryl (Fancryl) FA-PTG9A", "Fancryl (Fancryl) FA-PTG9A", "Fancryl (Fancryl) FA-PTG9A Fancryl FA-310A", "Fancryl FA-314A", "Fancryl FA-318A", "Fancryl FA-321A", "Fancryl FA-324A", "Fancryl FA-310M", "Fancryl FA-320M", "Fancryl FA-321M", "Fancryl FA-3218M", etc.

[0072] The content ratio of the component (C) is not limited within a range that can achieve the effects of the present invention. However, in order to obtain an active energy ray-curable composition capable of forming a lens having a high Abbe number and excellent heat resistance and heat and humidity resistance, the content ratio of the component (C) in the active energy ray-curable composition is preferably in the range of 1% by mass to 40% by mass, more preferably in the range of 3% by mass to 30% by mass, and particularly preferably in the range of 5% by mass to 20% by mass.

[0073] The active energy ray-curable composition of the present invention may contain, in addition to the components (A) and (B), a compound (D) having six or more (meth)acryloyl groups and a multi-branched structure in one molecule (hereinafter referred to as "component (D)") for the purpose of further improving crack resistance. Component (D) must contain six (meth)acryloyl groups and a multi-branched structure in one molecule.

[0074] In order to obtain an active energy ray-curable resin composition having excellent crack resistance, the number of (meth)acryloyl groups in one molecule of the component (D) is preferably in the range of 6 to 96, more preferably in the range of 8 to 64, and particularly preferably in the range of 9 to 48.

[0075] Examples of the multi-branched structure include a dendritic structure, a dendritic structure (dendritic structure), a hyperbranched structure (hyperbranched structure), and a star-shaped structure. These multi-branched structures may exist alone or in combination in a single molecule. Of these, dendritic and hyperbranched structures are preferred because they provide active energy ray-curable compositions capable of forming lenses with particularly excellent crack resistance.

[0076] There is no particular limitation on the method for producing the component (D), and the component can be produced by a suitable known method. For example, a divergent method in which molecules are bonded to a central core molecule to form branches, a convergent method in which pre-synthesized branch portions are bonded to core molecules, and a method in which a monomer ABx comprising a branch portion having two or more reaction points B and a linking portion having another reaction point A in one molecule is synthesized in one stage are mentioned. Among them, as one of the simple synthesis methods, the divergent method is preferred, such as obtaining a polyol compound (c) having a multi-branched structure by esterifying a polyol (a) with a compound (b) having one or more carboxyl groups and two or more hydroxyl groups in one molecule. Subsequently, the polyol compound (c) can be produced by an esterification reaction using a dehydration condensation of the terminal hydroxyl group of the polyol compound with (meth) acrylic acid, an ester exchange reaction of the terminal hydroxyl group of the polyol compound with (meth) acrylic ester, and an addition reaction of the terminal hydroxyl group of the polyol compound with an isocyanate compound having a (meth) acryloyl group.

[0077] Examples of the polyol (a) include glycerol, trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol, tris(2-hydroxyethyl)isocyanurate, sorbitol, mannitol, and alkylene oxide adducts or caprolactone ring-opening adducts of these alcohols. These polyols may be used alone or in combination of two or more.

[0078] Examples of the compound (b) having one or more carboxyl groups and two or more hydroxyl groups in one molecule 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 may be used alone or in combination of two or more.

[0079] Examples of commercially available products of the polyol compound (c) include "BOLTORN H20," "BOLTORN H30," "BOLTORN H40," "BOLTORN H311," "BOLTORN H2003," "BOLTORN H2004," "BOLTORN P500," "BOLTORN P501," and "BOLTORN P1000," all manufactured by Perstorp.

[0080] Examples of commercially available products of the component (D) include "Viscoat #1000LT" manufactured by Osaka Organic Chemical Industry Co., Ltd., "NK Ester A-HBR-5" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "Miramer SP1106" manufactured by MIWON, "CN2302," "CN2303," and "CN2304" manufactured by Arkema, and "Photomer 5500" manufactured by IGM.

[0081] The content of the component (D) is not particularly limited within a range that allows the effects of the present invention to be achieved. However, in order to obtain an active energy ray-curable composition capable of forming a lens having a high Abbe number, excellent heat resistance and moist heat resistance, and excellent crack resistance, the content of the component (D) in the active energy ray-curable composition is preferably in the range of 1% by mass to 50% by mass, more preferably in the range of 5% by mass to 40% by mass, and particularly preferably in the range of 10% by mass to 35% by mass.

[0082] The active energy ray-curable composition of the present invention may contain, in addition to the component (A) and the component (B), a compound (E) having one or two (meth)acryloyl groups in one molecule and at least one hydroxyl group in one molecule (hereinafter referred to as "component (E)"), if necessary, for the purpose of further improving moisture and heat resistance.

[0083] Examples of the component (E) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-phenylphenolpropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxy-3-methylbutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate. 3,5-dihydroxy-1-adamantyl acrylate, neopentyl glycol carbonate-modified (meth) acrylate 2-hydroxyethyl, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, di-trimethylolpropane mono(meth)acrylate, di-trimethylolpropane di(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, sorbitol mono(meth)acrylate, sorbitol di(meth)acrylate, mannitol mono(meth)acrylate, mannitol di(meth)acrylate, etc. In addition, compounds in which part or all of the hydroxyl groups of the above compounds are modified with alkylene oxide or caprolactone can also be used. These compounds can be used alone or in combination of two or more. Among these, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, neopentyl glycol carbonate-modified 2-hydroxyethyl (meth)acrylate, and sorbitol ethylene oxide-modified di(meth)acrylate are preferred from the viewpoint of obtaining a further higher Abbe number, heat resistance, and moist heat resistance.

[0084] As the component (E), epoxy (meth)acrylates such as reaction products of a compound having one or two glycidyl groups in one molecule and (meth)acrylic acid, and reaction products of a compound (d) having a (meth)acryloyloxy group and a glycidyl group in one molecule and carboxylic acid and / or dicarboxylic anhydride can also be used.

