Curable resin composition, cured film and imaging device

Abstract

Provided is a curable resin composition capable of forming a cured film having a high refractive index and good heat resistance. The present invention provides a curable resin composition containing titanium oxide particles, a resin, and a silane coupling agent. The content of the titanium oxide particles is more than 60% by mass and less than 90% by mass based on the total solid content of the curable resin composition.

Description

Technical Field

[0001] This invention relates to curable resin compositions, curable films, and photographic devices. Background Technology

[0002] Lenses, as optical products used in optical devices, have the functions of focusing and concentrating 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.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2016-164674 Summary of the Invention

[0006] The main objective of this invention is to provide a curable resin composition capable of forming a curable film with high refractive index and good heat resistance.

[0007] The present invention provides the curable resin composition described in [1], the curable film described in [2], and the imaging device described in [3].

[0008] [1] A curable resin composition comprising titanium dioxide particles, resin and silane coupling agent, wherein the content of the titanium dioxide particles is greater than 60% by mass and less than 90% by mass based on the total amount of solid components of the curable resin composition.

[0009] [2] A cured film formed from the curable resin composition described in [1].

[0010] [3] A photographing device comprising the cured film described in [2].

[0011] According to the present invention, a curable resin composition capable of forming a curable film having a high refractive index and good heat resistance is provided. Furthermore, according to the present invention, a curable film formed from this curable resin composition is provided. Moreover, according to the present invention, an imaging apparatus comprising this curable film is provided. Detailed Implementation

[0012] The embodiments of the present invention will now be described in detail. However, the present invention is not limited to the following embodiments.

[0013] In this specification, the numerical range represented by "~" indicates the range encompassing the minimum and maximum values, respectively, listed before and after the "~". Within the segmented numerical ranges described in this specification, the upper or lower limit of one numerical range can be replaced by the upper or lower limit of other segmented numerical ranges. Furthermore, the upper or lower limit of the numerical ranges described in this specification can be replaced by the values ​​shown in the embodiments.

[0014] In this specification, (meth)acrylic acid means acrylic acid or its corresponding methacrylic acid. The same applies to other similar expressions such as (meth)acryloyl, (meth)acrylate, etc.

[0015] In this specification, the materials exemplified below, unless otherwise stated, may be used alone or in combination of two or more, provided that the conditions are met. Where multiple corresponding substances are present in each component, unless otherwise stated, the content of each component refers to the total amount of those substances.

[0016] [Curing Resin Composition]

[0017] The curable resin composition of this embodiment contains titanium dioxide particles (A), resin (B), and a silane coupling agent (C). The curable resin composition of this embodiment may further contain a polymerization initiator (D), a polymerization initiation aid (E), a solvent (F), a leveling agent (G), an antioxidant (H), and other components. The curable resin composition of this embodiment is suitable for the formation of lenses (especially superlenses).

[0018] <Titanium oxide particles (A)>

[0019] The curable resin composition contains titanium dioxide (TiO2) particles (A). Because the curable resin composition contains titanium dioxide particles (A), the refractive index of the resulting cured film can be increased.

[0020] The titanium dioxide particles (A) are preferably rutile titanium dioxide particles. Rutile titanium dioxide tends to have a higher refractive index compared to titanium dioxide with other crystal structures (e.g., anatase, brookite), which can further improve the refractive index of the resulting cured film. The crystal structure of titanium dioxide can be identified, for example, by X-ray diffraction (XRD).

[0021] Commercially available rutile titanium dioxide particles include, for example, LDB-142 (manufactured by Ishihara Sangyo Co., Ltd.), ST-485SA15, and ST-605EC (manufactured by Titanium Industry Co., Ltd.).

[0022] From the viewpoint of dispersibility in curable resin compositions, titanium dioxide particles (A) can be surface-treated using organic or inorganic substances. Examples of organic substances include organosilicon compounds such as silane coupling agents. Examples of inorganic substances include alumina, silicon dioxide, and zirconium dioxide.

[0023] From the viewpoint of re-agglomeration, the average particle size of the titanium oxide particles (A) is preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 10 nm or more. From the viewpoint of precipitation, it is preferably 1000 nm (1 μm) or less, more preferably 500 nm (0.5 μm) or less, and even more preferably 100 nm (0.1 μm) or less.

[0024] In this specification, the average particle size of the titanium oxide particles (A) is the particle size at 50% of the cumulative value in the particle size distribution determined by laser diffraction / scattering. The average particle size is the total average particle size of the titanium oxide particles (A) including primary and secondary particles.

[0025] The content of titanium dioxide particles (A), based on the total solid content of the curable resin composition, is greater than 60% by mass and less than 90% by mass. If the content of titanium dioxide particles (A) is greater than 60% by mass, based on the total solid content of the curable resin composition, the refractive index of the resulting cured film can be sufficiently improved. If the content of titanium dioxide particles (A) is less than 90% by mass, based on the total solid content of the curable resin composition, the haze value of the resulting cured film can be suppressed from becoming excessively high. The content of titanium dioxide particles (A), based on the total solid content of the curable resin composition, can 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, less than 88% by mass, more than 85% by mass, or less than 82% by mass.

[0026] It should be noted that, in this specification, the solids content of the curable resin composition refers to the total amount of components after removing the solvent from the curable resin composition. The total amount of solids in the curable resin composition and the content of each component thereto can be determined, for example, by known analytical methods such as liquid chromatography and gas chromatography.

[0027] <Resin (B)>

[0028] 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 selected from at least one of resins [K1], [K2], [K3], [K4], [K4'], [K5], and [K6]. From the viewpoint of 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].

[0029] Resin [K1]: A copolymer having structural units of a monomer (a) (hereinafter sometimes simply referred to as "(a)") selected from at least one of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and structural units of a monomer (b) (hereinafter sometimes simply referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an olefinic unsaturated bond;

[0030] Resin [K2]: a copolymer having structural units from (a), structural units from (b), and structural units from monomer (c) that can copolymerize with (a) (wherein (a) and (b) are different) (hereinafter sometimes simply referred to as "(c)");

[0031] Resin [K3]: A copolymer having structural units from (a) and structural units from (c);

[0032] Resin [K4]: a copolymer having structural units obtained by adding (b) to structural units from (a) and structural units from (c), and comprising structural units from (a) without addition (b);

[0033] Resin [K4']: a copolymer having structural units obtained by adding (b) to structural units from (a) and structural units from (c), and being a copolymer that does not contain structural units from (a) that have not been added (b);

[0034] Resin [K5]: A copolymer having structural units obtained by adding (a) to structural units from (b) and structural units from (c) (may contain structural units from (b) without addition (a), but preferably not).

[0035] Resin [K6]: A copolymer having structural units obtained by adding (a) and further adding carboxylic anhydride to structural units from (b) and structural units from (c).

[0036] As a specific example of (a), for example:

[0037] Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho-, meta-, and p-vinylbenzoic acid;

[0038] Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, zeaxanthin, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexene dicarboxylic acid.

[0039] 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, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, etc., are bicyclic unsaturated compounds containing carboxyl groups;

[0040] 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, 5,6-dicarboxylic bicyclic [2.2.1]hept-2-enoic anhydride and other unsaturated dicarboxylic anhydrides;

[0041] Unsaturated mono[(meth)acryloyloxyethyl] esters of divalent or higher polycarboxylic acids, such as succinate mono[2-(meth)acryloyloxyethyl] ester and phthalate mono[2-(meth)acryloyloxyethyl] ester.

[0042] Unsaturated acrylates containing both hydroxyl and carboxyl groups in the same molecule, such as α-(hydroxymethyl)acrylic acid.

