Curable resin composition, cured film, and imaging device

Abstract

To provide a curable resin composition capable of forming a cured film having a high refractive index and good heat resistance. [Solution] A curable resin composition is provided that contains titanium dioxide particles, a resin, and a silane coupling agent. The content of titanium dioxide particles is greater than 60% by mass and less than 90% by mass, based on the total amount of solids in the curable resin composition.

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition, a cured film, and an imaging device. [Background technology]

[0002] Lenses, which are optical components used in optical instruments, function to collect and focus light, and play an important role in fields such as imaging and sensing. For example, Patent Document 1 discloses a curable resin composition for forming lenses. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2016-164674 [Overview of the project] [Problems that the invention aims to solve]

[0004] The main objective of this invention is to provide a curable resin composition capable of forming a cured film having a high refractive index and good heat resistance. [Means for solving the problem]

[0005] The present invention provides the curable resin composition described in [1], the cured film described in [2], and the imaging device described in [3]. [1] Contains titanium dioxide particles, resin, and silane coupling agent, A curable resin composition in which the content of titanium dioxide particles is greater than 60% by mass and less than 90% by mass, based on the total amount of solids in the curable resin composition. A cured film formed from the curable resin composition described in [2][1]. An imaging apparatus comprising the cured film described in [3][2]. [Effects of the Invention]

[0006] The present invention provides a curable resin composition capable of forming a cured film having a high refractive index and good heat resistance. Furthermore, the present invention provides a cured film formed from such a curable resin composition. Moreover, the present invention provides an imaging device containing such a cured film. [Modes for carrying out the invention]

[0007] The embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments described below.

[0008] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages within this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this specification, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples.

[0009] In this specification, (meth)acrylic acid means acrylic acid or the corresponding methacrylic acid. The same applies to other similar expressions such as (meth)acryloyl group and (meth)acrylate.

[0010] In this specification, unless otherwise specified, the materials exemplified below may be used individually or in combination of two or more, to the extent that the conditions are met. The content of each component refers to the total amount of multiple substances corresponding to each component, unless otherwise specified.

[0011] [Curable resin composition] The curable resin composition of the present embodiment contains titanium oxide particles (A), a resin (B), and a silane coupling agent (C). The curable resin composition of the present embodiment may further contain a polymerization initiator (D), a polymerization initiation assistant (E), a solvent (F), a leveling agent (G), an antioxidant (H), and other components. The curable resin composition of the present embodiment can be suitably used for forming lenses (especially, metal lenses).

[0012] <Titanium oxide particles (A)> The curable resin composition contains titanium oxide (TiO2) particles (A). By the curable resin composition containing titanium oxide particles (A), it becomes possible to increase the refractive index of the obtained cured film.

[0013] The titanium oxide particles (A) are preferably rutile-type titanium oxide particles. Rutile-type titanium oxide tends to have a larger refractive index compared to titanium oxide having other crystal structures (for example, anatase type, brookite type), and it becomes possible to further increase the refractive index of the obtained cured film. Discrimination of the crystal structure of titanium oxide can be performed, for example, by X-ray diffraction (XRD) measurement.

[0014] Examples of commercially available rutile-type titanium oxide particles include LDB-142 (manufactured by Ishihara Sangyo Co., Ltd.), ST-485SA15, ST-605EC (manufactured by Titanium Industry Co., Ltd.), and the like.

[0015] The titanium oxide particles (A) may be surface-treated with an organic substance, an inorganic substance, or the like from the viewpoint of dispersibility in the curable resin composition. Examples of the organic substance include organosilicon compounds such as silane coupling agents. Examples of the inorganic substance include aluminum oxide, silicon dioxide, and zirconium dioxide.

[0016] The average particle size of the titanium dioxide particles (A) is preferably 1 nm or larger, more preferably 5 nm or larger, and even more preferably 10 nm or larger, from the viewpoint of re-aggregation properties, and preferably 1000 nm (1 μm) or smaller, more preferably 500 nm (0.5 μm) or smaller, and even more preferably 100 nm (0.1 μm) or smaller, from the viewpoint of sedimentation properties.

[0017] In this specification, the average particle diameter of titanium oxide particles (A) refers to the particle size at 50% of the integrated value in the particle size distribution determined by laser diffraction-scattering. The average particle diameter is the average particle diameter of all titanium oxide particles (A), including primary and secondary particles.

[0018] The content of titanium dioxide particles (A) is greater than 60% by mass and less than 90% by mass, based on the total amount of solids in the curable resin composition. When the content of titanium dioxide particles (A) exceeds 60% by mass, based on the total amount of solids in the curable resin composition, the refractive index of the resulting cured film can be sufficiently increased. When the content of titanium dioxide particles (A) is less than 90% by mass, based on the total amount of solids in the curable resin composition, it is possible to suppress the haze of the resulting cured film from becoming too high. The content of titanium dioxide particles (A) may be 62% by mass or more, 65% by mass or more, 68% by mass or more, 70% by mass or more, or 72% by mass or more, based on the total amount of solids in the curable resin composition, and may also be 88% by mass or less, 85% by mass or more, or 82% by mass or less.

[0019] In this specification, the solid content of a curable resin composition refers to the total amount of components remaining after removing the solvent from the curable resin composition. The total amount of solid content of a curable resin composition and the content of each component thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0020] <Resin (B)> The curable resin composition contains resin (B). Resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of resin (B) include resins [K1], [K2], [K3], [K4], [K4'], [K5], and [K6]. Resin (B) is preferably at least one selected from the group consisting of resins [K1], [K2], [K3], [K4], [K4'], [K5], and [K6]. From the viewpoint of a high refractive index of the cured film, resin (B) may contain [K4] and / or [K4']. From the viewpoint of heat resistance of the cured film, resin (B) may contain resin [K6].

[0021] Resin [K1]: A copolymer having structural units derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes simply referred to as "(a)") and structural units derived from monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes simply referred to as "(b)"); Resin [K2]: A copolymer having structural units derived from (a) and structural units derived from (b) and a monomer (c) copolymerizable with (a) (however different from (a) and (b)) (hereinafter sometimes simply referred to as "(c)"); Resin [K3]: A copolymer having structural units derived from (a) and structural units derived from (c); Resin [K4]: A copolymer having structural units derived from (a) to which (b) is added, and structural units derived from (c), and containing structural units derived from (a) to which (b) is not added; Resin [K4']: A copolymer having structural units derived from (a) to which (b) is added, and structural units derived from (c), and not containing structural units derived from (a) to which (b) is not added; Resin [K5]: A copolymer having structural units obtained by adding (a) to structural units derived from (b) and structural units derived from (c) (it may also contain structural units derived from (b) to which (a) is not added, but it is preferable that it is not included). Resin [K6]: A copolymer having structural units obtained by adding (a) to a structural unit derived from (b), and further adding a carboxylic acid anhydride, and structural units derived from (c).