[0085] Examples of the compound having one or two glycidyl groups in one molecule include: dodecyl glycidyl ether, tetradecyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 1,2-epoxy-4-(4-nitropropane)-1,2-diol ... -Vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, 1,4-cyclohexanedimethanol monoglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 3,4,3,4-diepoxybiscyclohexyl, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bisphenol A monoglycidyl ether, bisphenol A diglycidyl ether, bisphenol A epoxy modified Bisphenol A monoglycidyl ether, bisphenol A alkylene oxide modified diglycidyl ether, bisphenol A caprolactone modified monoglycidyl ether, bisphenol A caprolactone modified diglycidyl ether, hydrogenated bisphenol A monoglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol A alkylene oxide modified monoglycidyl ether, hydrogenated bisphenol A caprolactone modified diglycidyl ether, hydrogenated bisphenol A caprolactone modified monoglycidyl ether, hydrogenated bisphenol A caprolactone modified diglycidyl ether, bisphenol F monoglycidyl ether, bisphenol F diglycidyl ether. Glycidyl ether, bisphenol F alkylene oxide modified monoglycidyl ether, bisphenol F alkylene oxide modified diglycidyl ether, bisphenol F caprolactone modified monoglycidyl ether, bisphenol F caprolactone modified diglycidyl ether, hydrogenated bisphenol F monoglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol F alkylene oxide modified monoglycidyl ether, hydrogenated bisphenol F alkylene oxide modified diglycidyl ether, hydrogenated bisphenol F caprolactone modified monoglycidyl ether, hydrogenated bisphenol F caprolactone modified diglycidyl ether, etc.

[0086] Examples of the compound (d) having a (meth)acryloyloxy group and a glycidyl group in one molecule include glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth)acrylate.

[0087] Examples of the carboxylic acid and / or dicarboxylic anhydride include (meth)acrylic acid, 1,2-cyclohexanedicarboxylic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, succinic anhydride, octenylsuccinic anhydride, tetrapropylene succinic anhydride, and the like. Amber anhydride, 3-dodecenylsuccinic anhydride, 3,3,4,4-tetrahydro-3,3-bifuran-2,2,5,5-tetraone, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, trimellitic anhydride, bis(1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid) 2-acetoxy-1,3-propanediyl, etc.

[0088] Examples of commercially available products of the component (E) include "Miramer M100" and "Miramer M1051" manufactured by Miwon Corporation, "NK Ester 702A," "NK Ester 401P," "NK Ester 701A," and "NK Ester EA-5521" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "HEA," "HPA," "4-HBA," and "Viscoat #540" manufactured by Osaka Organic Chemical Industry Co., Ltd., and "Light Ester HO-250(N)," "Light Ester HOP(N)," "Light Ester HOP-A(N)," "Light Ester HOA(N)," "Light Ester HOB(N)," and "Light Ester EA-5521" manufactured by Kyoeisha Chemical Co., Ltd. "Light Ester G-101P", "Light Ester G-201P", "Light Acrylate HOB-A", "Epoxy Ester M-600A", "HOA-MPE(N)", "New Frontier PGA" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., "KAYARAD R-128H" and "KAYARAD R-167" manufactured by Nippon Kayaku Co., Ltd., "Aronix M-920" and "Aronix M-926" manufactured by Toagosei Co., Ltd., "4HBA" and "CHDMMA" manufactured by Mitsubishi Chemical Corporation, "Placcel HEMAC1", "Resist monomer HMA", and "Resist monomer DHMA" manufactured by Daicel Corporation, etc.

[0089] The content of the component (E) is not particularly limited within a range that allows the effects of the present invention to be achieved. However, in order to obtain an active energy ray-curable composition capable of forming a lens having a high Abbe number and excellent heat resistance and heat and humidity resistance, the content of the component (E) is preferably in the range of 0.5% by mass to 20% by mass, and more preferably in the range of 1% by mass to 15% by mass in the active energy ray-curable composition.

[0090] The active energy ray-curable composition of the present invention may further contain other compounds in addition to the component (A), the component (B), the component (C), the component (D), and the component (E), as needed.

[0091] Examples of the other compounds include (meth)acrylates having a hydroxyl group, and the like. Examples of the (meth)acrylates having a hydroxyl group include pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and alkylene oxide-modified and / or caprolactone-modified compounds of the (meth)acrylates having a hydroxyl group, urethane acrylates, acrylic acid (meth)acrylates, polyester polyol (meth)acrylates, and epoxy acrylates.

[0092] In addition, a hardened material or lens can be obtained by irradiating the active energy ray curable composition of the present invention with active energy ray. The so-called active energy ray refers to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. In the case of irradiating ultraviolet rays as the active energy ray, it is preferred to add a photopolymerization initiator (F) to the active energy ray curable composition of the present invention to improve the curability. On the other hand, when using ionizing radiation such as electron beams, α rays, β rays, and γ rays, the material is cured rapidly even without using a photopolymerization initiator (F), so there is no need to specifically add a photopolymerization initiator (F).

[0093] Examples of the photopolymerization initiator (F) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholinyl(4-thiophene)phenylketone, Acetophenone compounds such as benzoin, benzoin methyl ether, benzoin isopropyl ether, etc.; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoin diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; diphenyldione (dibenzoyl), methyl benzoylformate, 2-(2-hydroxyethoxy)ethyl oxyphenylacetate, oxyphenylacetic acid Benzophenone compounds such as 2-(2-oxo-2-phenylacetoxyethoxy)ethyl ester; benzophenone, methyl o-benzoylbenzoate-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone Benzophenone compounds such as benzophenone; 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; aminobenzophenone compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1-[4-(4-benzoylphenylmercapto)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, etc. These photopolymerization initiators may be used alone or in combination of two or more.

[0094] Examples of commercially available products of the photopolymerization initiator (F) include IGM resin (IGM Resins) company's "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 907", "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad TPO-L", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad Omnirad 754", "Omnirad BP", "Omnirad 4MBZ", "Omnirad 4PBZ", "Omnirad 410", "Omnirad OMBB", "Omnirad BMS", "Omnirad 500", "Omnirad 81", "Omnirad ITX", "Omnirad DETX", "Omnirad MBF", "Omnirad EMK", "Omnirad 784", "Omnirad 1312", "Omnirad BCIM", "Omnirad BL 723", "Omnirad BL 724", "Omnirad BL 750", "Omnirad BL751", "Omnirad EDB", "Omnirad EHA", "Omnirad IADB", "Esacure KIP 150", "Esacure KIP 100F", "Esacure KIP 75LT", "Esacure KIP IT", "Esacure TZT", "Esacure KT55", "Esacure TZM", "Esacure ONE", "Esacure 1001M", "Esacure KIP160", "Esacure A 198", "Esacure KTO46", "Esacure DP 250", "Omnipol 910", "Omnipol 9210", "Omnipol BP", "Omnipol TX", "Omnipol 3TX", "Omnipol BL728", "Omnipol ASA", "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" manufactured by Nippon Kayaku Co., Ltd., and Stauffer Chemical. Examples of the photopolymerization initiators include "Vicure 10" and "Vicure 55" manufactured by Sigma Chemical, "Trigonal P1" manufactured by Akzo Nobel, "SANDORAY 1000" manufactured by Sandoz, "DEAP" manufactured by Upjohn Chemical, "Quantacure PDO," "Quantacure ITX," and "Quantacure EPD" manufactured by Ward Blenkinsop, and "Runtecure 1104" manufactured by Runtec. These photopolymerization initiators may be used alone or in combination of two or more.

