Metal oxide sol containing polymerizable silane compound and method for producing same

Abstract

To provide a highly dispersible sol containing metal oxide particles and a plurality of polymerizable functional group-containing silanes, and a varnish containing a thermosetting or photocurable resin using the same.　Provided is a metal oxide sol containing a silane compound and metal oxide particles, wherein the silane compound is represented by formula (1): (in formula (1), R1 each independently represent an alkoxy group, an acyloxy group, or a halogen group; R2 each independently are an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms; R3 is a hydrogen atom or a methyl group; A1 is an alkylene group; A2, A3, and A4 each independently are a methylene group or an oxygen atom; one of A2, A3, and A4 is an oxygen atom; and n is an integer of 1 to 3.). The varnish contains the metal oxide sol and a thermosetting or photocurable resin. The varnish is used for nanoimprinting.

Description

Metal oxide sol containing polymerizable silane compound and method for producing the same

[0001] The present invention relates to a metal oxide sol containing a polymerizable silane compound, a varnish using the sol, and a method for producing the same.

[0002] Compositions containing metal oxide particles and silane compounds (particularly silane coupling agents) are used in the field of coating resins and films. Examples of coating compositions include silane compounds containing polymerizable groups, such as acryloyl groups and glycidyl groups. The use of these compositions in photocurable resin compositions for nanoimprinting has been disclosed (see Patent Document 1). While the silane compounds often contain one polymerizable functional group per silane molecule, silane compounds containing two polymerizable functional groups per silane molecule (silanes containing multiple polymerizable functional groups) undergo cyclopolymerization upon the addition of a polymerization initiator, resulting in smooth curing reactions. It has also been disclosed that cyclization improves heat resistance and suppresses thermal weight loss of the resulting curable resin composition (see Patent Document 2).

[0003] JP 2008-266608 A International Publication No. 2022 / 158176

[0004] An object of the present invention is to provide a highly dispersible sol containing metal oxide particles and a silane containing multiple polymerizable functional groups, a varnish using the same, and a method for producing the same.

[0005] In a first aspect, the present invention provides a metal oxide sol containing a silane compound and metal oxide particles, wherein the silane compound is represented by the formula (1):

[0006]

[0007] (In formula (1), R １ each independently represents an alkoxy group, an acyloxy group, or a halogen group; R ２ are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ３ is a hydrogen atom or a methyl group, and A １ is an alkylene group, and A ２ , A ３ , and A４ are each independently a methylene group or an oxygen atom, and A ２ , A ３ , and A ４ one of which is an oxygen atom, and n is an integer of 1 to 3. As a second aspect, the metal oxide sol according to the first aspect, in which metal oxide particles are coated with a silane compound (1). As a third aspect, the metal oxide sol according to the first aspect, ２ and A ４ is a methylene group, and A ３is an oxygen atom; as a fourth aspect, the metal oxide sol according to any one of the first to third aspects, in which the metal oxide particles have an average primary particle diameter of 5 to 100 nm as measured by a nitrogen gas adsorption method and an average particle diameter of 5 to 200 nm as measured by a dynamic light scattering method; as a fifth aspect, the metal oxide sol according to any one of the first to fourth aspects, in which the metal oxide particles are oxide particles of one type of metal or composite oxide particles of two or more types of metal; as a sixth aspect, the metal oxide sol according to any one of the first to fifth aspects, in which the metal oxide is at least one metal oxide selected from the group consisting of titanium oxide, tin oxide, zirconium oxide, silicon dioxide, zinc oxide, antimony oxide, niobium oxide, and tungsten oxide; As a seventh aspect, the metal oxide sol according to any one of the first to sixth aspects, wherein the metal oxide particles are core-shell type metal oxide particles in which the surfaces of core metal oxide particles are coated with a coating layer of metal oxide particles having a metal oxide component or metal oxide content different from that of the core metal oxide, and wherein the core metal oxide particles, the metal oxide particles of the coating layer, or both contain a photoactive metal oxide; As an eighth aspect, the metal oxide sol according to the seventh aspect, wherein the photoactive metal oxide particles (A) are core-shell type metal oxide particles in which the surfaces of core metal oxide particles containing titanium oxide are coated with metal oxide particles containing silica, and wherein the total metal oxide content of the core metal oxide is 50 mol % or more; As a ninth aspect, the metal oxide sol according to the seventh or eighth aspect, wherein the core metal oxide particles are particles of titanium oxide, zirconium oxide, tin oxide, a composite oxide of titanium oxide-tin oxide, a composite oxide of zirconium oxide-tin oxide, a composite oxide of titanium oxide-zirconium oxide, or a composite oxide of titanium oxide-zirconium oxide-tin oxide; As a tenth aspect, the metal oxide sol according to any one of the seventh to ninth aspects, wherein the metal oxide particles of the coating layer are particles of at least one metal oxide selected from the group consisting of silicon dioxide, tin oxide, antimony oxide, tungsten oxide, aluminum oxide, and zirconium oxide, or particles of a composite metal oxide.As an eleventh aspect, the metal oxide sol according to any one of the first to tenth aspects, further comprising at least one additive a selected from the group consisting of a silane compound other than that of formula (1), an organic acid and a salt thereof, a phosphoric acid ester, an amine, and a surfactant; as a twelfth aspect, the metal oxide sol according to any one of the first to tenth aspects, in which metal oxide particles are coated with the silane compound of formula (1) and the additive a; as a thirteenth aspect, the silane compound other than that of formula (1) is selected from the group consisting of any one of formulas (2) to (4):