[0022] Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, p-vinylbenzoic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid; Bicyclounsaturated compounds containing carboxyl groups, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; Unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride; Unsaturated mono(meth)acryloyloxyalkyl) esters of divalent or higher polycarboxylic acids such as mono(2-(meth)acryloyloxyethyl) succinate and mono(2-(meth)acryloyloxyethyl) phthalate; Unsaturated acrylates containing both a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid; These are some examples.

[0023] Among these, acrylic acid, methacrylic acid, or maleic anhydride are preferred in terms of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

[0024] (b) may be a monomer having, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Preferably, (b) is a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0025] Examples of (b) include monomers having an oxyranyl group and an ethylenically unsaturated bond (b1) (hereinafter sometimes simply referred to as "(b1)"), monomers having an oxetanyl group and an ethylenically unsaturated bond (b2) (hereinafter sometimes simply referred to as "(b2)"), and monomers having a tetrahydrofuryl group and an ethylenically unsaturated bond (b3) (hereinafter sometimes simply referred to as "(b3)").

[0026] Examples of (b1) include monomers having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized (b1-1) (hereinafter sometimes simply referred to as "(b1-1)") and monomers having a cyclic unsaturated hydrocarbon structure that has been epoxidized (b1-2) (hereinafter sometimes simply referred to as "(b1-2)").

[0027] (b1-1) includes glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, α-methyl-o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2 Examples include 4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, and 4-hydroxybutyl acrylate glycidyl ether.

[0028] Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celoxide 2000, manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400, manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100, manufactured by Daicel Corporation), compounds represented by formula (BI), compounds represented by formula (BII), etc.

[0029] [ka]

[0030] In equations (BI) and (BII), R e and R f This represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X eand X f is a single bond, *-R g -, *-R g -O-, *-R g -S-, or *-R g -NH-. R g represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond to O.

[0031] Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, etc.

[0032] Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc.

[0033] R e and R f are preferably a hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group, or 2-hydroxyethyl group, more preferably a hydrogen atom or methyl group.

[0034] Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, etc.

[0035] X e and X f are preferably a single bond, methylene group, ethylene group, *-CH2-O-, or *-CH2CH2-O-, more preferably a single bond or *-CH2CH2-O- (* represents a bond to O).

[0036] Compounds represented by formula (BI) include those represented by formulas (BI-1) to (BI-15). Among these, the compounds represented by formula (BI) are preferably those represented by formulas (BI-1), (BI-3), (BI-5), (BI-7), (BI-9), or (BI-11) to (BI-15), and more preferably those represented by formulas (BI-1), (BI-7), (BI-9), or (BI-15).

[0037] [ka]

[0038] Compounds represented by formula (BII) include those represented by formulas (BII-1) to (BII-15). Among these, the compounds represented by formula (BII) are preferably those represented by formulas (BII-1), (BII-3), (BII-5), (BII-7), (BII-9), or (BII-11) to (BII-15), and more preferably those represented by formulas (BII-1), (BII-7), (BII-9), or (BII-15).

[0039] [ka]

[0040] The compound represented by formula (BI) and the compound represented by formula (BII) may be used individually or in combination of two or more. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, their content ratio [compound represented by formula (BI):compound represented by formula (BII)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20, on a molar basis.

[0041] (b2) is more preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. Examples of (b2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane.

[0042] (b3) is more preferably a monomer having a tetrahydrofurfuryl group and a (meth)acryloyloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0043] (b) is preferable to (b1) in that it can further improve the reliability of the resulting cured film in terms of heat resistance, chemical resistance, etc. Furthermore, (b) is preferable to (b1-2) in that it provides excellent storage stability for the curable resin composition.

[0044] (c) includes (meth)acrylic acid ester monomers, unsaturated carboxylic acid esters such as unsaturated dicarboxylic acid esters; vinyl monomers having an unsaturated aliphatic hydrocarbon ring, an unsaturated heterocycle, or an aromatic ring.

[0045] Examples of (meth)acrylic acid ester monomers include: (Meth)acrylic acid esters having linear or branched aliphatic saturated hydrocarbon groups, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; (Meth)acrylic acid esters having straight-chain or branched aliphatic unsaturated hydrocarbon groups, such as allyl (meth)acrylate and propargyl (meth)acrylate; Cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 (Meth)acrylic acid esters having cyclic saturated hydrocarbon groups, such as decane-8-yl(meth)acrylate (sometimes referred to as "dicyclopentanyl(meth)acrylate" or "tricyclodecyl(meth)acrylate" in the relevant technical field), isobornyl(meth)acrylate, and adamantyl(meth)acrylate; Tricyclo[5.2.1.0 2,6 (meth)acrylic acid esters having cyclic unsaturated aliphatic hydrocarbon groups, such as decen-8-yl (meth)acrylate (commonly known in the art as "dicyclopentenyl (meth)acrylate") and dicyclopentanyloxyethyl (meth)acrylate; Aromatic ring-containing (meth)acrylic acid esters such as phenyl(meth)acrylate, naphthyl(meth)acrylate, benzyl(meth)acrylate, and phenoxybenzyl(meth)acrylate; Hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Active methylene-containing (meth)acrylic acid esters such as 2-(acetoacetoxy)ethyl methacrylate; These are some examples.

[0046] Examples of unsaturated dicarboxylic acid esters include diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0047] Among these, unsaturated carboxylic acid esters are preferred, C acrylates such as methyl (meth)acrylate and 2-ethylhexyl (meth)acrylate.1-10 Alkyl (meth)acrylate; Tricyclo[5.2.1.0 2,6 (meth)acrylic acid esters having cyclic saturated hydrocarbon groups, such as decane-8-yl(meth)acrylate; Tricyclo[5.2.1.0 2,6 (meth)acrylic acid esters having cyclic unsaturated aliphatic hydrocarbon groups, such as decen-8-yl(meth)acrylate; (Meth)acrylic acid esters having aromatic rings, such as benzyl (meth)acrylate and phenoxybenzyl (meth)acrylate; That is the case.

[0048] Examples of vinyl monomers having an unsaturated aliphatic hydrocarbon ring include bicyclo[2.2.1]hept-2-ene (sometimes referred to as "2-norbornene"), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, and 5-(2'-Hy 5-Droxyethyl)bicyclo[2.2.1]hept-2-ene, 5-Methoxybicyclo[2.2.1]hept-2-ene, 5-Ethoxybicyclo[2.2.1]hept-2-ene, 5,6-Dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-Di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-Di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5, 6-Dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-Diethoxybicyclo[2.2.1]hept-2-ene, 5-Hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-Hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-Hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-Tert-Butoxycarbonylbicyclo[2.2.1 Examples include bicyclounsaturated compounds such as hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene.

[0049] Examples of vinyl monomers having unsaturated heterocycles include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and dicarbonylimide derivatives such as N-(9-acridinyl)maleimide.

[0050] Examples of vinyl monomers having aromatic rings include styrene-based monomers such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene; and vinyl monomers having condensed rings such as N-vinylcarbazole.