[0043] Among these, acrylic acid, methacrylic acid, or maleic anhydride are preferred, considering both copolymerization reactivity and solubility in the resulting resin in an alkaline aqueous solution.

[0044] (b) can be a monomer having, for example, a cyclic ether structure having 2 to 4 carbon atoms (e.g., selected from at least one of ethylene oxide ring, oxobutane ring, and tetrahydrofuran ring) and an olefinic unsaturated bond. (b) Preferably, it is a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0045] Examples of (b) include monomers having ethylene oxide and olefinic unsaturated bonds (b1) (hereinafter sometimes referred to as "(b1)"), monomers having oxobutyl and olefinic unsaturated bonds (b2) (hereinafter sometimes referred to as "(b2)"), and monomers having tetrahydrofuranyl and olefinic unsaturated bonds (b3) (hereinafter sometimes referred to as "(b3)").

[0046] Examples of (b1) include monomers (b1-1) (hereinafter sometimes referred to as "(b1-1)") having the structure of a straight-chain or branched aliphatic unsaturated hydrocarbons after epoxidation, and monomers (b1-2) (hereinafter sometimes referred to as "(b1-2)") having the structure of alicyclic unsaturated hydrocarbons after epoxidation.

[0047] Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, and 2,3-bis(glycidoxymethyl)styrene. Alkenes, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, 4-hydroxybutylacrylate glycidyl ether, etc.

[0048] Examples of compounds represented by formula (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000, manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (e.g., Cyclomer A400, manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (e.g., Cyclomer M100, manufactured by Daicel Co., Ltd.), compounds represented by formula (BI), compounds represented by formula (BII), etc.

[0049]

[0050] In equations (BI) and (BII), R e and R fIt represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms, wherein the hydrogen atoms in the alkyl group may be replaced by hydroxyl groups.

[0051] X e and X f Indicates a single key, -R g -、 -R g -O-、 -R g -S- or -R g -NH-.

[0052] R g Denotes alkyldiyl groups with 1 to 6 carbon atoms.

[0053] This indicates the bonding site with O.

[0054] Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl.

[0055] Examples of alkyl groups in which hydrogen atoms are replaced by hydroxyl groups include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, and 4-hydroxybutyl.

[0056] R e and R f Preferably, it is a hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl or 2-hydroxyethyl, more preferably a hydrogen atom or methyl.

[0057] Examples of alkyl dimethyl groups include methylene, ethylene, propane-1,2-dimethyl, propane-1,3-dimethyl, butane-1,4-dimethyl, pentane-1,5-dimethyl, and hexane-1,6-dimethyl.

[0058] X e and X f Preferred components include single bonds, methylene, and ethylene. -CH2-O- or -CH2CH2-O-, more preferably a single bond or -CH2CH2-O- ( (Indicates the binding site with O).

[0059] Examples of compounds represented by formula (BI) include compounds represented by formulas (BI-1) to (BI-15). Among these, compounds represented by formula (BI) are preferably compounds represented by formulas (BI-1), (BI-3), (BI-5), (BI-7), (BI-9), or (BI-11) to (BI-15), and more preferably compounds represented by formulas (BI-1), (BI-7), (BI-9), or (BI-15).

[0060]

[0061] Examples of compounds represented by formula (BII) include compounds represented by formulas (BII-1) to (BII-15). Among these, compounds represented by formula (BII) are preferably compounds represented by formulas (BII-1), (BII-3), (BII-5), (BII-7), (BII-9), or (BII-11) to (BII-15), and more preferably compounds represented by formulas (BII-1), (BII-7), (BII-9), or (BII-15).

[0062]

[0063] The compounds represented by formula (BI) and formula (BII) can be used individually or in combination of two or more. When the compounds represented by formula (BI) and formula (BII) are used in combination, their content ratio [compound represented by formula (BI):compound represented by formula (BII)] on a molar basis is preferably 5:95 to 95:5, more preferably 20:80 to 80:20.

[0064] (b2) More preferably, it is a monomer having an oxetyl group and a (meth)acryloyloxy group. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc.

[0065] (b3) More preferably, it is a monomer having a tetrahydrofuran group and a (meth)acryloyloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Osaka Organic Chemical Industry Co., Ltd., Viscoat V#150), tetrahydrofurfuryl methacrylate, etc.

[0066] From the perspective of further improving the reliability of the obtained cured film, such as heat resistance and chemical resistance, (b) is preferably (b1). Furthermore, from the perspective of excellent storage stability of the cured resin composition, (b) is preferably (b1-2).

[0067] Examples of (c) include (meth)acrylate monomers, unsaturated carboxylic acid esters such as unsaturated dicarboxylic acid esters, and vinyl monomers having unsaturated aliphatic hydrocarbon rings, unsaturated heterocycles, or aromatic rings.

[0068] Examples of (meth)acrylate monomers include:

[0069] Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, and other (meth)acrylates with straight or branched aliphatic saturated hydrocarbon groups;

[0070] (Meth)acrylates such as allyl methacrylate and propargyl methacrylate are aliphatic unsaturated hydrocarbon groups with straight or branched chains;

[0071] Cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo(meth)acrylate [5.2.1.0] 2,6 Decane-8-yl ester (in this technical field, it is sometimes referred to as "(meth)acrylate dicyclopentyl ester" as a common name. In addition, it is sometimes referred to as "(meth)acrylate tricyclodecyl ester"), isobornyl ester of (meth)acrylate, adamantyl ester of (meth)acrylate, and other (meth)acrylates with cyclic saturated hydrocarbon groups;

[0072] (Meth)acrylic acid tricyclic [5.2.1.0] 2,6 ] Decen-8-yl ester (in this technical field, it is commonly referred to as "(meth)acrylate dicyclopentenyl ester"), (meth)acrylate dicyclopentoxyethyl ester and other (meth)acrylates having cyclic unsaturated aliphatic hydrocarbon groups;

[0073] (Meth)acrylates such as phenyl methacrylate, naphthyl methacrylate, benzyl methacrylate, and phenoxybenzyl methacrylate contain aromatic rings.

[0074] Hydroxyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; methacrylates containing active methylene groups such as 2-(acetylacetoxy)ethyl methacrylate; etc.

[0075] Examples of unsaturated dicarboxylic acid esters include diethyl maleate, diethyl fumarate, and diethyl itaconic acid.

[0076] Among these, unsaturated carboxylic acid esters are preferred:

[0077] Methyl methacrylate, 2-ethylhexyl methacrylate, etc. C 1-10 Alkyl (meth)acrylates;

[0078] (Meth)acrylic acid tricyclic [5.2.1.0] 2,6 Decane-8-yl esters and other (meth)acrylates with cyclic saturated hydrocarbon groups;

[0079] (Meth)acrylic acid tricyclic [5.2.1.0] 2,6 [Decene-8-yl ester and other (meth)acrylates containing cyclic unsaturated aliphatic hydrocarbon groups;]

[0080] Phenoyl methacrylate, benzyl methacrylate, and other methacrylates containing aromatic rings.

[0081] Examples of vinyl monomers with unsaturated aliphatic hydrocarbon rings include bicyclo[2.2.1]hept-2-ene (or sometimes called "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, 5-(2'-hydroxyethyl)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, and 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]. 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- Bicyclic unsaturated compounds such as tert-butoxycarbonylbicyclo[2.2.1]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.

[0082] Examples of dicarbonyl imide derivatives that are vinyl monomers with unsaturated heterocycles include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N-succinimide-6-maleimide hexanoate, N-succinimide-3-maleimide propionate, and N-(9-acridyl)maleimide.

[0083] Examples of vinyl monomers with aromatic rings include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and other styrene-based monomers; and vinyl monomers with fused rings such as N-vinylcarbazole.