[0095] The amount of the photopolymerization initiator (F) used is preferably in the range of 0.05 to 20 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and particularly preferably in the range of 0.5 to 5 parts by mass in the active energy ray-curable composition, from the viewpoint of obtaining sufficient curability.

[0096] The active energy ray-curable composition of the present invention may further contain other additives in addition to the above-mentioned components (A) to (F), as needed.

[0097] Examples of the other additives include polymerization inhibitors, photosensitizers, surface conditioners, antistatic agents, defoamers, viscosity modifiers, light stabilizers, weathering stabilizers, heat stabilizers, UV absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, silica beads, organic beads, and inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, cerium oxide, and antimony oxide. These other additives may be used alone or in combination of two or more. Of these, heat stabilizers and antioxidants are preferably added in order to improve heat resistance and resistance to moist heat.

[0098] Examples of the heat-resistant stabilizer include ethanethiol, 2-methylpropane-2-thiol, n-dodecyl mercaptan, 2,3,3,4,4,5-hexamethylhexane-2-thiol, 2-mercaptoethanol, 4-mercapto-1-butanol, methyl thioglycolate, 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, benzyl mercaptan, 3-methylbenzenethiol, 4-methylbenzenethiol, naphthalene-2-thiol, pyridine-2-thiol, benzimidazole-2-thiol, benzothiazole 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 Thiol, 4,5-dimethyl-O-xylenedithiol, toluene-3,4-dithiol, 4,4'-biphenylthiol, 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, Compounds having a mercapto group such as 5-dithiol, bis(2-mercaptoethyl) ether, trimethylolethane tris(3-mercaptopropionate), trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), 1,3,5-benzenetrichiol, 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 hexa(3-mercaptopropionate), and dipentaerythritol hexa(3-mercaptobutyrate). These heat stabilizers may be used alone or in combination of two or more.

[0099] Examples of commercially available heat-resistant stabilizers include "Thiokalchol 20" manufactured by Kao Corporation, "Karenz MT PE1," "Karenz MT BD1," "Karenz MT NR1," "TPMB," and "TEMB" manufactured by Showa Denko Co., Ltd., and "TMMP," "TEMPIC," "PEMP," "EGMP-4," "DPMP," "TMMP II-20P," and "PEMP II-20P" manufactured by SC Organic Chemical Co., Ltd.

[0100] The amount of the heat-resistant stabilizer used is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and particularly preferably 0.5 to 3 parts by mass in the active energy ray-curable composition from the viewpoint of obtaining sufficient heat resistance.

[0101] Examples of the antioxidant include phenolic antioxidants, phosphite antioxidants, and sulfur antioxidants. These antioxidants may be used alone or in combination of two or more.

[0102] Examples of the phenolic antioxidant include styrenated phenol, 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-bis(octylthiomethyl)-6-methylphenol, 2,2-methylenebis(6-tert-butyl-p-cresol), 2,2-methylenebis(6-tert-butyl-4-ethylphenol), 4,4-Butylenebis(6-tert-butyl-m-cresol), 4,4-thiobis(6-tert-butyl-m-cresol), 2,2-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate][ethylenebis(oxyethylene)], bis[3-[3-(tert-butyl- )-4-hydroxy-5-methylphenyl]propionic acid] 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl), N,N-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxalamide, N,N-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4,6-tris(3,5- di-tert-butyl-4-hydroxybenzyl) mesitylene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], diethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphate, etc.

[0103] Examples of commercially available products of the phenolic antioxidant include "IRGANOX 1010," "IRGANOX 1010FF," "IRGANOX 1035," "IRGANOX 1035FF (W&C)," "IRGANOX 1076," "IRGANOX 1076FD," "IRGANOX 1098," "IRGANOX 1135," "IRGANOX 1330," and "IRGANOX 1520L," all manufactured by BASF. 、"IRGANOX 245","IRGANOX 245FF","IRGANOX 259","IRGANOX 3114","ANTAGE BHT","ANTAGE DAH","ANTAGE DBH","ANTAGE W-300","ANTAGE W-400","ANTAGE W-500","ANTAGE CRYSTAL","ANTAGE SP"manufactured by Kawaguchi Chemical Industry Co., Ltd. "ANTAGE HP-200", "ANTAGE HP-300", "Adekastab AO-20", "Adekastab AO-30", "Adekastab AO-40", "Adekastab AO-50", "Adekastab AO-50F", "Adekastab AO-50T", "Adekastab AO-60", "Adekastab AO-70" and "Adekastab AO-80" manufactured by ADEKA Co., Ltd. "Adekastab AO-60G", "Adekastab AO-80", "Adekastab AO-330", "SUMILIZER GA-80", "SUMILIZER GP", "SUMILIZER MDP-S", "SUMILIZER WX-R", "SUMILIZER WX-RC" manufactured by Sumitomo Chemical Co., Ltd., "Yoshinox BB" manufactured by Mitsubishi Chemical Corporation, and "JC-356" manufactured by Johoku Chemical Industry Co., Ltd.

[0104] Examples of the phosphite-based antioxidant include tris(2-ethylhexyl) phosphite, tridecyl phosphite, triisodecyl phosphite, trilauryl phosphite, tritridecyl phosphite, tristearyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl isodecyl phosphite, diphenyl mono(tridecyl) phosphite, triphenyl phosphite, tricresyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetraphenyldipropylene glycol diphosphite, 4,4-butylenebis(3-methyl-6-tert-butylphenyl di-tridecyl phosphite), tetra(C12-C15 alkyl)-4,4-isopropylidene diphenyl dioxaphosphocin, bis(decyl)pentaerythritol diphosphite, bis(tridecadecyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, hydrogenated bisphenol A-pentaerythritol phosphite polymer, and the like.