[0051] Other vinyl monomers are preferably, Nitrile group-containing monomers such as acrylonitrile and methacrylonitrile; Halogen atom-containing monomers such as vinyl chloride and vinylidene chloride; Acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. That is the case.

[0052] Among these, vinyl monomers are preferred in terms of copolymerization reactivity and heat resistance. Styrene-based monomers such as styrene and vinyltoluene; Dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide; Bicyclounsaturated compounds such as bicyclo[2.2.1]hept-2-ene (or sometimes referred to as "2-norbornene"); Active methylene-containing (meth)acrylic acid esters such as 2-(acetoacetoxy)ethyl methacrylate; Vinyl monomers having a condensed ring, such as N-vinylcarbazole; Therefore, from the viewpoint of the high refractive index of the cured film, a vinyl monomer having a condensed ring is more preferable.

[0053] "A structural unit obtained by adding (b) to a structural unit derived from (a)" means a unit formed by adding (b) to a structural unit derived from (a) that constitutes the main chain of the copolymer. The structural unit has a pendant unsaturated group derived from (b). In the structural unit, (a) may be any of the above examples, and (b) may also be any of the above examples. (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid. (b) is preferably a monomer (b1) having an oxiranil group and an ethylenically unsaturated bond, more preferably a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized.

[0054] "A structural unit obtained by adding (a) to a structural unit derived from (b)" means a unit formed by adding (a) to a structural unit derived from (b) that constitutes the main chain of the copolymer. The structural unit has a pendant unsaturated group derived from (a). In the structural unit, (b) may be any of the above examples, and (a) may also be any of the above examples. (b) is preferably a monomer (b1) having an oxiranil group and an ethylenically unsaturated bond, and more preferably a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized. (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid.

[0055] The "structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride" refers to a structural unit in which a hydroxyl group formed by the addition of (a) to a structural unit derived from (b) constituting the main chain of the copolymer is bonded to by half-esterification of the carboxylic acid anhydride. This structural unit has a pendant carboxyl group derived from the carboxylic acid anhydride and a pendant unsaturated group derived from (a). In this structural unit, (b) may be any of the above examples, and (a) may also be any of the above examples. (b) is preferably a monomer (b1) having an oxyranyl group and an ethylenically unsaturated bond, more preferably a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized. (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid.

[0056] As for carboxylic acid anhydrides, Saturated aliphatic polycarboxylic acid anhydrides such as malonic acid anhydride, succinic acid anhydride, glutaric acid anhydride, and adipic acid anhydride; Unsaturated aliphatic polycarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, and itaconic anhydride; Aromatic polycarboxylic acid anhydrides such as 3-vinylphthalic anhydride and 4-vinylphthalic anhydride; Alicyclic polycarboxylic acid anhydrides such as 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; Examples include polycarboxylic acid anhydrides.

[0057] In resin [K1], the ratio of structural units derived from each is, out of all structural units constituting resin [K1], (a) Structural units derived from: 2-60 mol% (b) Structural units derived from: 40-98 mol% It is preferable that this be the case. (a) Structural units derived from: 10-50 mol% (b) Structural units derived from: 50-90 mol% It is more preferable that this is the case. Furthermore, it is preferable that the structural units derived from (c) are substantially absent.

[0058] The sum of structural units derived from (a) and structural units derived from (b) is, for example, 90 mol% or more of the total structural units constituting the resin [K1], preferably 95 mol% or more, more preferably 98 mol% or more, and even more preferably 100 mol%.

[0059] When the ratio of structural units of resin [K1] falls within the above range, the storage stability of the curable resin composition and the solvent resistance of the resulting cured film tend to be excellent.

[0060] The resin [K1] can be manufactured, for example, by referring to the method described in the literature "Experimental Methods for Polymer Synthesis" (by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, March 1, 1972) and the cited literature.

[0061] Specifically, a method involves placing predetermined amounts of (a) and (b), a polymerization initiator, and a solvent into a reaction vessel, creating a deoxygenated atmosphere by, for example, replacing oxygen with nitrogen, and heating and maintaining the temperature while stirring. The polymerization initiator and solvent used here are not particularly limited and can be those commonly used in the field. For example, examples of polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc.). The solvent can be any solvent that dissolves each monomer, and solvent (F) can be a solvent described later.

[0062] The resulting copolymer may be used as is after the reaction, as a concentrated or diluted solution, or as a solid (powder) obtained by methods such as reprecipitation. In particular, by using the solvent contained in the curable resin composition of the present invention as the solvent during polymerization, the solution after the reaction can be used directly in the preparation of the curable resin composition of the present invention, thereby simplifying the manufacturing process of the curable resin composition of the present invention.

[0063] In resin [K2], the ratio of structural units derived from each is, among all structural units constituting resin [K2], (a) Structural units derived from: 1-70 mol% (b) Structural units derived from: 1-60 mol% (c) Structural units derived from: 20-95 mol% It is preferable that this be the case. (a) Structural units derived from: 3-50 mol% (b) Structural units derived from: 3-40 mol% (c) Structural units derived from: 30-90 mol% It is more preferable that, (a) Structural units derived from: 5-40 mol% (b) Structural units derived from: 5-30 mol% (c) Structural units derived from: 40-80 mol% It is even more preferable that it be so.

[0064] The sum of structural units derived from (a), (b), and (c) is, for example, 90 mol% or more of the total structural units constituting the resin [K2], preferably 95 mol% or more, more preferably 98 mol% or more, and even more preferably 100 mol%.

[0065] When the ratio of structural units of resin [K2] is within the above range, the curable resin composition tends to have excellent storage stability, as well as excellent solvent resistance, heat resistance, and mechanical strength of the resulting cured film.

[0066] In resin [K2], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid. (b) is preferably a monomer (b1) having an oxiranil group and an ethylenically unsaturated bond, more preferably a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized. (c) is preferably a (meth)acrylic acid ester having a cyclic unsaturated aliphatic hydrocarbon group, a (meth)acrylic acid ester having an aromatic ring, or a dicarbonylimide derivative.

[0067] Resin [K2] can be manufactured, for example, by the same method as described for the manufacturing of resin [K1].

[0068] In resin [K3], the ratio of structural units derived from each is, among all structural units constituting resin [K3], (a) Structural units derived from: 2-70 mol% (c) Structural units derived from: 30-98 mol% It is preferable that this be the case. (a) Structural units derived from: 10-60 mol% (c) Structural units derived from: 40-90 mol% It is more preferable that, (a) Structural units derived from: 35-60 mol% (c) Structural units derived from: 40-65 mol% It is even more preferable that this is the case. It is also preferable that the structural units derived from (b) are substantially absent.

[0069] The sum of structural units derived from (a) and structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and even more preferably 100 mol% of the total structural units constituting the resin [K3].

[0070] In resin [K3], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid. (c) is preferably an (meth)acrylic acid ester having an aromatic ring.

[0071] Resin [K3] can be manufactured, for example, by the same method as described for the manufacturing of resin [K1].