[0008]

[0009] (In formula (2), R １１ are each an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having a polyether group, an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and are bonded to a silicon atom by a Si—C bond, and R １２ represents an alkoxy group, an acyloxy group, or a halogen group, and a represents an integer of 1 to 3. In formulas (3) and (4), R １３ and R １５ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, and R １４ and R １６each represents an alkoxy group, an acyloxy group, or a halogen group; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer of 1 to 3; c is an integer of 0 or 1; and d is an integer of 1 to 3. a metal oxide sol according to an eleventh or twelfth aspect, wherein the organic acid is at least one organic acid selected from the group consisting of a divalent aliphatic carboxylic acid, an aliphatic oxycarboxylic acid, an amino acid, and a chelating agent, the divalent aliphatic carboxylic acid being selected from the group consisting of oxalic acid, malonic acid, and succinic acid, the aliphatic oxycarboxylic acid being selected from the group consisting of glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid, the amino acid being selected from the group consisting of glycine, alanine, valine, leucine, serine, and threonine, and the chelating agent being selected from the group consisting of ethylenediaminetetraacetic acid, L-aspartic acid-N,N-diacetic acid, and diethylenetriaminepentaacetic acid; and a metal oxide sol according to a fifteenth aspect, wherein the phosphate ester is represented by any one of formulas (5) to (7):

[0010]

[0011] (In formulas (5) to (7), X １ , X ２ , and X ３ each represents an alkylene group having 2 to 20 carbon atoms; f, h, and j each represent an integer of 1 to 100; e, g, and i each represent an integer of 1 to 3; Y １ , Y ２ , and Y ３represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a (meth)acrylic group. a metal oxide sol according to the eleventh or twelfth aspect, in which the surfactant is at least one phosphoric acid ester selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or a silicon-based surfactant; a metal oxide sol according to the eleventh or twelfth aspect, in which the surfactant is an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or a silicon-based surfactant; a metal oxide sol according to the eleventh or twelfth aspect, in which the amine is a secondary amine or a tertiary amine having a total of 5 to 35 carbon atoms; a metal oxide sol according to any one of the first to seventeenth aspects, in which a dispersion medium of the sol is water, an alcohol, an ester, a ketone, an amide, or a hydrocarbon; a varnish according to any one of the first to eighteenth aspects, in which the dispersion medium of the sol is water, an alcohol, an ester, a ketone, an amide, or a hydrocarbon; a varnish according to the nineteenth aspect, in which the metal oxide sol is used for nanoimprinting; and a varnish according to the nineteenth aspect, in which the varnish is used for nanoimprinting, The method for producing a metal oxide sol according to any one of the first to eighteenth aspects, comprising: step (i): step (i) of solvent-substituting an aqueous solvent of an aqueous sol of metal oxide particles with an alcohol having 1 to 4 carbon atoms which may have an ether bond; step (ii): step (ii) of mixing the alcohol sol of metal oxide particles obtained in step (i) with a silane compound of formula (1); and step (iii): step (iii) of solvent-substituting the alcohol solvent of the alcohol sol of metal oxide particles obtained in step (ii) with an organic solvent other than the alcohol.

[0012] In a composition containing metal oxide particles and a silane containing multiple polymerizable functional groups, if the dispersibility of the metal oxide particles is low during production of the coating composition, the particle components will be unevenly distributed in the coating, and if the particle components have the function of controlling optical properties such as refractive index and transparency, or heat resistance, a uniform coating will not be formed.The above problem was solved by combining metal oxide particles having a colloidal particle size, rather than a metal oxide having a powder-level particle size, with a silane containing multiple polymerizable functional groups.

[0013] In the present invention, metal oxide particles are colloidally converted into a highly dispersible sol, and this sol is combined with a silane containing multiple polymerizable functional groups to form a composition. When this composition is applied to a substrate and cured, the metal oxide particles in the colloidal regions are uniformly distributed in the coating. Cyclopolymerization of the multiple polymerizable functional groups forms smooth bonds between the metal oxide particles in the colloidal regions, between those particles and the matrix-forming resin, and between those particles, the matrix-forming resin, and the substrate. This reduces uneven bonding and component distribution, and further reduces thermal weight loss, resulting in the formation of a highly heat-resistant, uniform, and highly functional coating. This allows the inherent properties of the metal oxide particles themselves (e.g., refractive index, particle size, and heat resistance) to be fully reflected in the coating.

[0014] Preferred embodiments of the present invention will be described below. However, the following embodiments are merely examples for explaining the present invention, and the present invention is not limited to the following embodiments. One embodiment of the present invention is a metal oxide sol containing a silane compound and metal oxide particles, wherein the silane compound is represented by formula (1).