[0084] Other vinyl monomers are preferably:

[0085] Monomers containing nitrile groups, such as acrylonitrile and methacrylonitrile;

[0086] Monomers containing halogen atoms, such as vinyl chloride and vinylidene chloride;

[0087] Acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

[0088] Among these, considering copolymerization reactivity and heat resistance, vinyl monomers are preferred:

[0089] Styrene, vinyltoluene, and other styrene monomers;

[0090] N-Phenylacetimide, N-Cyclohexylmaleimide, N-Benzylmaleimide and other dicarbonylimide derivatives;

[0091] Bicyclic unsaturated compounds such as bicyclic [2.2.1]hept-2-ene (or sometimes called "2-norbornene"); (meth)acrylates containing active methylene groups such as 2-(acetylacetoxy)ethyl methacrylate;

[0092] N-vinylcarbazole and other vinyl monomers with fused rings;

[0093] From the perspective of the high refractive index of the cured film, a vinyl monomer with fused rings is more preferred.

[0094] "A structural unit obtained by adding (b) to a structural unit from (a)" refers to a unit formed by bonding (b) through addition to a structural unit from (a) constituting the main chain of the copolymer. This structural unit has a suspended unsaturated group from (b). In this structural unit, (a) can be any of the examples described above, and (b) can also be any of the examples described above. (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid. (b) is preferably a monomer (b1) having ethylene oxide and olefinic unsaturated bonds, more preferably a monomer (b1-1) having a structure of a linear or branched aliphatic unsaturated hydrocarbon after epoxidation.

[0095] "A structural unit obtained by adding (a) to a structural unit from (b)" refers to a unit formed by bonding (a) through addition to a structural unit from (b) constituting the main chain of the copolymer. This structural unit has a suspended unsaturated group from (a). In this structural unit, (b) can be any of the examples described above, and (a) can also be any of the examples described above. (b) is preferably a monomer (b1) having ethylene oxide and olefinic unsaturated bonds, more preferably a monomer (b1-1) having a structure of a linear or branched aliphatic unsaturated hydrocarbon after epoxidation. (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid.

[0096] "A structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic anhydride" refers to a structural unit obtained by combining a carboxylic anhydride with a hydroxyl group generated by adding (a) to a structural unit derived from (b) constituting the main chain of the copolymer through a half-esterification process. This structural unit has a suspended carboxyl group from the carboxylic anhydride and a suspended unsaturated group from (a). In this structural unit, (b) can be any of the examples described above, and (a) can also be any of the examples described above. (b) is preferably a monomer (b1) having ethylene oxide and olefinic unsaturated bonds, more preferably a monomer (b1-1) having a structure of a linear or branched aliphatic unsaturated hydrocarbon after epoxidation. (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid.

[0097] As carboxylic anhydrides, the following polycarboxylic anhydrides can be cited:

[0098] Saturated aliphatic polycarboxylic anhydrides such as malonic anhydride, succinic anhydride, glutaric anhydride, and adipic anhydride;

[0099] Maleic anhydride, citracic anhydride, itaconic anhydride and other unsaturated aliphatic polycarboxylic anhydrides;

[0100] Aromatic polycarboxylic anhydrides such as 3-vinyl phthalic anhydride and 4-vinyl phthalic anhydride;

[0101] Alicyclic polycarboxylic anhydrides such as 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxylic bicyclic [2.2.1]hept-2-ene anhydride.

[0102] In resin [K1], the ratio of structural units from each unit is preferably, among all structural units constituting resin [K1]:

[0103] Structural units from (a): 2–60 mol%

[0104] Structural units from (b): 40–98 mol%.

[0105] More preferably:

[0106] Structural units from (a): 10–50 mol%

[0107] Structural units from (b): 50–90 moles.

[0108] In addition, it is preferable that the structure does not actually contain any structural units from (c).

[0109] The total of the structural units from (a) and the structural units from (b) 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 all structural units constituting resin [K1].

[0110] If the ratio of the structural units of the resin [K1] is 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.

[0111] The resin [K1] can be manufactured by referring to, for example, the method described in the literature "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Doujin Co., Ltd., 1st edition, 1st printing, March 1, 1972) and the references cited in that literature.

[0112] Specifically, one method involves adding specified amounts of (a) and (b), the polymerization initiator, and the solvent to a reaction vessel, for example, by replacing oxygen with nitrogen to create a deoxygenated atmosphere, and heating and maintaining the temperature while stirring. It should be noted that the polymerization initiator and solvent used herein are not particularly limited, and commonly used polymerization initiators and solvents in the art can be used. For example, as polymerization initiators, examples include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile) etc.) and organic peroxides (benzoyl peroxide, tert-butyl peroxide-2-ethylhexanoate, etc.). As solvents, any solvent capable of dissolving the monomers is acceptable; solvents described later can be used as solvent (F).

[0113] It should be noted that the obtained copolymer can be used directly from the reaction solution, or from a concentrated or diluted solution, or from a substance extracted in solid (powder) form by methods such as reprecipitation. In particular, by using the solvent contained in the curable resin composition of the present invention as a solvent during polymerization, the reaction solution can be directly used to prepare the curable resin composition of the present invention, thus simplifying the manufacturing process of the curable resin composition of the present invention.

[0114] In resin [K2], the ratio of structural units from each unit is preferably, among all structural units constituting resin [K2]:

[0115] Structural units from (a): 1–70 mol%

[0116] Structural units from (b): 1–60 mol%

[0117] Structural units from (c): 20–95 mol%.

[0118] More preferably:

[0119] Structural units from (a): 3–50 mol%

[0120] Structural units from (b): 3–40 mol%

[0121] Structural units from (c): 30–90 mol%.

[0122] Further preferred options are:

[0123] Structural units from (a): 5–40 mol%

[0124] Structural units from (b): 5–30 mol%

[0125] Structural units from (c): 40–80 moles.

[0126] The total of the structural units from (a), (b), and (c) constitutes, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and even more preferably 100 mol% of all structural units constituting resin [K2].

[0127] If the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the curable resin composition, as well as the solvent resistance, heat resistance and mechanical strength of the resulting cured film tend to be excellent.

[0128] In resin [K2], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid. (b) is preferably a monomer having ethylene oxide and olefinic unsaturated bonds (b1), more preferably a monomer having an alicyclic unsaturated hydrocarbon structure after epoxidation (b1-2). (c) is preferably a (meth)acrylate having cyclic unsaturated aliphatic hydrocarbon groups, a (meth)acrylate having aromatic rings, or a dicarbonylimide derivative.

[0129] Resin [K2] can be manufactured, for example, in the same way as resin [K1].

[0130] In resin [K3], the ratio of structural units from each unit is preferably, among all structural units constituting resin [K3]:

[0131] Structural units from (a): 2–70 mol%

[0132] Structural units from (c): 30–98 mol%.

[0133] More preferably:

[0134] Structural units from (a): 10–60 mol%

[0135] Structural units from (c): 40–90 mol%.

[0136] A further preferred option is:

[0137] Structural units from (a): 35–60 mol%

[0138] Structural units from (c): 40–65 moles.

[0139] In addition, it is preferable that the structural units from (b) are substantially absent.

[0140] The total of the structural units from (a) and the structural units 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 all structural units constituting resin [K3].

[0141] In the resin [K3], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid. (c) is preferably a (meth)acrylate having an aromatic ring.

[0142] Resin [K3] can be manufactured, for example, in the same way as resin [K1].

[0143] In resin [K4], the ratio of structural units from each unit is preferably, among all structural units constituting resin [K4]:

[0144] Structural units from (a) (unadded to (b)): 1–60 mol%.