[0072] In resin [K4], the ratio of structural units derived from each is, among all structural units constituting resin [K4], (a) Structural units derived from (b) (without addition of (b)): 1-60 mol% Structural units obtained by adding (b) to structural units derived from (a): 1-50 mol% (c) Structural units derived from: 30-90 mol% It is preferable that this be the case. (a) Structural units derived from (b) (without addition): 5-50 mol% Structural units obtained by adding (b) to structural units derived from (a): 5-40 mol% (c) Structural units derived from: 35-80 mol% It is more preferable that, (a) Structural units derived from (b) (without addition): 10-40 mol% Structural units obtained by adding (b) to structural units derived from (a): 10-25 mol% (c) Structural units derived from: 40-75 mol% It is even more preferable that it be so. The sum of structural units derived from (a) (without (b) added), structural units derived from (a) with (b) added, and structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and even more preferably 100 mol% of the total structural units constituting the resin [K4].

[0073] The structural unit derived from (a) (without (b) being added) is preferably a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid. The structural unit obtained by adding (b) to the structural unit derived from (a) is a structural unit obtained by adding a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure to a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid. The structural unit derived from (c) is preferably one or more selected from the group consisting of (meth)acrylic acid esters having linear or branched aliphatic saturated hydrocarbon groups, (meth)acrylic acid esters having cyclic saturated hydrocarbon groups, (meth)acrylic acid esters having aromatic rings, bicyclounsaturated compounds, and styrene monomers, and preferably two or more. When (c) has two or more structural units derived from (c), (c) is preferably two or more selected from the group consisting of unsaturated carboxylic acid esters such as (meth)acrylic acid esters, (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, and (meth)acrylic acid esters having an aromatic ring, and is more preferably includes (meth)acrylic acid esters having a cyclic saturated hydrocarbon group and (meth)acrylic acid esters having an aromatic ring.

[0074] The resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms of (b) to the carboxylic acid and / or carboxylic acid anhydride of (a).

[0075] First, a copolymer of (a) and (c) is produced by the same method as described for the production of resin [K1]. In this case, it is preferable that the ratio of structural units derived from each is the same as the ratio exemplified for resin [K3].

[0076] Next, a portion of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms in (b). Following the production of the copolymer of (a) and (c), the atmosphere inside the flask is replaced from nitrogen to air, and (b), a reaction catalyst for the reaction between the carboxylic acid or carboxylic acid anhydride and the cyclic ether (e.g., tris(dimethylaminomethyl)phenol, triphenylphosphine, etc.), and a polymerization inhibitor (e.g., hydroquinone, methoquinone, etc.) are added to the flask and reacted at, for example, 60 to 130°C for 1 to 20 hours to produce resin [K4].

[0077] The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 55 moles, per 100 moles of (a). When the amount of (b) used is within this range, the storage stability of the curable resin composition and the balance of solvent resistance, heat resistance, and mechanical strength of the resulting cured film tend to be good.

[0078] The amount of reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b), and (c). The amount of polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b), and (c).

[0079] The reaction conditions, such as the preparation method, reaction temperature, and time, can be adjusted as appropriate, taking into account the manufacturing equipment, the amount of heat generated by polymerization, etc. Similarly, the preparation method and reaction temperature can be adjusted as appropriate, taking into account the manufacturing equipment, the amount of heat generated by polymerization, etc.

[0080] In resin [K4'], the ratio of structural units derived from each is, among all structural units constituting resin [K4'], Structural units obtained by adding (b) to structural units derived from (a): 5-95 mol% (c) Structural units derived from: 5-95 mol% It is preferable that this be the case. Structural units obtained by adding (b) to structural units derived from (a): 15-90 mol% (c) Structural units derived from: 10-85 mol% It is more preferable that, Structural units obtained by adding (b) to structural units derived from (a): 20-80 mol% (c) Structural units derived from: 20-80 mol% It is even more preferable that this is the case. Furthermore, structural units derived from (a) but without (b) attached are substantially excluded.

[0081] The sum of structural units derived from (a) with (b) added and structural units derived from (c) is, for example, 90 mol% or more of the total structural units constituting the resin [K4'], preferably 95 mol% or more, more preferably 98 mol% or more, and even more preferably 100 mol%.

[0082] The structural unit obtained by adding (b) to the structural unit derived from (a) is preferably a structural unit obtained by adding a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure to a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid. The structural unit derived from (c) is preferably one or more selected from the group consisting of (meth)acrylic acid esters having linear or branched aliphatic saturated hydrocarbon groups and (meth)acrylic acid esters having cyclic saturated hydrocarbon groups, and more preferably two or more.

[0083] The resin [K4'] may be prepared by referring to the method for producing the resin [K4] described above. The amount of (b) used is preferably 100 moles per 100 moles of (a).

[0084] In resin [K5], the ratio of structural units derived from each is, among all structural units constituting resin [K5], (b) Structural units derived from (a) (without addition of (a)): 0-30 mol% Structural units obtained by adding (a) to structural units derived from (b): 5-95 mol% (c) Structural units derived from: 5-95 mol% It is preferable that this be the case. (b) Structural units derived from (a) (without addition): 0-10 mol% Structural units derived from (b) with (a) added: 15-90 mol% (c) Structural units derived from: 10-85 mol% It is more preferable that, (b) Structural units derived from (a) (without addition): 0-5 mol% Structural units obtained by adding (a) to structural units derived from (b): 20-80 mol% (c) Structural units derived from: 20-80 mol% It is even more preferable that it be so.

[0085] The sum of structural units derived from (b) (without (a) added), structural units derived from (b) with (a) added, and structural units derived from (c) is, for example, 90 mol% or more of the total structural units constituting the resin [K5], preferably 95 mol% or more, more preferably 98 mol% or more, and even more preferably 100 mol%.

[0086] The structural unit derived from (b) (without (a) attached) is preferably a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized. The structural unit obtained by attaching (a) to the structural unit derived from (b) is preferably a structural unit obtained by attaching an unsaturated monocarboxylic acid such as (meth)acrylic acid to a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized. The structural unit derived from (c) is preferably one or more selected from the group consisting of (meth)acrylic acid esters having linear or branched aliphatic saturated hydrocarbon groups and (meth)acrylic acid esters having cyclic saturated hydrocarbon groups, and more preferably two or more.

[0087] As a first step, resin [K5] is produced in the same manner as the production method for resin [K1] described above to obtain a copolymer of (b) and (c). As described above, the obtained copolymer may be used as is after the reaction, as a concentrated or diluted solution, or as a solid (powder) obtained by methods such as reprecipitation.

[0088] The ratios of structural units derived from (b) and (c) are, in relation to the total number of moles of all structural units constituting the copolymer, respectively: (b) Structural units derived from: 5-95 mol% (c) Structural units derived from: 5-95 mol% It is preferable that this be the case. (b) Structural units derived from: 10-90 mol% (c) Structural units derived from: 10-90 mol% It is preferable that it be so.