[0105] Examples of commercially available products of the phosphite-based antioxidant include "IRGAFOS 168" and "IRGAFOS 168FF" manufactured by BASF, and "Adekastab PEP-8," "Adekastab PEP-36," "Adekastab HP-10," "Adekastab 2112," "Adekastab 2112RG," "Adekastab 1178," "Adekastab 1500," "Adekastab C," and "Adekastab 1500" manufactured by ADEKA Co., Ltd. Adekastab 135A", "Adekastab 3010", "Adekastab TPP", "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. manufactured by Chengbei Chemical Industry Co., Ltd.

[0106] Examples of the sulfur-based antioxidant include didodecyl 3,3-thiodipropionate, ditridecyl 3,3-thiodipropionate, dioctadecyl 3,3-thiodipropionate, and pentaerythritol tetrakis[3-(dodecylthio)propionate].

[0107] Examples of commercially available sulfur-based antioxidants include "IRGANOX PS800FL" and "IRGANOX PS802FL" manufactured by BASF, "Adekastab AO-412S" and "Adekastab AO-503" manufactured by ADEKA Co., Ltd., "KEMINOX PLS" manufactured by Chemipro Kasei Co., Ltd., and "SUMILIZER TP-D" manufactured by Sumitomo Chemical Co., Ltd.

[0108] The amount of the antioxidant used is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and particularly preferably 0.5 to 3 parts by mass in the active energy ray-curable composition from the viewpoint of obtaining sufficient heat resistance.

[0109] As the other additives, inorganic fillers are preferably used to adjust the refractive index or thermal expansion coefficient. Examples of such inorganic fillers include silica particles, zirconium oxide particles, and other particles, each of which can be used alone 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.

[0110] Examples of commercially available products of the silica fine particles include "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", "MIBK-ST", "MIBK-ST-L", "CHO-ST-M", "EAT-ST" manufactured by Nissan Chemical Co., Ltd. ”, “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”, “Epostar KE-E10”, “Epostar KE-E30”, “Epostar KE-E150”, “Epostar KE-W” manufactured by Japan Catalyst Co., Ltd. 10", "Epostar KE-W30", "Epostar KE-W50", "Epostar KE-P10", "Epostar KE-P30", "Epostar KE-P50", "Epostar KE-P100", "Epostar KE-P150", "Epostar KE-P250", "Epostar KE-S10", "Epostar KE-S30", "Epostar KE-S10" and "Epostar KE-S30". "tar)KE-S50", "Epostar KE-S100", "Epostar KE-S150", "Epostar KE-S250", "QSG-10", "QSG-30", "QSG-100", "QSG-170" manufactured by Shin-Etsu Chemical Co., Ltd., "admanano YA010C", "YA050C", "YA100C" manufactured by Admatechs Co., Ltd., "DLSB-001", "DLSB-002" manufactured by Daiken Chemical Industry Co., Ltd., etc.

[0111] Examples of commercially available zirconium oxide microparticles 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 Catalyst Co., Ltd., "SZR-W," "SZR-M," "SZR-CW," "SZR-CM," "SZR-KM," and "SZR-K" manufactured by Sakai Chemical Industry Co., Ltd., and "Daiken Kagaku Co., Ltd." "DLZ-001", "DLZ-007", "DLZ-003U", "DLM-001", and "DLM-002" manufactured by Daiichi Rare Earth Chemical Co., Ltd., "ZSL-10A", "ZSL-10T", "ZSL-20N", and "ZSL-00014" manufactured by Daiichi Rare Earth Chemical Co., Ltd., "Zirconeo-Cw" and "Zirconeo-Ck" manufactured by iTEC, and "TZP-103" manufactured by Dacheng Chemical Co., Ltd.

[0112] As commercially available products of the other microparticles, for example, there are: "TTP-113" and "TTP-1132" manufactured by Daiichi Chemical Industry Co., Ltd. as titanium dioxide microparticles, "DLB-001", "DLB-002" and "DLB-003" manufactured by Daiichi Rare Earth Chemical Industry Co., Ltd. as barium titanate microparticles, "DLAT-001" manufactured by Daiichi Rare Earth Chemical Industry Co., Ltd. as antimony tin oxide microparticles, and "DLIT-001" manufactured by Daiichi Rare Earth Chemical Industry Co., Ltd. as indium tin oxide microparticles.

[0113] Examples of a method for obtaining a cured product of the active energy ray-curable composition include a method of applying the active energy ray-curable composition on a substrate and then irradiating the substrate with active energy rays.

[0114] 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 nitrocellulose; 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; polysulfone; polyethersulfone; and polyetheretherketone. ; Polyimide-based resins such as polyimide and polyetherimide; resin films such as norbornene-based resins (for example, "Zeonor" manufactured by Zeon Co., Ltd. of Japan), modified norbornene-based resins (for example, "Arton" manufactured by JSR Co., Ltd.), and cyclic olefin copolymers (for example, "APEL" manufactured by Mitsui Chemicals, Inc.); semiconductor wafers such as silicon, silicon carbide, silicon nitride, sapphire, aluminum nitride, gallium nitride, gallium phosphide, gallium arsenide, and indium phosphide; glasses such as quartz glass, borosilicate glass, soda-lime glass, silicate glass, and optical glass (crown glass, flint glass), etc.

[0115] Examples of methods for applying the active energy ray-curable composition of the present invention to the substrate include die coating, micro-gravure coating, gravure coating, roll coating, notch wheel coating, air knife coating, kiss coating, spray coating, dip coating, spin coating, brush coating, full-surface coating using a screen, wire bar coating, flow coating, dispenser, inkjet printing, screen printing, and offset printing.

[0116] As described above, the active energy rays used to cure the active energy ray-curable composition 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, examples of devices for irradiating the active energy rays include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, electrodeless lamps (fusion lamps), chemical lamps, blacklight lamps, mercury-xenon lamps, short arc lamps, helium-cadmium lasers, argon lasers, sunlight, and light-emitting diode (LED) lamps.

[0117] The irradiation dose (integrated light dose) of the active energy ray is preferably 100 mJ / cm 2 ~10,000mJ / cm 2 , more preferably 300 mJ / cm 2 ~8,000mJ / cm 2. Furthermore, the irradiation amount of the active energy ray is based on a value measured by a light meter suitable for the desired excitation wavelength. For example, the EYE UV integrated illuminance meter UVPF-A2 series manufactured by Iwasaki Electric Co., Ltd., the ultraviolet light meter C9536 / H9535 series, the C9536 / H9958 series, the C10427 / H10428 series manufactured by Hamamatsu Photonics, the ultraviolet integrated illuminance meter UIT-201, the UIT-250, the UIT-θ series manufactured by Ushio Electric Co., Ltd., etc. can be used. In particular, in the present invention, the integrated light amount measured using the EYE UV integrated illuminance meter UVPF-A2 (PD-365) manufactured by Iwasaki Electric Co., Ltd. is used as the reference.