[0145] The structural unit obtained by adding (b) to the structural unit from (a): 1–50 mol%.

[0146] Structural units from (c): 30–90 mol%.

[0147] More preferably:

[0148] Structural units from (a) (unadded to (b)): 5–50 mol%.

[0149] The structural unit obtained by adding (b) to the structural unit from (a): 5–40 mol%.

[0150] Structural units from (c): 35–80 mol%.

[0151] A further preferred option is:

[0152] Structural units from (a) (unadded to (b)): 10–40 mol%.

[0153] The structural unit obtained by adding (b) to the structural unit from (a): 10–25 mol%.

[0154] Structural units from (c): 40–75 moles.

[0155] The total of the structural units from (a) (without addition (b)), the structural units obtained by adding (b) to the structural units from (a), and the structural units 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% in all structural units constituting resin [K4].

[0156] The structural unit from (a) (without addition (b)) is preferably a structural unit derived from an unsaturated monocarboxylic acid, such as (meth)acrylic acid. The structural unit added to the structural unit from (a) is a structural unit obtained by adding a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure after epoxidation to a structural unit derived from an unsaturated monocarboxylic acid, such as (meth)acrylic acid. The structural unit from (c) is preferably selected from one or more of (meth)acrylic esters having linear or branched aliphatic saturated hydrocarbon groups, (meth)acrylic esters having cyclic saturated hydrocarbon groups, (meth)acrylic esters having aromatic rings, bicyclic unsaturated compounds, and styrene monomers, preferably two or more. When (c) has two or more structural units, (c) is preferably selected from two or more unsaturated carboxylic acid esters such as (meth)acrylates, (meth)acrylates having cyclic saturated hydrocarbon groups, and (meth)acrylates having aromatic rings, and more preferably includes (meth)acrylates having cyclic saturated hydrocarbon groups and (meth)acrylates having aromatic rings.

[0157] The resin [K4] can be manufactured by obtaining a copolymer of (a) and (c) and adding the cyclic ether having 2 to 4 carbon atoms in (b) to the carboxylic acid and / or carboxylic anhydride in (a).

[0158] First, copolymers of (a) and (c) are manufactured using the same method as that used for manufacturing resin [K1]. In this case, the ratio of the respective structural units is preferably the same as that exemplified for resin [K3].

[0159] Next, the cyclic ether having 2 to 4 carbon atoms in (b) is reacted with a portion of the carboxylic acid and / or carboxylic anhydride from (a) in the copolymer described above. After the copolymer of (a) and (c) is produced, the atmosphere in the flask is replaced with air from nitrogen, and (b), the reaction catalyst of the carboxylic acid or carboxylic anhydride with the cyclic ether (e.g., tris(dimethylaminomethyl)phenol, triphenylphosphine, etc.) and the polymerization inhibitor (e.g., hydroquinone, formquinone, etc.) are placed in the flask, and the reaction is carried out, for example, at 60 to 130°C for 1 to 20 hours, thereby producing resin [K4].

[0160] The amount of (b) used is preferably 5 to 80 moles relative to 100 moles of (a), more preferably 10 to 55 moles. If the amount of (b) used is within such a range, the storage stability of the curable resin composition and the balance between the solvent resistance, heat resistance and mechanical strength of the resulting cured film tend to be good.

[0161] The amount of reaction catalyst used is preferably 0.001 to 5 parts by mass relative to the total mass of (a), (b), and (c) 100 parts by mass. The amount of polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to the total mass of (a), (b), and (c) 100 parts by mass.

[0162] The reaction conditions, such as the charging method, reaction temperature, and time, can be appropriately adjusted by taking into account the manufacturing equipment and the heat generated during polymerization. It should be noted that, similarly, the polymerization conditions can be appropriately adjusted by taking into account the manufacturing equipment and the heat generated during polymerization, including the charging method and reaction temperature.

[0163] In resin [K4'], the ratio of structural units from each unit is preferably, among all structural units constituting resin [K4']:

[0164] The structural unit obtained by adding (b) to the structural unit from (a): 5–95 mol%.

[0165] Structural units from (c): 5–95 mol%.

[0166] More preferably:

[0167] The structural unit obtained by adding (b) to the structural unit from (a): 15–90 mol%.

[0168] Structural units from (c): 10–85 mol%.

[0169] A further preferred option is:

[0170] The structural unit obtained by adding (b) to the structural unit from (a): 20–80 mol%.

[0171] Structural units from (c): 20–80 mol%.

[0172] In addition, it does not actually contain structural units from (a) and does not add structural units from (b).

[0173] The total of the structural units obtained by adding (b) to the structural unit from (a) and the structural units 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% in all structural units constituting resin [K4'].

[0174] The structural unit obtained by adding (b) to the structural unit from (a) is preferably a structural unit obtained by adding a monomer (b1-1) having a structure of a straight-chain or branched aliphatic unsaturated hydrocarbon after epoxidation to a structural unit of an unsaturated monocarboxylic acid such as (meth)acrylic acid. The structural unit from (c) is preferably selected from one or more of (meth)acrylates having a straight-chain or branched aliphatic saturated hydrocarbon groups and (meth)acrylates having cyclic saturated hydrocarbon groups, more preferably two or more.

[0175] The resin [K4'] can be manufactured according to the above-described method for manufacturing resin [K4]. The amount of (b) used is preferably 100 moles relative to 100 moles of (a).

[0176] In resin [K5], the ratio of structural units from each unit is preferably, among all structural units constituting resin [K5]:

[0177] Structural units from (b) (unadded to (a)): 0–30 mol%

[0178] The structural unit obtained by adding (a) to the structural unit from (b): 5–95 mol%.

[0179] Structural units from (c): 5–95 mol%.

[0180] More preferably:

[0181] Structural units from (b) (unadded to (a)): 0–10 mol%

[0182] The structural unit obtained by adding (a) to the structural unit from (b): 15–90 mol%.

[0183] Structural units from (c): 10–85 moles.

[0184] A further preferred option is:

[0185] Structural units from (b) (without addition to (a)): 0–5 mol%.

[0186] The structural unit obtained by adding (a) to the structural unit from (b): 20–80 mol%.

[0187] Structural units from (c): 20–80 mol%.

[0188] The total of the structural units from (b) (without addition (a)), the structural units obtained by adding (a) to the structural units from (b), and the structural units 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% in all structural units constituting resin [K5].

[0189] The structural unit from (b) (without addition (a)) is preferably a structural unit from a monomer (b1-1) having a structure derived from the epoxidation of a linear or branched aliphatic unsaturated hydrocarbon. The structural unit obtained by adding (a) to the structural unit from (b) is preferably a structural unit obtained by adding an unsaturated monocarboxylic acid such as (meth)acrylic acid to the structural unit from the monomer (b1-1), wherein the monomer (b1-1) has a structure derived from the epoxidation of a linear or branched aliphatic unsaturated hydrocarbon. The structural unit from (c) is preferably selected from one or more of (meth)acrylates having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylates having a cyclic saturated hydrocarbon group, more preferably two or more.

[0190] For resin [K5], as the first stage, the same method as for manufacturing resin [K1] described above is followed to obtain copolymers of (b) and (c). Similarly, for the obtained copolymer, the solution after the reaction can be used directly, or the concentrated or diluted solution can be used, or a substance extracted in solid (powder) form by methods such as reprecipitation can be used.

[0191] The ratios of the structural units from (b) and (c) relative to the total molar number of all structural units constituting the copolymer are preferably as follows:

[0192] Structural units from (b): 5–95 mol%

[0193] Structural units from (c): 5–95 mol%.

[0194] More preferably:

[0195] Structural units from (b): 10–90 mol%

[0196] Structural units from (c): 10–90 moles.