[0089] Furthermore, resin [K5] can be obtained by reacting a cyclic ether derived from (b) in a copolymer of (b) and (c) with a carboxylic acid or carboxylic acid anhydride from (a) under the same conditions as for the production of resin [K4] or resin [K4'].

[0090] The amount of (a) used to react with the copolymer is preferably 5 to 100 moles per 100 moles of (b). Since the cyclic ether is highly reactive and unreacted (b) is less likely to remain, the (b) used in the resin [K5] is preferably (b1), more preferably (b1-1).

[0091] In resin [K6], the ratio of structural units derived from each is, among all structural units constituting resin [K6], (b) Structural units derived from (a) (without addition of (a)): 0-30 mol% Structural units obtained by adding (a) to structural units derived from (b) (without adding carboxylic acid anhydride): 20-85 mol% A structural unit obtained by adding (a) to a structural unit derived from (b), and then adding a carboxylic acid anhydride: 2-40 mol% (c) Structural units derived from: 10-60 mol% It is preferable that this be the case. (b) Structural units derived from (a) (without addition): 0-10 mol% Structural units obtained by adding (a) to structural units derived from (b) (without adding carboxylic acid anhydride): 40-80 mol% A structural unit obtained by adding (a) to a structural unit derived from (b), and then adding a carboxylic acid anhydride: 3-30 mol% (c) Structural units derived from: 15-50 mol% It is more preferable that, (b) Structural units derived from (a) (without addition): 0-5 mol% Structural units obtained by adding (a) to structural units derived from (b) (without adding carboxylic acid anhydride): 50-70 mol% A structural unit obtained by adding (a) to a structural unit derived from (b), and then adding a carboxylic acid anhydride: 5-20 mol% (c) Structural units derived from: 20-40 mol% It is even more preferable that it be so.

[0092] The sum of structural units derived from (b) (without (a) added), structural units obtained by adding (a) to structural units derived from (b) (without carboxylic acid anhydride added), structural units obtained by adding (a) to structural units derived from (b) and further adding carboxylic acid anhydride, and structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and even more preferably 100 mol% of the total structural units constituting the resin [K6].

[0093] A structural unit derived from (b) (without (a) added) is preferably a structural unit derived from a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized. A structural unit obtained by adding (a) to a structural unit derived from (b) (without carboxylic acid anhydride added) is preferably a structural unit obtained by adding an unsaturated monocarboxylic acid such as (meth)acrylic acid to a structural unit derived from a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized. A structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride is preferably a structural unit obtained by adding an unsaturated monocarboxylic acid such as (meth)acrylic acid to a structural unit derived from a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized, and further adding a saturated aliphatic polycarboxylic acid anhydride such as succinic anhydride. The structural unit derived from (c) is preferably one or more selected from the group consisting of (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, and more preferably two or more.

[0094] As a first step, resin [K6] is produced in the same manner as the method for producing resin [K1] described above to obtain a copolymer of (b) and (c). As described above, the obtained copolymer may be used as is after the reaction, as a concentrated or diluted solution, or as a solid (powder) obtained by methods such as reprecipitation.

[0095] The ratios of structural units derived from (b) and (c) are, in relation to the total number of moles of all structural units constituting the copolymer, respectively: (b) Structural units derived from: 5-95 mol% (c) Structural units derived from: 5-95 mol% It is preferable that this be the case. (b) Structural units derived from: 10-90 mol% (c) Structural units derived from: 10-90 mol% It is preferable that it be so.

[0096] Furthermore, under the same conditions as for the production of resin [K4], the cyclic ether derived from (b) in the copolymer of (b) and (c) is reacted with the carboxylic acid or carboxylic acid anhydride contained in (a). The amount of (a) used is preferably 80 to 100 moles per 100 moles of (b).

[0097] The hydroxyl group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic acid anhydride of (a) is reacted with the carboxylic acid anhydride. The amount of carboxylic acid anhydride used is preferably 0.05 to 1 mole, more preferably 0.10 to 0.8 moles, and even more preferably 0.13 to 0.7 moles, relative to 1 mole of (a) used (in other words, 1 mole of hydroxyl group generated by the use of (a)).

[0098] A specific example of resin (B) is: 3,4-Epoxycyclohexylmethyl(meth)acrylate / (meth)acrylic acid copolymer, 3,4-Epoxytricyclo[5.2.1.0 2,6 ] Resins such as decyl acrylate / (meth)acrylic acid copolymer [K1]; Glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 Decyl acrylate / (meth)acrylic acid / N-cyclohexyl maleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 Decyl acrylate / (meth)acrylic acid / N-cyclohexyl maleimide / tricyclo[5.2.1.0 2,6 ] Decen-8-yl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 Decyl acrylate / (meth)acrylic acid / benzyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6] Resins such as decyl acrylate / (meth)acrylic acid / phenoxybenzyl(meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyl oxetane / (meth)acrylic acid / styrene copolymer [K2]; Resins such as benzyl (meth)acrylate / (meth)acrylic acid copolymers and styrene / (meth)acrylic acid copolymers [K3]; Resins obtained by adding glycidyl (meth)acrylate to some of the carboxylic acid groups of benzyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to some of the carboxylic acid groups of benzyl (meth)acrylate / dicyclopentanyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to some of the carboxylic acid groups of tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic Resins such as those in which glycidyl (meth)acrylate is added to some of the carboxylic acid groups of an acid copolymer, resins in which glycidyl (meth)acrylate is added to some of the carboxylic acid groups of norbornene / vinyltoluene / (meth)acrylic acid copolymer, resins in which glycidyl (meth)acrylate is added to some of the carboxylic acid groups of norbornene / styrene / (meth)acrylic acid copolymer, and resins in which 4-hydroxybutyl acrylate glycidyl ether is added to some of the carboxylic acid groups of N-vinylcarbazole / 2-(acetoacetoxy)ethyl methacrylate / methacrylic acid copolymer [K4]; Resins such as those obtained by reacting a tricyclodecyl (meth)acrylate / (meth)acrylic acid copolymer with glycidyl (meth)acrylate, a resin obtained by reacting a tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer with glycidyl (meth)acrylate, and a resin obtained by adding 4-hydroxybutyl acrylate glycidyl ether to an N-vinylcarbazole / 2-(acetoacetoxy)ethyl methacrylate / methacrylic acid copolymer [K4']; Resins such as resins obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid, and resins obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate with (meth)acrylic acid [K5]; Resins such as those obtained by reacting a tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymer with (meth)acrylic acid and then reacting it with tetrahydrophthalic anhydride; resins obtained by reacting a 2-ethylhexyl (meth)acrylate / tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymer with (meth)acrylic acid and then reacting it with succinic anhydride; and resins obtained by reacting a methyl (meth)acrylate / 2-ethylhexyl (meth)acrylate / tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymer with (meth)acrylic acid and then reacting it with succinic anhydride [K6]; These are some examples.