[0118] The irradiation with the active energy rays may be performed in one step or in two or more steps.

[0119] The film thickness of the cured product of the active energy ray-curable composition of the present invention is preferably in the range of 1 μm to 1000 μm, more preferably in the range of 50 μm to 500 μm, in order to ensure sufficient hardness of the cured product.

[0120] As the refractive index (n d ), preferably in the range of 1.40 to 1.60, more preferably in the range of 1.45 to 1.55. The refractive index of the cured product is a value measured according to the A method of Japanese Industrial Standards (JIS) test method K7142:2014.

[0121] As the Abbe number (ν d ), preferably 53 or more, more preferably in the range of 53 to 60, further preferably in the range of 55 to 59, and particularly preferably in the range of 56 to 58. The Abbe number of the cured product is a value calculated based on the refractive index measured by method A in accordance with JIS test method K7142:2014.

[0122] The light transmittance of the cured product is preferably 85% or higher, more preferably 88% or higher, and particularly preferably 90% or higher at a wavelength of 410 nm, from the perspective of being preferably used in optical lenses. The method for measuring light transmittance is described in detail in the Examples.

[0123] The light transmittance of the cured product after the heat resistance test is preferably within ±5% of the initial light transmittance at a wavelength of 410 nm, more preferably within ±3%, and particularly preferably within ±1%, from the perspective of being suitable for use in optical lenses with reflow resistance. The method for measuring the light transmittance after the heat resistance test is described in detail in the Examples.

[0124] The water absorption rate of the cured product is preferably in the range of 0.1% to 4.0%, more preferably in the range of 0.3% to 3.5%, and particularly preferably in the range of 0.5% to 3.0%, in order to prevent internal defects in the cured product under high temperature and high humidity environments. The water absorption rate of the cured product is a value calculated by adding the dissolved components in water to the measured value using Method C in accordance with JIS Test Method K7209:2000.

[0125] Regarding the moisture and heat resistance of the cured product, a moisture and heat test was conducted under the conditions of 85°C, 85% RH, and 1000 hours to prevent internal defects in the cured product under high temperature and high humidity conditions. The results showed that the cured product preferably exhibited no peeling from the substrate, more preferably no defects at the interface between the cured product and the substrate, and even more preferably no defects within the cured product. The method for evaluating the moisture and heat resistance of the cured product is described in detail in the Examples.

[0126] The lens of the present invention comprises the above-mentioned cured product. In addition, the lens may have an inorganic layer containing an inorganic compound on at least one surface of the cured product, and may further have a substrate, if necessary.

[0127] Furthermore, the lens of the present invention can also be used as a wafer-level lens by imprint molding.

[0128] There are no particular restrictions on the method for manufacturing the lens of the present invention, and any method can be used for manufacturing. For example, the following method can be cited: the active energy ray curable composition is applied to a substrate such as a wafer or glass, and after being formed into a desired shape using a mold, the composition is temporarily cured by irradiating with active energy rays. After demolding the mold, the uncured active energy ray curable composition is cleaned with a solvent through a development process, and then irradiated with active energy rays again for formal curing. Furthermore, if necessary, an inorganic layer containing an inorganic compound is formed on the surface of the cured product by physical vapor deposition or the like. In addition, when the inorganic layer is formed, a pretreatment such as ashing of the surface of the cured product is performed as needed. Finally, the substrate is monolithicized.

[0129] Examples of the solvent include ketone solvents such as methyl ethyl ketone, acetone, isobutyl ketone, cyclopentanone, and cyclohexanone; cyclic ether solvents such as tetrahydrofuran, dioxolane, and dioxane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropyl alcohol, butanol, and propylene glycol monomethyl ether; and glycol ether solvents such as alkanediol monoalkyl ethers, dialkylene glycol monoalkyl ethers, and dialkylene glycol monoalkyl ether acetates. These solvents may be used alone or in combination of two or more.

[0130] The inorganic layer refers to a layer containing an inorganic compound, and generally has functions such as antireflection and scratch resistance.

[0131] Examples of the inorganic compound include metal oxides, composite oxides, metal nitrides, metal fluorides, composite fluorides, silicon oxides, silicon nitrides, and mixtures thereof.

[0132] Examples of the metal include lithium, sodium, magnesium, aluminum, titanium, yttrium, indium, tin, zirconium, niobium, cerium, hafnium, and tantalum.

[0133] When the inorganic layer is used as an anti-reflection film layer, the anti-reflection film layer may be a single layer, but may also include a low refractive index layer and a high refractive index layer. Furthermore, the low refractive index layer and the high refractive index layer may each be a single layer or multiple layers. Furthermore, the lamination order of the low refractive index layer and the high refractive index layer is not particularly limited.

[0134] Examples of the inorganic compound used in the high refractive index layer include lanthanum titanate, zirconium oxide, titanium oxide, tantalum oxide, niobium oxide, hafnium oxide, cerium oxide, yttrium oxide, and mixtures thereof.

[0135] Examples of the inorganic compound used in the low refractive index layer include silicon oxide, silicon nitride, magnesium fluoride, aluminum fluoride, and mixtures thereof.

[0136] The inorganic layer is formed by forming a film on the surface of the resin layer. The method for forming the inorganic layer is not particularly limited, and any known film-forming method can be used as appropriate. However, it is preferably formed by physical vapor deposition (physical vapor deposition (PVD)) or chemical vapor deposition (chemical vapor deposition (CVD)).

[0137] From the viewpoint of consistency and simplification of the film formation process, the film formation method is more preferably physical vapor deposition (PVD), and examples thereof include vacuum deposition, ion plating, and sputtering.

[0138] As the vacuum deposition, for example, a resistance heating method, a high-frequency induction heating method, an electron beam heating method, or the like can be used.

[0139] The sputtering method may be direct current (DC) sputtering, radio frequency (RF) sputtering, magnetron sputtering, or ion beam sputtering. Furthermore, it may be a parallel plate target method or an opposed target method. Examples of gases introduced into the vacuum chamber include argon, krypton, oxygen, and nitrogen, each of which may be used alone or in combination.