[0197] Furthermore, resin [K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride contained in (a) with the cyclic ether from (b) contained in the copolymer of (b) and (c) under the same conditions as the manufacturing method of resin [K4] or resin [K4'].

[0198] The amount of (a) that reacts with the above copolymer is preferably 5 to 100 moles of (b) relative to 100 moles. Cyclic ethers are highly reactive, and unreacted (b) is difficult to remain. Therefore, (b) used in resin [K5] is preferably (b1), and more preferably (b1-1).

[0199] In resin [K6], the ratio of structural units from each unit is preferably, among all structural units constituting resin [K6]:

[0200] Structural units from (b) (unadded to (a)): 0–30 mol%

[0201] The structural unit (unadditional carboxylic anhydride) obtained by adding (a) to the structural unit from (b): 20–85 mol%.

[0202] The structural unit obtained by adding (a) and further adding carboxylic anhydride to the structural unit from (b): 2–40 mol%.

[0203] Structural units from (c): 10–60 mol%.

[0204] More preferably:

[0205] Structural units from (b) (unadded to (a)): 0–10 mol%

[0206] The structural unit (unadditional carboxylic anhydride) obtained by adding (a) to the structural unit from (b): 40–80 mol%.

[0207] The structural unit obtained by adding (a) and further adding a carboxylic anhydride to the structural unit from (b): 3–30 mol%.

[0208] Structural units from (c): 15–50 mol%.

[0209] A further preferred option is:

[0210] Structural units from (b) (without addition to (a)): 0–5 mol%.

[0211] The structural unit (unadditional carboxylic anhydride) obtained by adding (a) to the structural unit from (b): 50–70 mol%.

[0212] The structural unit obtained by adding (a) and further adding carboxylic anhydride to the structural unit from (b): 5–20 mol%.

[0213] Structural units from (c): 20–40 mol%.

[0214] The total of the structural units from (b) (without addition (a)), the structural units obtained by adding (a) to the structural units from (b) (without addition of carboxylic anhydride), the structural units obtained by adding (a) to the structural units from (b), further adding carboxylic anhydride, and the structural units 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% in all structural units constituting resin [K6].

[0215] The structural unit from (b) (without addition (a)) is preferably a structural unit from a monomer (b1-1) having a structure derived from an epoxidized aliphatic unsaturated hydrocarbon with a straight or branched chain. The structural unit obtained by adding (a) to the structural unit from (b) (without addition carboxylic anhydride) is preferably a structural unit obtained by adding an unsaturated monocarboxylic acid such as (meth)acrylic acid to the structural unit from the monomer (b1-1), wherein the monomer (b1-1) has a structure derived from an epoxidized aliphatic unsaturated hydrocarbon with a straight or branched chain. The structural unit obtained by adding (a) to the structural unit from (b) and further adding a carboxylic anhydride is preferably a structural unit obtained by adding an unsaturated monocarboxylic acid such as (meth)acrylic acid to the structural unit from the monomer (b1-1) and further adding a saturated aliphatic polycarboxylic anhydride such as succinic anhydride, wherein the monomer (b1-1) has a structure derived from an epoxidized aliphatic unsaturated hydrocarbon with a straight or branched chain. The structural unit from (c) is preferably selected from one or more of (meth)acrylates having a straight-chain or branched aliphatic saturated hydrocarbon groups and (meth)acrylates having cyclic saturated hydrocarbon groups, more preferably two or more.

[0216] For resin [K6], as the first stage, the same method as for manufacturing resin [K1] is followed to obtain copolymers (b) and (c). Similarly, for the obtained copolymer, the solution after the reaction can be used directly, or the concentrated or diluted solution can be used, or a substance extracted in solid (powder) form by methods such as reprecipitation can be used.

[0217] The ratio of structural units from (b) and (c) relative to the total molar number of all structural units constituting the copolymer described above,

[0218] The preferred options are:

[0219] Structural units from (b): 5–95 mol%

[0220] Structural units from (c): 5–95 mol%.

[0221] More preferably:

[0222] Structural units from (b): 10–90 mol%

[0223] Structural units from (c): 10–90 moles.

[0224] Furthermore, under the same conditions as the manufacturing method of resin [K4], the carboxylic acid or carboxylic anhydride contained in (a) is reacted with the cyclic ether from (b) contained in the copolymer of (b) and (c). The amount of (a) used is preferably 80 to 100 moles relative to (b).

[0225] The carboxylic anhydride is reacted with the hydroxyl group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride contained in (a). The amount of carboxylic anhydride used is preferably 0.05 to 1 mole relative to the amount of (a) used (in other words, 1 mole of hydroxyl group generated by using (a)), more preferably 0.10 to 0.8 moles, and even more preferably 0.13 to 0.7 moles.

[0226] As a specific example of resin (B), the following can be cited:

[0227] 3,4-Epoxycyclohexylmethyl methacrylate / (meth)acrylic acid copolymer, 3,4-epoxytricyclic [5.2.1.0] 2,6 [K1] decyl acrylate / (meth)acrylic acid copolymer and other resins;

[0228] Glycidyl methacrylate / benzyl methacrylate / methacrylic acid copolymer, glycidyl methacrylate / styrene / methacrylic acid copolymer, 3,4-epoxytricyclic [5.2.1.0] 2,6 Decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxy tricyclic [5.2.1.0] 2,6 [Decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide / (meth)acrylic acid tricyclic [5.2.1.0]] 2,6 [Decane-8-yl ester copolymer, 3,4-epoxy tricyclic [5.2.1.0]] 2,6 Decyl acrylate / (meth)acrylate / (meth)acrylate benzyl acrylate copolymer, 3,4-epoxy tricyclic [5.2.1.0] 2,6 Resins of decyl acrylate / (meth)acrylic acid / phenoxybenzyl (meth)acrylic acid copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer, etc. [K2];

[0229] Resins such as benzyl methacrylate / methacrylic acid copolymer and styrene / methacrylic acid copolymer [K3];

[0230] Resins obtained by adding glycidyl methacrylate to a portion of the carboxylic acid group of a benzyl methacrylate / (meth)acrylic acid copolymer; resins obtained by adding glycidyl methacrylate to a portion of the carboxylic acid group of a benzyl methacrylate / (meth)acrylic acid copolymer; resins obtained by adding glycidyl methacrylate to a portion of the carboxylic acid group of a tricyclodecyl methacrylate / styrene / (meth)acrylic acid copolymer; resins obtained by adding glycidyl methacrylate to a portion of the carboxylic acid group of a tricyclodecyl methacrylate / (meth)acrylic acid copolymer. Resins obtained by adding glycidyl methacrylate to a portion of a carboxylic acid group, resins obtained by adding glycidyl methacrylate to a portion of a norbornene / vinyltoluene / (meth)acrylic acid copolymer, resins obtained by adding glycidyl methacrylate to a portion of a carboxylic acid group of a norbornene / styrene / (meth)acrylic acid copolymer, resins obtained by adding 4-hydroxybutyl acrylate glycidyl ether to a portion of a carboxylic acid group of an N-vinylcarbazole / 2-(acetylacetoxy)ethyl methacrylate / methacrylic acid copolymer, etc. [K4];

[0231] Resins obtained by reacting glycidyl methacrylate with a copolymer of tricyclodecyl methacrylate / methacrylic acid, resins obtained by reacting glycidyl methacrylate with a copolymer of tricyclodecyl methacrylate / styrene / methacrylic acid, and resins obtained by adding 4-hydroxybutyl acrylate glycidyl ether to a copolymer of N-vinylcarbazole / 2-(acetylacetoxy)ethyl methacrylate / methacrylic acid, etc. [K4'];

[0232] Resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylic acid / glycidyl (meth)acrylic acid, and resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylic acid / styrene / glycidyl (meth)acrylic acid, etc. [K5];

[0233] Resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylic acid / glycidyl (meth)acrylic acid, and further reacting the resulting resin with tetrahydrophthalic anhydride; resins obtained by reacting (meth)acrylic acid with a copolymer of 2-ethylhexyl (meth)acrylic acid / tricyclodecyl (meth)acrylic acid / glycidyl (meth)acrylic acid, and further reacting the resulting resin with anhydrous succinic acid; resins obtained by reacting (meth)acrylic acid with a copolymer of methyl (meth)acrylic acid / 2-ethyl (meth)acrylic acid / tricyclodecyl (meth)acrylic acid / glycidyl (meth)acrylic acid), and further reacting the resin with succinic anhydride, etc. [K6] etc.