[0099] The weight-average molecular weight of resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the weight-average molecular weight is within this range, the hardness of the cured film tends to improve.

[0100] The degree of dispersion of resin (B) (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is preferably 1.1 to 6, and more preferably 1.2 to 4.

[0101] The acid value of resin (B) is preferably 20 to 170 mg-KOH / g, more preferably 25 to 150 mg-KOH / g, and even more preferably 30 to 135 mg-KOH / g, based on solid content. Here, the acid value is measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

[0102] The content of resin (B) is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and even more preferably 15 to 30% by mass, based on the total amount of solids in the curable resin composition. When the content of resin (B) is within the above range, the resulting cured film tends to have excellent heat resistance.

[0103] <Silane coupling agent (C)> The curable resin composition contains a silane coupling agent (C). The inclusion of the silane coupling agent (C) in the curable resin composition makes it possible to improve the heat resistance of the resulting cured film.

[0104] Examples of silane coupling agents (C) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 Examples include (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethylsilane.

[0105] Examples of commercially available silane coupling agents (C) include KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, Examples of silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. include KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007.

[0106] The content of the silane coupling agent (C) is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, and even more preferably 0.1 to 0.3% by mass, based on the total amount of solids in the curable resin composition.

[0107] <Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound that generates active radicals, acids, etc., upon the action of light or heat and can initiate polymerization of resin (B), etc., and any known polymerization initiator can be used. Preferably, the polymerization initiator (D) is at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds, more preferably an O-acyloxime compound. When these polymerization initiators are used, high sensitivity and a tendency for high transmittance in the visible light region are obtained.

[0108] O-acyloxime compounds are compounds having a substructure represented by formula (D1). Hereafter, * represents a bond.

[0109] [ka]

[0110] Examples of O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy Examples include -1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-one-2-imine. Commercially available products such as Irgacure OXE01, Irgacure OXE02, Irgacure OXE03 (all manufactured by BASF), PBG-327 (N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Arcluz N-1919, Adeka Arcluz NCI-831, Adeka Arcluz NCI-930, and Adeka Optomer N-1919 (all manufactured by ADEKA Corporation) may also be used.

[0111] Alkylphenone compounds are compounds having a substructure represented by formula (D2-1) or formula (D2-2). In these substructures, the benzene ring may have substituents.

[0112] [ka]

[0113] Examples of compounds having the substructure represented by formula (D2-1) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure® 369, 907, and 379 (all manufactured by BASF) may also be used. Alternatively, polymerization initiators having chain-transferable groups as described in Japanese Patent Publication No. 2002-544205 may be used.

[0114] Examples of compounds having a substructure represented by formula (D2-2) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethyl ketal. Alkylphenone compounds are preferably those having a structure represented by formula (D2-1) in terms of sensitivity.

[0115] Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[ Examples include 2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0116] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure 819 (manufactured by BASF) may also be used.

[0117] Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Publication No. 6-75372, Japanese Patent Publication No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, and 2,2'-bis(2- Examples include chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), and biimidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Application Publication No. 7-10913, etc.).

[0118] Furthermore, examples of polymerization initiators (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; and 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These can be used in combination with polymerization initiators (E) (especially amine compounds) described later.

[0119] Acid generators can also be used as polymerization initiators (D). Examples of acid generators include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl·methyl·benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate, as well as nitrobenzyl tosylates and benzoin tosylates.

[0120] The content of the polymerization initiator (D) is preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by mass, and even more preferably 0 to 10 parts by mass, based on 100 parts by mass of the resin (B).

[0121] <Polymerization initiator (E)> Polymerization initiator (E) is a compound or sensitizer used together with polymerization initiator (D) to promote the polymerization of resin (B) or the like, which has been polymerized by polymerization initiator (D).

[0122] Examples of polymerization initiators (E) include thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0123] Examples of thiazoline compounds include those represented by formulas (E1-1) to (E1-3), and those described in Japanese Patent Publication No. 2008-65319.

[0124] [ka]

[0125] Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michla's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, with 4,4'-bis(diethylamino)benzophenone being preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.

[0126] Examples of alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

[0127] Examples of thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0128] Examples of carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0129] The content of the polymerization initiator (E) is preferably 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, based on 100 parts by mass of the resin (B).

[0130] <Solvent (F)> The solvent (F) is not particularly limited and can be any solvent commonly used in the field. For example, ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing both -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule but not -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxides are examples.

[0131] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0132] Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethole, methylanisole, and the like.

[0133] Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethyl ester ester Examples include ethyl toxic-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0134] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0135] Examples of alcoholic solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0136] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene. Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0137] Among these, solvent (F) is preferably a solvent with a boiling point of 100 to 200°C at 1 atmosphere (atm) from the viewpoint of applicability and drying properties. Such solvents are preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol ethyl methyl ether, cyclohexanone, methoxybutanol, or methoxybutyl acetate, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, methoxybutanol, or methoxybutyl acetate.

[0138] The solvent (F) content is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, based on the total amount of the curable resin composition. In other words, the solid content of the curable resin composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, based on the total amount of the curable resin composition.

[0139] <Leveling agent (G)> Examples of leveling agents (G) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants containing fluorine atoms. These may have polymerizable groups in their side chains.

[0140] Examples of silicone-based surfactants include surfactants that have siloxane bonds in their molecules. Specifically, examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan LLC).

[0141] Examples of fluorine-based surfactants include surfactants that have fluorocarbon chains in their molecules. Specifically, these include Florard® FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac® F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), F-Top® EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon® S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.), and others.

[0142] Examples of silicone-based surfactants containing fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in their molecules. Specifically, examples include Megafac® R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0143] The leveling agent (G) content is preferably 0.0001 to 0.1% by mass, more preferably 0.0005 to 0.05% by mass, and even more preferably 0.001 to 0.02% by mass, based on the total amount of solids in the curable resin composition.

[0144] <Antioxidant (H)> Examples of antioxidants (H) include phenolic antioxidants, sulfuric antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. In one embodiment, antioxidant (H) may be a latent antioxidant.

[0145] Examples of phenolic antioxidants include 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2 Examples include '-thiobis(6-tert-butyl-4-methylphenol), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol, and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosfepine. As phenolic antioxidants, commercially available products may be used, for example, Sumirizer® BHT, GM, GS, GP (manufactured by Sumitomo Chemical Co., Ltd.) and Irganox® 1010, 1076, 1330, 3114 (manufactured by BASF).

[0146] Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, and pentaerythrityltetrakis(3-laurylthiopropionate). Commercially available sulfur-based antioxidants may also be used. Examples of commercially available sulfur-based antioxidants include Sumirizer® TPL-R and TP-D (manufactured by Sumitomo Chemical Co., Ltd.).

[0147] Examples of phosphorus-based antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris(nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, and tetra(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butanediphosphite. Commercial phosphorus-based antioxidants may also be used. Examples of commercially available phosphorus-based antioxidants include Irgaphos® 168, 12, 38 (manufactured by BASF), Adekastab 329K, and Adekastab PEP36 (manufactured by ADEKA Corporation).