[0140] The thickness of the inorganic layer can be appropriately adjusted according to the target function. When the anti-reflection function is the purpose, it is preferably in the range of 10nm to 5,000nm. From the perspective of the film strength and productivity of the inorganic layer, it is more preferably in the range of 100nm to 2,000nm, and particularly preferably in the range of 250nm to 1,000nm.

[0141] From the viewpoint of interlayer adhesion with the inorganic layer, the pretreatment by ashing of the surface of the cured product may be performed by methods such as photoexcitation ashing and plasma ashing, or these methods may be used in combination.

[0142] Regarding the adhesion between the inorganic layer and the cured product, from the perspective of suppressing peeling of the inorganic layer, the remaining area ratio of the inorganic layer after peeling of a 100-mesh grid of 1 mm width cellophane tape is preferably 50% or more, more preferably 70% or more, and particularly preferably 90% or more. Furthermore, the evaluation method for the remaining rate of the inorganic layer is described in detail in the Examples.

[0143] As for the crack resistance of the inorganic layer, from the perspective of suppressing crack formation in the inorganic layer, it is preferred that no cracks be observed on the surface of the inorganic layer after film formation, and more preferably no cracks be observed on the surface of the inorganic layer after reflow. Furthermore, the evaluation method for the crack resistance of the inorganic layer will be described in detail in the Examples.

[0144] As described above, the cured product formed from the active energy ray-curable composition of the present invention has a high Abbe number and high light transmittance, excellent heat resistance and resistance to heat and moisture, and the inorganic layer formed on the surface of the cured product has excellent crack resistance and excellent adhesion to the inorganic layer. Moreover, the composition can be easily cured by irradiation with active energy rays, and therefore can be preferably used in lens production by photoimprinting.

[0145] Example

[0146] Hereinafter, the present invention will be described in more detail with reference to examples.

[0147] In addition, in this Example, the weight average molecular weight (Mw) is a value measured using gel permeation chromatography (GPC) under the following conditions.

[0148] Measuring device: HLC-8220 manufactured by Tosoh Corporation

[0149] Column: Protective column H manufactured by Tosoh Co., Ltd. XL -H

[0150] +TSKgel G5000HXL manufactured by Tosoh Corporation

[0151] +TSKgel G4000HXL manufactured by Tosoh Corporation

[0152] +TSKgel G3000HXL manufactured by Tosoh Corporation

[0153] +TSKgel G2000HXL manufactured by Tosoh Corporation

[0154] Detector: RI (differential refractometer)

[0155] Data processing: SC-8010 manufactured by Tosoh Corporation

[0156] Measurement conditions: column temperature 40°C

[0157] Solvent tetrahydrofuran

[0158] Flow rate 1.0ml / min

[0159] Standard: Polystyrene

[0160] Sample: A tetrahydrofuran solution containing 0.4% by mass in terms of resin solid content was filtered using a microfilter (100 μl)

[0161] [Synthesis Example 1: Production of Compound (D-1) Having Acryloyl Group and Multibranched Structure]

[0162] A reactor equipped with a thermometer, a stirring rod, a Dean-Stark apparatus, and an air inlet was charged with 134 parts by mass (1 mol) of pentaerythritol-ethylene oxide adduct, 17 parts by mass (0.1 mol) of p-toluenesulfonic acid, and 200 parts by mass of toluene. The reactor was heated to an internal temperature of 110°C while stirring. Next, while maintaining the internal temperature at 110°C, 1,073 parts by mass (8 mol) of dimethylolpropionic acid was added to the reaction system in four portions every two hours. The reaction was allowed to proceed for 10 hours while simultaneously removing the generated water. The reaction mixture was then cooled, and 1,081 parts by mass (15 mol) of acrylic acid, 1.24 parts by mass (10 mmol) of methoxyphenol, 34 parts by mass (0.2 mol) of p-toluenesulfonic acid, and 500 parts by mass of toluene were added to the reactor. Air was then blown into the reaction solution, and the reactor was heated to an internal temperature of 110°C while stirring. The generated water was removed while maintaining the internal temperature, and the reaction was allowed to proceed for 8 hours. Next, the mixture was neutralized with a 20% by mass aqueous sodium hydroxide solution, extracted and washed three times with brine, and unreacted acrylic acid and toluene were distilled off under reduced pressure to obtain a compound (D-1) having an acryloyl group and a multi-branched structure. The compound (D-1) had a weight average molecular weight of 2200 g / mol and an ester value of 200 mgKOH / g.

[0163] [Example 1]

[0164] A siloxane compound ("KR-513" manufactured by Shin-Etsu Chemical Co., Ltd.) as component (A) was mixed; 10 parts by mass of polycarbonate diol diacrylate ("UM-90(1 / 3)DA" manufactured by Ube Industries, Ltd.: R in the general formula (1) is 10 parts by mass of polycarbonate diol diacrylate) as component B was mixed; 2 is a hydrogen atom, R 3 (a) a straight-chain hydrocarbon group having 6 carbon atoms and a cyclohexane structure randomly independently of each other, and n is 4 to 5); 50 parts by mass of polyethylene glycol diacrylate ("A-400" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) as the component (C); 20 parts by mass of a compound (D-1) having an acryloyl group and a multi-branched structure as the component (D); 30 parts by mass of 1-hydroxycyclohexyl phenyl ketone ("I-184" manufactured by BASF) as the component (F); and 1 part by mass of the mixture were heated to 50° C. and stirred and mixed at 1,000 rpm for 10 minutes using a homodisperse to prepare an active energy ray-curable composition.

[0165] [Example 2 to Example 14, Comparative Example 1 to Comparative Example 8]

[0166] Active energy ray-curable compositions were prepared in the same manner as in Example 1, except that the types and / or amounts of (A), (B), (C), (D), and (E) were changed as shown in Tables 1 to 3. Furthermore, KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.; methyltrimethoxysilane; no (meth)acryloyl group), KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.; 3-acryloyloxypropyltrimethoxysilane; one (meth)acryloyl group), and KBM-5803 (manufactured by Shin-Etsu Chemical Co., Ltd.; methacryloyloctyltrimethoxysilane; one (meth)acryloyl group) prepared in Comparative Examples 6 to 8 described in Table 3 do not correspond to component (A) of the present application and were used as comparative components.

[0167] [Method for measuring refractive index]

[0168] The active energy ray-curable compositions obtained in Examples and Comparative Examples were poured into a triangular prism mold (5 mm thick, 10 mm long on one side) and irradiated with 3,000 mJ / cm using a conveyor-type ultraviolet irradiation device (120 W metal halide lamp) manufactured by EyeGraphics Co., Ltd. 2 The triangular prism was made by ultraviolet light. The refractive index of the obtained triangular prism at 25°C, d-line, F-line, and C-line was measured using a Kalnew precision refractometer "KPR-3000" manufactured by Shimadzu Corporation. d )The closest refractive index (n d ) of the matching fluid.