[0234] The weight-average molecular weight of the polystyrene-converted resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. If the weight-average molecular weight is within this range, the hardness of the cured film tends to increase.

[0235] The dispersion of resin (B) [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1 to 6, more preferably 1.2 to 4.

[0236] The acid value of resin (B), converted from solid content, 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. Here, the acid value is a value determined as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B), and can be obtained, for example, by titration using an aqueous solution of potassium hydroxide.

[0237] The content of resin (B) is based on the total amount of solid components in the curable resin composition, preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and even more preferably 15 to 30% by mass. If the content of resin (B) is within the above range, the heat resistance of the obtained cured film tends to be excellent.

[0238] <Silane Coupling Agent (C)>

[0239] The curable resin composition contains a silane coupling agent (C). Because the curable resin composition contains a silane coupling agent (C), the heat resistance of the resulting cured film can be improved.

[0240] 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-dimethyl-butylene)propylamine, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. 3-methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, 3-epoxypropoxypropyldimethoxymethylsilane, 3-epoxypropoxypropylethoxydimethylsilane.

[0241] Commercially available silane coupling agents (C) include, for example, 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- Silane coupling agents manufactured by Shin-Etsu Chemical Industry Co., Ltd., including 503, 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.

[0242] The content of silane coupling agent (C) is based on the total amount of solid components in the curable resin composition, 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.

[0243] <Polymerization Initiator (D)>

[0244] The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active free radicals, acids, etc., by means of light or heat to initiate the polymerization of the resin (B), etc., and known polymerization initiators can be used. The polymerization initiator (D) is preferably selected from at least one of O-acyl oxime compounds, alkyl phenyl ketone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds, and more preferably O-acyl oxime compounds. Using these polymerization initiators tends to result in high sensitivity and increased transmittance in the visible light region.

[0245] O-acyl oxime compounds are compounds having a partial structure represented by formula (D1). Below, Indicates the bonding site.

[0246]

[0247] Examples of O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, and N-acetoxy-1-[ 9-Ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-one-2-imine. Commercially available products such as IRGACUREOXE01, IRGACURE OXE02, IRGACURE OXE03 (all manufactured by BASF Corporation), PBG-327 (N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), ADEKA ARKLSN-1919, ADEKA ARKLS NCI-831, ADEKA ARKLS NCI-930, and ADEKA OPTOMER N-1919 (all manufactured by ADEKA Corporation) can be used.

[0248] Alkylphenyl ketone compounds are compounds having a partial structure represented by formula (D2-1) or a partial structure represented by formula (D2-2). In these partial structures, the benzene ring may have substituents.

[0249]

[0250] Examples of compounds having a partial structure represented by formula (D2-1) include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one. Commercially available products such as IRGACURE (registered trademarks) 369, 907, and 379 (all manufactured by BASF) can be used. Alternatively, polymerization initiators having chain-transferable groups as described in Japanese Patent Publication No. 2002-544205 can also be used.

[0251] Examples of compounds having a partial structure represented by formula (D2-2) include, for instance, oligomers of 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzoyladium dimethyl ketal. Alkylphenyl ketone compounds are preferably those having a structure represented by formula (D2-1) in terms of sensitivity.

[0252] Examples of triazine compounds include, for instance, 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-piperyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6- [2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine.

[0253] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as IRGACURE 819 (manufactured by BASF) can also be used.

[0254] Examples of biimidazole compounds include, for example, 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 Application Publication Nos. 6-75372 and 6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (e.g., see 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 carbonyl alkoxy group (e.g., see Japanese Patent Application Publication No. 7-10913, etc.).

[0255] Furthermore, examples of polymerization initiators (D) include benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as methyl benzoyl peroxide, 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-phenanthroquinone, 2-ethylanthraquinone, and camphorquinone; and compounds such as 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanium decene compounds. These can be used in combination with polymerization initiators (E) (especially amine compounds) described later.

[0256] As a polymerization initiator (D), an acid-generating agent can also be used. Examples of acid-generating agents include 4-hydroxyphenyl dimethyl sulfonium p-toluenesulfonate, 4-hydroxyphenyl dimethyl sulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethyl sulfonium p-toluenesulfonate, 4-acetoxyphenyl-methyl-benzyl sulfonium hexafluoroantimonate, triphenyl sulfonium p-toluenesulfonate, triphenyl sulfonium hexafluoroantimonate, and diphenyl iodide. p-Toluenesulfonate, diphenyliodine Hexafluoroantimonates, etc. Salts; nitrobenzyl toluenesulfonate, benzoin toluenesulfonate, etc.

[0257] The content of polymerization initiator (D) is 100 parts by mass relative to the content of resin (B), 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.

[0258] <Polymerization Initiator (E)>

[0259] Polymerization initiator (E) is used in conjunction with polymerization initiator (D) and is a compound or sensitizer used to promote the polymerization of resin (B) and the like initiated by polymerization initiator (D).

[0260] Examples of polymerization initiators (E) include thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0261] Examples of thiazoline compounds include compounds represented by formulas (E1-1) to (E1-3) and compounds described in Japanese Patent Application Publication No. 2008-65319.

[0262]

[0263] 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-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as michalcone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, among which 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

[0264] 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.

[0265] Examples of thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0266] Examples of carboxylic acid compounds include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0267] The content of polymerization initiator (E) is 100 parts by weight relative to the content of resin (B), preferably 0 to 30 parts by weight, more preferably 0 to 10 parts by weight.

[0268] <Solvent (F)>

[0269] As for the solvent (F), there are no particular limitations, and solvents commonly used in this field can be used. Examples include ester solvents (solvents containing -COO- and not -O-), ether solvents (solvents containing -O- and not -COO-), ether ester solvents (solvents containing both -COO- and -O-), ketone solvents (solvents containing -CO- and not -COO-), alcohol solvents (solvents containing OH and not -O-, -CO-, and COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

[0270] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0271] 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, phenethyl ether, methyl anisole, etc.

[0272] 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, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-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.

[0273] 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.

[0274] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

[0275] Examples of solvents that can be used to process aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene. Examples of solvents that can be used to process amides include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0276] From the viewpoint of coatability and drying properties, the solvent (F) is preferably a solvent with a boiling point of 100–200 °C at 1 atm. Such a solvent is 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.

[0277] The content of solvent (F) 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 content of solid components in 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.

[0278] <Leveling Agent (G)>

[0279] Examples of leveling agents (G) include silicone surfactants, fluorinated surfactants, and silicone surfactants containing fluorine atoms. They may also have polymerizable groups on their side chains.

[0280] As organosilicon surfactants, examples include surfactants with intramolecular siloxane bonds. Specifically, examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

[0281] As fluorinated surfactants, examples include surfactants with intramolecular fluorocarbon chains. Specifically, examples include Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFACE (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Co., Ltd.), EFTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.).