[0148] Examples of amine-based antioxidants include N,N'-di-sec-butyl-p-phenylenediamine, N,N'-diisopropyl-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, and N,N'-bis(2-naphthyl)-p-phenylenediamine. Commercially available amine-based antioxidants may also be used. Examples of commercially available amine-based antioxidants include Sumirizer® BPA, BPA-M1, and 4ML (manufactured by Sumitomo Chemical Co., Ltd.).

[0149] Examples of latent antioxidants include compounds in which the antioxidant portion is protected by a protecting group, and which function as antioxidants when heated at 100-250°C or at 80-200°C in the presence of an acid / base catalyst, thereby removing the protecting group and enabling the antioxidant to function. A commercially available latent antioxidant is ADEKA Arclus GPA-5001 (manufactured by ADEKA Corporation).

[0150] The content of the antioxidant (H) is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the resin (B).

[0151] <Other ingredients> The curable resin composition may optionally contain additives known in the art, such as fillers other than titanium dioxide particles (A), polymerizable compounds, other polymer compounds (resins), ultraviolet absorbers, and chain transfer agents.

[0152] [Method for producing a curable resin composition] A curable resin composition can be produced by mixing titanium dioxide particles (A), resin (B), and a silane coupling agent (C), as well as, if necessary, a polymerization initiator (D), a polymerization initiator aid (E), a solvent (F), a leveling agent (G), an antioxidant (H), and other components, using a known method. It is preferable to filter the curable resin composition through a filter with a pore size of approximately 0.01 to 10 μm after mixing the components.

[0153] [Cured products and molded products] <Cured products and molded products (cured films)> The cured product of this embodiment can preferably be obtained by curing the resin (B) in the curable resin composition by heating. The molded product (cured film) of this embodiment is formed from the curable resin composition and includes the cured product of the curable resin composition. The shape of the molded product may be a film, lens shape, plate shape, powder shape, granular shape, non-spherical particle shape, crushed particle shape, porous shape, continuous mass, fibrous shape, tubular shape, hollow fiber shape, etc., and may be any shape depending on the application of the molded product.

[0154] When forming a cured film as a molded product on a substrate, a curable resin composition is applied to the substrate, and volatile components such as solvents are removed by heating and drying (pre-baking) and / or vacuum drying to form a coating film, and the cured film can be obtained by curing the coating film.

[0155] Examples of substrates include glass plates such as quartz glass, borosilicate glass, aluminasilate glass, and soda-lime glass with a silica coating on the surface; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon substrates; and substrates on which thin films of aluminum, silver, silver / copper / palladium alloy, etc., are formed. Other cured films, resin films, transistors, circuits, etc., may be formed on these substrates.

[0156] Coating methods include spin coating, slit coating, and slit and spin coating. When performing heat drying (pre-baking), the temperature is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When performing vacuum drying, it is preferable to do so under a pressure of 50 to 150 Pa and at a temperature range of 20 to 25°C.

[0157] The film thickness of the coating is not particularly limited and can be appropriately selected according to the desired thickness of the cured film.

[0158] Next, the coating film is cured. The coating film may be cured by heating (post-bake) or light irradiation, and heating is preferred. The heating temperature is preferably 150 to 250°C, more preferably 160 to 235°C. The heating time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

[0159] The thickness of the cured film is not particularly limited and can be adjusted as appropriate depending on the purpose and application. The thickness of the cured film may be, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

[0160] A lens as a molded product can be obtained, for example, by forming a cured film on a substrate as described above, and then applying nanoimprint lithography, dry etching, or the like to the cured film.

[0161] Since the cured product or molded product containing it (cured film) is formed from the above-mentioned curable resin composition, it can exhibit a high refractive index, and its refractive index can be controlled to a desired value by adjusting the composition of the composition, etc. The refractive index of the cured film at a wavelength of 550 nm may be 1.86 or higher, 1.88 or higher, 1.90 or higher, 1.92 or higher, 1.94 or higher, 1.96 or higher, 1.98 or higher, or 2.00 or higher. For example, the refractive index of the cured film at a wavelength of 550 nm may be 2.30 or lower, or 2.20 or lower.

[0162] The refractive index of a cured film at a wavelength of 550 nm can be measured, for example, by the following method. First, a coating film is formed on a substrate, and the coating film is cured to obtain a substrate with a cured film. Next, the Δψ spectrum in the range of 400 nm to 800 nm is measured on the substrate with the cured film using an ellipsometer (JAWoollam, M-2000). The Δψ spectrum is then analyzed using the accompanying analysis software to determine the refractive index dispersion from 400 nm to 800 nm. The Cauchy model is applied to the analysis model. The refractive index at 550 nm is then determined from the obtained refractive index dispersion. This allows the refractive index of the cured film at a wavelength of 550 nm to be determined.

[0163] <Usage> The cured or molded product (cured film) is suitably used as a lens, which is an optical component used in optical instruments. Examples of optical instruments include imaging devices and display devices. In imaging devices, lenses are used to improve the light-gathering efficiency to each photoelectric conversion element. In display devices, lenses are used to improve the light extraction efficiency from pixels. The lens may be, for example, a metalens. A metalens is a lens formed using a material with a nanoscale structure, and has features such as a thin design, high resolution, operation over a wide wavelength range, and design flexibility, and is expected to have applications in various fields.

[0164] [Imaging device and display device] The imaging device of this embodiment includes the above-described cured film. The display device of this embodiment includes the above-described cured film.

[0165] Examples of imaging devices include CCD and CMOS sensors. Examples of display devices include liquid crystal displays, electroluminescent displays, and plasma displays. [Examples]

[0166] The present invention will be described in more detail below with reference to examples, but the present invention is not limited by the following examples, and it is certainly possible to implement it with appropriate modifications within the scope that is consistent with the spirit of the above and below, and all such modifications are included within the technical scope of the present invention. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "percent mass".

[0167] (Synthesis Example 1) <Synthesis of resin (B-1)> A flask equipped with a stirring blade, reflux condenser, thermometer, and dropping funnel was charged with 100.0 parts by mass of cyclopentanone and heated to 90°C. A mixture of 63.1 parts by mass of N-vinylcarbazole, 19.9 parts by mass of 2-(acetoacetoxy)ethyl methacrylate, 17.0 parts by mass of methacrylic acid, 5.0 parts by mass of azobis(isobutyronitrile), and 51.0 parts by mass of cyclopentanone was added dropwise into the flask using the dropping funnel. The flask temperature was maintained at 90±1°C during the addition of the mixed solution, and the addition was stopped after 3 hours. After the addition was completed, the flask temperature was reduced to 90±1°C and the reaction was allowed to mature for 6 hours. After the reaction, the reaction solution was cooled to below 40°C, and 0.12 parts by mass of polymerization inhibitor, 12.4 parts by mass of 4-hydroxybutyl acrylate glycidyl ether, 4.5 parts by mass of triphenylphosphine, and 15.6 parts by mass of cyclopentanone were added. The flask temperature was then raised to 110°C, and the addition reaction was carried out at a flask temperature of 110±1°C to obtain a copolymer (resin (B-1)) solution. The weight-average molecular weight (Mw) of the resulting resin (B-1) was 6.8 × 10⁶. 3 The dispersion (Mw / Mn) was 2.7, and the acid value on a solid content basis was 92 mg-KOH / g.