[0169] [Calculation method of Abbe number]

[0170] The Abbe number (ν d ).

[0171]

[0172] [Measurement method of transmittance]

[0173] The active energy ray-curable compositions obtained in Examples and Comparative Examples were dripped onto glass plates that had been subjected to a mold release treatment using octadecyltrichlorosilane. 1 mm thick spacers were placed on both sides of the oil droplet as spacers. The oil droplet was then sandwiched between the glass plates that had also been subjected to a mold release treatment using 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 using a UV-LED irradiation device "LHPUV365 / 2501" manufactured by Iwasaki Electric Co., Ltd.2 , cumulative light intensity 8000mJ / cm 2 The coin-shaped cured product having a thickness of approximately 1 mm was obtained. The coin-shaped cured product was heated in a forced air 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.

[0174] [Measurement method of transmittance after heat resistance test]

[0175] After heating the coin-shaped cured product measured in the transmittance measurement method (1) at 175°C for 10 minutes in a forced air oven, the transmittance at a wavelength of 410 nm was measured using a UV-visible-near-infrared spectrophotometer "V-770" manufactured by JASCO Corporation as transmittance after heat resistance test 1 and transmittance after heat resistance test 2. The heating temperature was 175°C, which was set based on the temperature of the reflow process of low-temperature melting solder and normal melting solder.

[0176] [Measurement method of water absorption]

[0177] The active energy ray-curable compositions obtained in Examples and Comparative Examples were applied to an acrylic plate using a 0.5 mm thick backing plate and a glass rod. The plates were then irradiated with a conveyor-type ultraviolet irradiation device (120 W metal halide lamp) manufactured by EyeGraphics Co., Ltd. at a cumulative light intensity of 3,000 mJ / cm 2 The obtained sheet-like cured product was irradiated with ultraviolet light to obtain a film thickness of 0.2 mm. The obtained sheet-like cured product was cut into 5 cm long x 5 cm wide pieces using a dumbbell cutter to prepare a test piece for measuring water absorption. The prepared test piece was dried in a forced air oven at 50°C for 24 hours, and the weight of the test piece was measured and set as the initial weight m1. After measuring the initial weight, it was immersed in 300 ml of pure water at 23°C for 24 hours. The residual moisture on the test piece extracted from the pure water was wiped with a non-woven fabric "bemcot" manufactured by Asahi Kasei Corporation, and the weight of the test piece was measured and set as the weight after immersion m2. After measuring the weight after immersion, the test piece was dried in a forced air oven at 50°C for 24 hours, and the weight of the test piece was measured and set as the dry weight m3. Using the above m1 to m3, the water absorption rate was calculated according to the following formula.

[0178]

[0179] [Evaluation method for moist heat resistance]

[0180] The active energy ray-curable compositions obtained in Examples and Comparative Examples were dropped onto a cover glass that had been subjected to a contact treatment using a silane coupling agent "KBM-5103" manufactured by Shin-Etsu Chemical Co., Ltd., and after forming a lens replica, the active energy ray-curable compositions were irradiated with an intensity of 50 mW / cm using a UV-LED irradiation device "LHPUV365 / 2501" manufactured by Iwasaki Electric Co., Ltd. 2 , cumulative light intensity 450mJ / cm 2 After demolding the lens replica, it was developed with propylene glycol monomethyl ether to remove the uncured resin composition. 2 After the formal curing, the wafer-level lens was post-baked at 100°C for 90 minutes in a forced air oven to obtain a wafer-level lens. The obtained wafer-level lens was subjected to a 1000-hour heat and humidity test at 85°C and 85% relative humidity using a small environmental tester "SH-222" manufactured by Espec Co., Ltd. After the test, the lens was observed using a microscope "VHX900" manufactured by Keyence Co., Ltd. and a laser microscope "OLS5000" manufactured by Olympus Co., Ltd., and evaluated according to the following criteria.

[0181] ◎: No peeling, interface defects, or internal defects were observed.

[0182] ○: No peeling or interface defects were observed, but there were approximately 1 to 10 internal defects.

[0183] △: The degree of peeling, interface abnormality, and internal defects is moderate.

[0184] ×: Peeling, interface abnormality, and serious internal defects.

[0185] [Evaluation method for crack resistance]

[0186] Wafer-level lenses were produced using the same lens production procedure as described in the method for evaluating heat and moisture resistance. Sputtering was performed using a Shimadzu Corporation ternary magnetron sputtering system "HSR-522" under the following conditions: a target of SiO2, an argon gas flow rate of 15 sccm, a room temperature of 25°C, and a sputtering time of 40 minutes. A laminate was obtained in which a 0.5 μm thick silicon oxide thin film was laminated on the surface of the cured product. The surface of the laminate was observed using a Keyence Corporation "VHX900" microscope, and the initial appearance of the laminate was evaluated according to the following criteria. Subsequently, after heat treatment at 175°C for 5 minutes in a forced air oven, the surface of the laminate was observed using a Keyence Corporation "VHX900" microscope, and the appearance of the laminate after heat resistance was evaluated according to the following criteria.

[0187] ⊚: No cracks or wrinkles were observed in the sputtered film.

[0188] ○: Very slight cracks and wrinkles occurred in the sputtered film.

[0189] Δ: Slight cracks and wrinkles occurred in the sputtered film.

[0190] ×: Cracks and wrinkles occurred in the sputtered film.