[0282] As organosilicon surfactants containing fluorine atoms, examples include surfactants with siloxane bonds and fluorocarbon chains within their molecules. Specifically, examples include MEGAFAC (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0283] The content of leveling agent (G) is based on the total amount of solid components in the curable resin composition, 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.

[0284] <Antioxidant (H)>

[0285] Examples of antioxidants (H) include phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. In one embodiment, the antioxidant (H) may also be a potential antioxidant.

[0286] 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), and 2,2 '-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''-(trimethylbenzene-2,4,6-triyl)tri-p-cresol, pentaerythritol tetra[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-butyldibenzo[d,f][1,3,2]dioxaphosphacycloheptane. As phenolic antioxidants, commercially available products can be used, such as Sumilizer (registered trademark) BHT, GM, GS, GP (manufactured by Sumitomo Chemical Co., Ltd.), and Irganox (registered trademark) 1010, 1076, 1330, 3114 (manufactured by BASF).

[0287] Examples of sulfur-based antioxidants include dilaurate 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearate 3,3'-thiodipropionate, and pentaerythritol tetra(3-lauryl thiopropionate). Commercially available sulfur-based antioxidants can also be used. Examples of commercially available sulfur-based antioxidants include Sumilizer (registered trademark) TPL-R and TP-D (manufactured by Sumitomo Chemical Co., Ltd.).

[0288] Examples of phosphorus-based antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tri(nonylphenyl) phosphite, distearate pentaerythritol diphosphite, and tetra(tetranyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite. Commercially available phosphorus-based antioxidants can also be used. Examples of commercially available phosphorus-based antioxidants include Irgafos (registered trademark) 168, 12, 38 (manufactured by BASF), and Adekastab 329K / Adekastab PEP36 (manufactured by ADEKA Corporation).

[0289] 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 can also be used. Examples of commercially available amine-based antioxidants include Sumilizer (registered trademark) BPA, BPA-M1, and 4ML (manufactured by Sumitomo Chemical Co., Ltd.).

[0290] As potential antioxidants, examples include compounds in which the antioxidant site is protected by a protecting group, and which exhibit antioxidant activity after heating at 100–250°C or at 80–200°C in the presence of an acid / base catalyst, thereby removing the protecting group. Commercially available potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA Corporation).

[0291] The content of antioxidant (H) is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, relative to the content of resin (B) per 100 parts by weight.

[0292] <Other Ingredients>

[0293] The curable resin composition may also contain fillers other than titanium dioxide particles (A), polymerizable compounds, other polymeric compounds (resins), ultraviolet absorbers, chain transfer agents, and other additives known in the art, as needed.

[0294] [Method for manufacturing curable resin composition]

[0295] The curable resin composition can be manufactured by mixing titanium dioxide particles (A), resin (B), and silane coupling agent (C) using known methods, as well as polymerization initiator (D), polymerization initiation aid (E), solvent (F), leveling agent (G), antioxidant (H), and other components as needed. The curable resin composition is preferably filtered using a filter with a pore size of approximately 0.01 to 10 μm after mixing the components.

[0296] [Curing film and molded product]

[0297] <Curved film and molded product (cured film)>

[0298] The cured film of this embodiment can preferably be obtained by heating to cure the resin (B) or the like in the curable resin composition. The molded article (cured film) of this embodiment is a substance formed from the curable resin composition, and is a cured film containing the curable resin composition. In addition to film (thin film) shape, the shape of the molded article can also include lens shape, plate shape, powder, granule, non-spherical particle shape, crushed particle shape, porous shape, blocky continuous body, fibrous shape, tubular shape, hollow filament shape, etc., and can be any shape corresponding to the application of the molded article.

[0299] When a cured film is formed on a substrate as a molded product, a curable resin composition can be coated onto the substrate, and then heated and dried (pre-baked) and / or dried under reduced pressure to remove volatile components such as solvents and dry the film, thereby forming a coating film. A cured film is obtained by curing the coating film.

[0300] Examples of substrates include glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda-lime glass with a silica coating; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon substrates; and substrates on which thin films of aluminum, silver, or silver / copper / palladium alloys are formed. Other cured films, resin films, transistors, and circuits can also be formed on these substrates.

[0301] Examples of coating methods include spin coating, slot coating, and slot spin coating. The preferred temperature for heat drying (pre-baking) is 30–120°C, more preferably 50–110°C. The preferred heating time is 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. For reduced pressure drying, it is preferably carried out at a pressure of 50–150 Pa and a temperature range of 20–25°C.

[0302] There is no particular limitation on the thickness of the coating; it can be appropriately selected based on the desired thickness of the cured film.

[0303] Next, the coating is cured. Curing can be achieved by heating (baking) or light exposure, preferably by heating. The heating temperature is preferably 150–250°C, more preferably 160–235°C. The heating time is preferably 1–120 minutes, more preferably 10–60 minutes.

[0304] The thickness of the cured film is not particularly limited and can be appropriately adjusted according to the purpose and application. For example, the thickness of the cured film can be 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

[0305] As described above, a lens as a molded object can be obtained, for example, by forming a cured film on a substrate and applying nanoimprint lithography, dry etching, or the like to the cured film.

[0306] The cured film or the molded article containing the cured film (cured film) is formed from the above-described curable resin composition, and therefore can exhibit a high refractive index. Furthermore, its refractive index can be controlled by the composition of the preparation composition, etc., to achieve the desired refractive index. The refractive index of the cured film at a wavelength of 550 nm can 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. The refractive index of the cured film at a wavelength of 550 nm can be, for example, 2.30 or lower, or 2.20 or lower.

[0307] The refractive index of the cured film at a wavelength of 550 nm can be determined, for example, by the following method: First, a film is coated on a substrate and cured to obtain a substrate with a cured film. Next, using an ellipsometer (JA Woollam, M-2000), the Δψ spectrum in the range of 400 nm to 800 nm is measured on the substrate with the cured film. The Δψ spectrum is analyzed using the accompanying analysis software to determine the refractive index dispersion from 400 nm to 800 nm. The Cauchy mode is used for the analysis. The refractive index at a wavelength of 550 nm is then determined based on the determined refractive index dispersion. Therefore, the refractive index of the cured film at a wavelength of 550 nm can be calculated.

[0308] <Purpose of Use>

[0309] Cured films or molded products (cured films) are suitable for use as lenses in optical devices. Examples of optical devices include imaging devices and display devices. In imaging devices, lenses can be used to improve the light-gathering efficiency of various photoelectric conversion elements. Similarly, in display devices, lenses can be used to improve the efficiency of light extraction from pixels. Lenses can be, for example, superlenses. Superlenses are lenses formed using materials with nanoscale structures, featuring thin designs, high resolution, operability over a wide wavelength range, and design flexibility, and are expected to be used in various fields.

[0310] [Filming device and display device]

[0311] The imaging device of this embodiment includes the curing film described above. The display device of this embodiment includes the curing film described above.

[0312] Examples of imaging devices include CCD and CMOS sensors. Examples of display devices include liquid crystal displays, electroluminescent displays, and plasma displays.

[0313] Example

[0314] The present invention will be described in more detail below with examples, but the present invention is of course not limited to the following examples. Appropriate modifications can be made to implement the invention without departing from the spirit of the above / below, and all such modifications are included within the technical scope of the present invention. It should be noted that, unless otherwise stated, "part" refers to "parts by mass" and "%" refers to "% by mass".