[0168] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the obtained resin were measured using the GPC method under the following conditions. Equipment: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40℃ Solvent: THF (tetrahydrofuran) Flow rate: 1.0mL / min Test liquid solid content concentration: 0.001~0.01% by mass Injection volume: 50μL Detector: RI Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation) The ratio of the weight-average molecular weight to the number-average molecular weight (Mw / Mn) obtained above in polystyrene terms was defined as the degree of dispersion.

[0169] (Synthesis Example 2) <Synthesis of resin (B-2)> 276.8 parts of propylene glycol monomethyl ether acetate were placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and stirred while purging with nitrogen, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate, and 12.3 parts of dicyclopentanyl methacrylate was mixed with 35.3 parts of t-butyl peroxy-2-ethylhexanoate (polymerization initiator), and this mixture was added dropwise to the flask from the dropping funnel over a period of 2 hours. After the addition was complete, the mixture was stirred at 120°C for a further 30 minutes to carry out the copolymerization reaction and produce an addition copolymer. Subsequently, the flask was purged with air, and 93.7 parts of acrylic acid, 1.5 parts of triphenylphosphine (catalyst), and 0.8 parts of methoquinone (polymerization inhibitor) were added to the above addition copolymer solution. The reaction was continued at 110°C for 10 hours, during which the epoxy groups derived from glycidyl methacrylate reacted with acrylic acid to cleave the epoxy groups and simultaneously introduce polymerizable unsaturated bonds into the polymer side chains. Next, 83.8 parts of succinic anhydride were added to the reaction system, and the reaction was continued at 110°C for 1 hour, during which the hydroxyl groups generated by the cleavage of the epoxy groups reacted with succinic anhydride to introduce carboxyl groups into the side chains, thereby obtaining the polymer. Finally, 383.3 parts of propylene glycol monomethyl ether acetate were added to the reaction solution to obtain a copolymer (resin (B-2)) solution with a polymer solids content of 40%. The weight-average molecular weight (Mw) of the produced resin (B-2) was 6.6 × 10⁶. 3The acid value, calculated on a solid content basis, was 92 mg-KOH / g.

[0170] (Examples 1-12 and Comparative Example 1) <Preparation of curable resin composition> Titanium dioxide particles (A), resin (B), silane coupling agent (C), polymerization initiator (D), solvent (F), leveling agent (G), antioxidant (H), and polymerizable compound (I) were mixed in the proportions shown in Table 1 and filtered using a 4.5 μm PS (polysulfone) filter to obtain the curable resin compositions of Examples 1 to 12 and Comparative Example 1. In Table 1, the parts of each component represent parts by mass on a solid content basis.

[0171] The components shown in Table 1 are as follows: Titanium oxide particles (A): (A-1) Titanium dioxide 35% propylene glycol monomethyl ether acetate dispersion (manufactured by Ishihara Sangyo Co., Ltd., LDB-142) Resin (B): (B-1) Resin of Synthesis Example 1 (B-1) (B-2) Resin of Synthesis Example 2 (B-2) (B-3) Reactive acrylic polymer (manufactured by Negami Kogyo Co., Ltd., RA-4101) (B-4) Benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio 80:20 (mass%), weight-average molecular weight: 24400) Silane coupling agent (C): (C-1)3-Methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) Polymerization initiator (D): (D-1) ADEKA Arcules NCI-930 (N-acetyloxy-1-(4-(4-(2-hydroxyethoxy)phenylsulfanyl)phenyl)propan-1-one-2-imine, manufactured by ADEKA Corporation) (D-2) Irgacure OXE01 (1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime), manufactured by BASF) Solvent (F): (F-1) Propylene glycol monomethyl ether acetate (PGMEA) (F-2) Propylene glycol monomethyl ether (PGME) Leveling agent (G): (G-1) Toray Silicone SH8400 (Polyether-modified silicone oil, manufactured by Toray Dow Corning Co., Ltd.) Antioxidant (H): (H-1) ADEKA Arclus GPA-5001 (Latent antioxidant, manufactured by ADEKA Corporation) Polymerizable compound (I): (I-1) Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA)

[0172] <Fabrication and evaluation of cured films> (Preparation of hardened film) The curable resin compositions of Examples 1-12 and Comparative Example 1 were applied to a 5cm square glass substrate (Corning Eagle 2000) by spin coating. A pre-bake was then performed at 85°C for 2 minutes to form a coating film. Subsequently, the coating film was post-baked at 220°C for 10 minutes to obtain a cured film. The thickness of the obtained cured film was measured using a film thickness measuring device (ULVAC, DEKTAK3) and confirmed to be 1 μm.

[0173] (Transmittance measurement) For the obtained cured film, an integrating sphere (ISV-922, manufactured by JASCO Corporation) was attached to a UV-Vis spectrophotometer (V-770, manufactured by JASCO Corporation), and the transmittance at wavelengths of 400-700 nm was measured at 1 nm intervals. The average value was then calculated. The results are shown in Table 1.

[0174] (Heat resistance test) The obtained cured film was heat-treated at 260°C for 30 minutes. After heat treatment, the transmittance of the cured film was measured at 1 nm intervals from 400 to 700 nm, and the average value was calculated. Heat resistance was evaluated by calculating the change in transmittance before and after heat treatment (change in transmittance = transmittance of the cured film before heat treatment - transmittance of the cured film after heat treatment). A smaller change in transmittance before and after heat treatment indicates better heat resistance. The results are shown in Table 1.

[0175] (Refractive index measurement) The Δψ spectrum in the wavelength range of 400 nm to 800 nm was measured from the obtained cured film using an ellipsometer (JAWoolham, M-2000). The Δψ spectrum was analyzed using the accompanying analysis software to determine the refractive index dispersion from 400 nm to 800 nm. The Cauchy model was applied to the analysis model. The refractive index at 550 nm among the determined refractive index dispersions is shown in Table 1.

[0176] [Table 1]

[0177] As shown in Table 1, the curable resin composition of the example was superior to the curable resin composition of the comparative example in terms of heat resistance and also had a sufficiently high refractive index. These results confirm that the curable resin composition of the present invention is capable of forming a cured film with a high refractive index and good heat resistance.

Claims

1. It contains titanium dioxide particles, resin, and a silane coupling agent. A curable resin composition in which the content of titanium oxide particles is greater than 60% by mass and less than 90% by mass, based on the total amount of solids in the curable resin composition.

2. A cured film formed from the curable resin composition described in claim 1.

3. An imaging apparatus comprising the cured film described in claim 2.

Images