[0191] [Evaluation method for adhesion]

[0192] The active energy ray-curable compositions obtained in Examples and Comparative Examples were dripped onto glass sheets that had been subjected to a contact treatment using a silane coupling agent "KBM-5103" manufactured by Shin-Etsu Chemical Co., Ltd. After placing 0.5 mm thick spacers on both sides of the oil droplet as spacers, the oil droplet was sandwiched between glass sheets that had been subjected to a mold release treatment using octadecyltrichlorosilane. The oil droplet of the active energy ray-curable composition sandwiched between the two glass sheets was irradiated with an irradiation intensity of 50 mW / cm using a UV-LED irradiation device "LHPUV365 / 2501" manufactured by Iwasaki Electric Co., Ltd. 2 , cumulative light intensity 8000mJ / cm 2The mold-released glass plate was peeled off and heated in a forced-air oven at 100°C for 90 minutes to obtain a flat film-like cured product approximately 0.5 mm thick. The resulting flat film-like cured product was sputtered using a Shibaura Mechatronics Co., Ltd. CFS-12P-100 sputtering system using a SiO2 target, argon (gas flow rate 27 sccm) and oxygen (gas flow rate 3 sccm), room temperature 25°C, and sputtering time 26 minutes. The result was a laminate with a 0.1 μm-thick silicon oxide thin film laminated on the surface of the flat film-like cured product. Eleven vertical and horizontal cracks were cut into the surface of the laminate using a cutter and a cutter guide at 1 mm intervals, creating a 100-mesh checkerboard pattern. Next, one end of a 3M cellophane tape (Scotch 610), cut into 8 cm lengths, was placed firmly against the grid surface. The other end was then momentarily pulled vertically to peel the inorganic film. The laminate surface after peeling was observed using an Olympus laser microscope (OLS5000). The remaining area of ​​the inorganic film remaining on the grid was evaluated according to the following criteria.

[0193] 5: The residual area ratio is 90% or more.

[0194] 4: The residual area ratio is in the range of 70% to 89%.

[0195] 3: The residual area ratio is in the range of 50% to 69%.

[0196] 2: The residual area ratio is in the range of 20% to 49%.

[0197] 1: The residual area ratio is in the range of 1% to 19%.

[0198] 0: The residual area ratio is 0%.

[0199]

[0200]

[0201]

[0202] The abbreviations in Tables 1 to 3 are as follows.

[0203] "X-12-1048";

[0204] Acryloyl-modified polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0205] "X-40-2761";

[0206] Acryloyl-modified polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0207] "4-HBA";

[0208] 4-Hydroxybutyl acrylate (manufactured by Mitsubishi Chemical Corporation)

[0209] The evaluation results in Tables 1 to 3 clearly demonstrate that the cured products formed from the active energy ray-curable compositions of Examples 1 to 14 of the present invention exhibit high Abbe numbers, high heat resistance, controlled water absorption to below 4%, and high resistance to moist heat. Furthermore, the lens samples of Examples 1 to 14 exhibited no post-curing warping, cracking, or breakage, and exhibited excellent appearance. Furthermore, it was demonstrated that the laminates exhibited minimal cracking and wrinkling, both initially and after heat resistance testing. Furthermore, Examples 1 to 14 demonstrated high interlayer adhesion with the inorganic layer.

[0210] On the other hand, Comparative Examples 1 and 2 are examples of active energy ray-curable compositions that do not contain the component (A) specified in the present invention, but it was confirmed that the interlayer adhesion with the inorganic layer was insufficient.

[0211] In addition, Comparative Examples 3 and 4 are examples of active energy ray-curable compositions in which the amount of component (A) specified in the present invention was increased to 50 parts by mass. However, it was confirmed that interface abnormalities and internal defects occurred during the moisture and heat resistance test, resulting in insufficient moisture and heat resistance. Wrinkles and cracks occurred in the appearance after the heat resistance test, indicating that the crack resistance was clearly insufficient.

[0212] Comparative Example 5 is an example of an active energy ray-curable composition not containing the component (B) specified in the present invention. However, the transmittance decreased in the heat resistance test, indicating insufficient heat resistance. Cracks occurred in the laminate after the heat resistance test, indicating insufficient crack resistance.

[0213] Comparative Examples 6 to 8 are examples of active energy ray-curable compositions containing silane compounds that do not comply with the (A) component specified in the present invention. However, it was confirmed that wrinkles and cracks appeared on the surface of the laminated body after the heat resistance test, the crack resistance was significantly insufficient, and the interlayer adhesion with the inorganic layer was insufficient.

Claims

1. An active energy ray-curable composition comprising a compound having a (meth)acryloyl group, wherein the active energy ray-curable composition comprises: Compound (A) has, in one molecule, at least one structure selected from the group consisting of the following general formula (1), general formula (2), and general formula (3) and two or more (meth)acryloyl groups; Polycarbonate diol di(meth)acrylate (B) is represented by the following general formula (4); A compound (C) having one or two (meth)acryloyl groups and an alkanediol structure in one molecule; and A compound (D) having six or more (meth)acryloyl groups and a multi-branched structure in one molecule, The component (A) is contained in an amount of 5 to 30% by mass relative to 100% by mass of the total mass of the compounds having a (meth)acryloyl group other than the component (A), The active energy ray-curable composition comprises 20% by mass to 50% by mass of the component (B), The active energy ray-curable composition comprises 5% by mass to 20% by mass of the component (C), The active energy ray-curable composition comprises 30% by mass to 40% by mass of the component (D), Where R 1 Each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a (meth)acryloyloxyalkyl group, or a (meth)acryloyloxyalkyloxy group; X represents a methylene group or an oxygen atom, Where R 2 Each independently represents a hydrogen atom or a methyl group, R 3 Each independently represents a hydrocarbon group having 1 to 10 carbon atoms; and n is an integer of 1 to 10.

2. The active energy ray-curable composition according to claim 1, wherein R in the general formula (4) 3 Each independently represents a linear hydrocarbon group having 5 to 6 carbon atoms, a cyclohexane structure, or an isosorbide structure. 3 . The active energy ray-curable composition according to claim 1 , wherein the alkanediol structure is at least one selected from the group consisting of ethylene glycol, propylene glycol, and neopentyl glycol. 4 . The active energy ray-curable composition according to claim 1 , wherein the number of repeating units of the alkanediol structure is an integer of 2 to 15. The active energy ray-curable composition according to claim 1 , wherein the multi-branched structure is at least one selected from the group consisting of a dendritic structure, a tree structure, a hyperbranched structure, and a star structure.

6. The active energy ray-curable composition according to claim 1 or 2, further comprising a compound (E) having one or two (meth)acryloyl groups in one molecule and one or more hydroxyl groups in one molecule, The compound (E) is at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, neopentyl glycol carbonate-modified 2-hydroxyethyl (meth)acrylate, and ethylene oxide-modified sorbitol di(meth)acrylate. 7 . A cured product comprising the active energy ray-curable composition according to claim 1 .

8. A lens, characterized in that: A cured product according to claim 7.

9. A wafer-level lens, characterized in that: A cured product according to claim 7.

10. A lens, characterized in that: A cured product according to claim 7 having an inorganic compound layer provided on at least one surface thereof. The lens according to claim 10 , wherein the inorganic compound layer is an anti-reflection layer.

12. A camera module, characterized in that: A lens according to claim 10 or 11.

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