[0315] (Synthesis example 1)

[0316] <Synthesis of Resin (B-1)>

[0317] 100.0 parts by weight of cyclopentanone were added to a flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, and the mixture was heated to 90°C. 63.1 parts by weight of N-vinylcarbazole, 19.9 parts by weight of 2-(acetylacetoxy)methacrylate, 17.0 parts by weight of methacrylic acid, 5.0 parts by weight of azobis(isobutyronitrile), and 51.0 parts by weight of cyclopentanone were mixed, and the resulting solution was continuously added dropwise to the flask through the dropping funnel. The temperature inside the flask was maintained at 90±1°C during the dropwise addition, and the addition was completed after 3 hours. After the addition was completed, the temperature inside the flask was maintained at 90±1°C, and the mixture was allowed to mature for 6 hours. After the reaction, the reaction solution was cooled to below 40°C, and then 0.12 parts by weight of polymerization inhibitor, 12.4 parts by weight of 4-hydroxybutyl acrylate glycidyl ether, 4.5 parts by weight of triphenylphosphine, and 15.6 parts by weight of cyclopentanone were added. The temperature inside the flask was then raised to 110°C, and an addition reaction was carried out at 110±1°C to obtain a copolymer (resin (B-1)) solution. The weight-average molecular weight (Mw) of the generated resin (B-1) was 6.8 × 10⁻⁶. 3 The dispersion (Mw / Mn) is 2.7, and the acid value converted from solid components is 92 mg-KOH / g.

[0318] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the obtained resin were determined using the GPC method under the following conditions.

[0319] Device: HLC-8120GPC (manufactured by Tosoh Corporation)

[0320] Column: TSK-GELG2000HXL

[0321] Column temperature: 40℃.

[0322] Solvent: THF (tetrahydrofuran)

[0323] Flow rate: 1.0 mL / min

[0324] Concentration of solid components in the tested liquid: 0.001–0.01% by mass

[0325] Injection volume: 50μL

[0326] Detector: RI

[0327] Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

[0328] The ratio of the weight-average molecular weight to the number-average molecular weight (Mw / Mn) of the polystyrene obtained above is used as the dispersity.

[0329] (Synthesis example 2)

[0330] <Synthesis of Resin (B-2)>

[0331] In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 276.8 parts of propylene glycol monomethyl ether acetate were taken and stirred while being purged with nitrogen, and the temperature was raised to 120°C. Next, over a period of 2 hours, 35.3 parts of tert-butyl peroxide-2-ethylhexanoate (a polymerization initiator) were added dropwise to the flask from a monomer mixture consisting of 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate, and 12.3 parts of dicyclopentyl methacrylate. After the addition was complete, the mixture was stirred further at 120°C for 30 minutes to carry out a copolymerization reaction, generating an addition copolymer. Then, the flask was purged with air, and 93.7 parts of acrylic acid, 1.5 parts of triphenylphosphine (catalyst), and 0.8 parts of methylquinone (polymerization inhibitor) were added to the above addition copolymer solution. The reaction was continued at 110°C for 10 hours. The epoxy groups from glycidyl methacrylate reacted with acrylic acid, causing the epoxy groups to crack and simultaneously introducing polymerically 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. The hydroxyl groups generated from the cracking of the epoxy groups reacted with the succinic anhydride, introducing carboxyl groups into the side chains, thus 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 generated resin (B-2) was 6.6 × 10⁻⁶. 3 The acid value calculated from the solid components is 92 mg-KOH / g.

[0332] (Examples 1-12 and Comparative Example 1)

[0333] <Preparation of Curable Resin Compositions>

[0334] Titanium oxide 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 through a 4.5 μm PS (polysulfone) filter to obtain the curable resin compositions of Examples 1-12 and Comparative Example 1. In Table 1, the parts of each component represent the parts by mass converted from solid components.

[0335] The components shown in Table 1 are as follows.

[0336] Titanium oxide particles (A):

[0337] (A-1) Titanium oxide 35% propylene glycol monomethyl ether acetate dispersion (manufactured by Ishihara Sangyo Co., Ltd., LDB-142)

[0338] Resin (B):

[0339] (B-1) Resin of Synthetic Example 1 (B-1)

[0340] (B-2) Resin of Synthetic Example 2 (B-2)

[0341] (B-3) Reactive acrylic polymer (manufactured by Nekami Kogyo Co., Ltd., RA-4101)

[0342] (B-4) Benzyl methacrylate / methacrylic acid copolymer (copolymer ratio 80:20 (mass%), weight average molecular weight: 24400)

[0343] Silane coupling agent (C):

[0344] (C-1)3-Methacryloyloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-503)

[0345] Polymerization initiator (D):

[0346] (D-1) ADEKA ARKLS NCI-930 (N-acetoxy-1-(4-(4-(2-hydroxyethoxy)phenylthio)phenyl)propane-1-one-2-imine, manufactured by ADEKA Corporation)

[0347] (D-2) IRGACURE OXE01 (1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), manufactured by BASF)

[0348] Solvent (F):

[0349] (F-1) Propylene glycol monomethyl ether acetate (PGMEA)

[0350] (F-2) Propylene glycol monomethyl ether (PGME)

[0351] Leveling agent (G):

[0352] (G-1) Toray silicone SH8400 (polyether modified silicone oil, manufactured by Toray-Dow Corning Co., Ltd.)

[0353] Antioxidant (H):

[0354] (H-1) ADEKA ARKLS GPA-5001 (Potential antioxidant, manufactured by ADEKA Corporation)

[0355] Polymer compound (I):

[0356] (I-1) Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA)

[0357] <Preparation and Evaluation of Cured Films>

[0358] (Preparation of the curing film)

[0359] The curable resin compositions of Examples 1-12 and Comparative Example 1 were coated onto a 5 cm square glass substrate (CORNING, EAGLE2000) using a spin coating method. The coating was then pre-baked at 85°C for 2 minutes to form a film. Next, the film was baked at 220°C for 10 minutes to obtain a cured film. The thickness of the cured film was measured using a film thickness measuring device (ULVAC, DEKTAK3) and confirmed to be 1 μm.

[0360] (Transmittance measurement)

[0361] For the obtained cured film, an integrating sphere (Japan Spectrophotometer Co., Ltd., ISV-922) was installed on a UV-Vis spectrophotometer (Japan Spectrophotometer Co., Ltd., V-770), and the transmittance within the wavelength range of 400-700 nm was measured at 1 nm intervals, and the average value was calculated. The results are shown in Table 1.

[0362] (Heat resistance test)

[0363] The resulting cured film was heat-treated at 260℃ for 30 minutes. The transmittance of the heat-treated cured film was measured at 1 nm intervals within the wavelength range of 400–700 nm, and the average value was calculated. The heat resistance was evaluated by calculating the change in transmittance before and after heat treatment (transmittance change = 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.

[0364] (Refractive index measurement)

[0365] For the obtained cured film, an ellipsometer (JA Woolham M-2000) was used to measure the Δψ spectrum in the range of 400 nm to 800 nm. The Δψ spectrum was analyzed using the accompanying analysis software, and the refractive index dispersion from 400 nm to 800 nm was calculated as follows. The Cauchy mode was used for the analysis. The refractive index at 550 nm in the calculated refractive index dispersion is shown in Table 1.

[0366]

[0367] As shown in Table 1, the curable resin compositions of the embodiments exhibit superior heat resistance and a sufficiently high refractive index compared to the curable resin compositions of the comparative examples. Based on these results, it can be confirmed that the curable resin compositions of the present invention can form a cured film with a high refractive index and good heat resistance.

Claims

1. A curable resin composition comprising titanium dioxide particles, resin, and a silane coupling agent, Based on the total amount of solid components in the curable resin composition, the content of titanium dioxide particles is greater than 60% by mass and less than 90% by mass.

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

3. A photographing device comprising the cured film as described in claim 2.

Images