[0015] In formula (1), R １ each independently represents an alkoxy group, an acyloxy group, or a halogen group; R ２ are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ３ is a hydrogen atom or a methyl group, and A １ is an alkylene group, and A ２ , A ３ , and A ４ are each independently a methylene group or an oxygen atom, and A ２ , A ３ , and A ４ One of the groups is an oxygen atom, and n is an integer of 1 to 3. As the alkoxy group, acyloxy group, halogen group, alkyl group, alkylene group, and aryl group, those exemplified below can be used.

[0016] The silane compound of formula (1) is a silane compound containing multiple polymerizable functional groups and functions as a silane coupling agent.

[0017] In formula (1), A ２ and A ４ is a methylene group, and A ３ It is preferable to use a silane coupling agent in which n is an oxygen atom and n is an integer of 3, which is available as a product name X-12-1333A manufactured by Shin-Etsu Chemical Co., Ltd. and represented by the following formula (1-1).

[0018]

[0019] One embodiment of the present invention is a metal oxide sol containing a silane compound and metal oxide particles, and the metal oxide particles may be coated (also referred to as surface-modified) with the silane compound (1).

[0020] In one embodiment of the present invention, the metal oxide particles preferably have an average primary particle size of 5 to 100 nm as measured by nitrogen gas adsorption and an average particle size of 5 to 200 nm as measured by dynamic light scattering.

[0021] The metal oxide particles may be oxide particles of one metal or composite oxide particles of two or more metals. Oxide particles of one metal refer to particles consisting of only a metal oxide of one metal or metal oxides containing metal oxide particles of one metal as the main component.

[0022] The composite oxide particles of two or more metals are composite oxide particles containing two or more metal components, and exhibit a state in which metal oxide particles are bonded to each other at the interface or in which metal oxides are in a solid solution state.

[0023] The metal oxide can be at least one metal oxide selected from the group consisting of titanium oxide, tin oxide, zirconium oxide, silicon dioxide, zinc oxide, antimony oxide, niobium oxide, and tungsten oxide. The metal oxide particles are core-shell metal oxide particles (the "core" refers to the core, and the "shell" refers to the coating layer or coating) in which the surface of a core metal oxide particle is coated with a coating layer of a metal oxide particle having a metal oxide component or metal oxide content different from that of the core metal oxide, and the core metal oxide particle, the metal oxide particle of the coating layer, or both, can contain a photoactive metal oxide. The photoactive metal oxide particles (A) can contain at least one photoactive metal oxide selected from the group consisting of titanium oxide, tin oxide, and zirconium oxide in an amount of 50 mol% or more based on the total metal oxide.

[0024] The core-shell metal oxide particles are core-shell metal oxide particles in which the surface of a core metal oxide particle is coated with a coating layer of metal oxide particles having a metal oxide component or metal oxide content different from that of the core metal oxide, and the core metal oxide particle, the metal oxide particle of the coating layer, or both may contain a photoactive metal oxide. The photoactive metal oxide particles may be metal oxide particles consisting of photoactive metal oxide particles (i) or metal oxide particles containing photoactive metal oxide particles (i). Furthermore, when the photoactive metal oxide particles are core-shell metal oxide particles, the core metal oxide particle, the metal oxide particle of the coating layer, or both may contain photoactive metal oxide particles (i).

[0025] Metal oxide particles made of a photoactive metal oxide refer to cases where the metal oxide particles are made solely of a photoactive metal oxide (or photoactive metal oxide particles (i)) at a ratio of 100 mol %. Metal oxide particles containing a photoactive metal oxide particle refer to cases where the metal oxide particles (A) contain a photoactive metal oxide (or photoactive metal oxide particles (i)) at a ratio of 50 mol % or more but less than 100 mol % based on the total metal oxide. Core-shell metal oxide particles in which the surface of a core metal oxide particle is coated with a coating layer of metal oxide particles having a metal oxide component or metal oxide content different from that of the core metal oxide refer to cases where the core metal oxide particle, the metal oxide particles of the coating layer, or both, contain a photoactive metal oxide (or photoactive metal oxide particles (i)) at a ratio of 50 mol % or more but 100 mol % based on the total metal oxide.

[0026] For example, the photoactive metal oxide particles may be core-shell metal oxide particles in which the surface of a titanium oxide-containing metal oxide particle serving as a core is coated with metal oxide particles containing silica, and the titanium oxide content of the total metal oxide may be 50 mol % or more. Examples of metal oxide particles used as the core include particles containing titanium oxide, zirconium oxide, tin oxide, a titanium oxide-tin oxide composite oxide, a zirconium oxide-tin oxide composite oxide, a titanium oxide-zirconium oxide composite oxide, or a titanium oxide-zirconium oxide-tin oxide composite oxide. These particles have an average primary particle size of 5 to 100 nm or 5 to 60 nm as determined by transmission electron microscope observation.

[0027] Examples of the metal oxide particles contained in the coating layer include metal oxide particles or composite metal oxide particles of at least one type selected from the group consisting of silicon dioxide, tin oxide, antimony oxide, tungsten oxide, aluminum oxide, and zirconium oxide. These particles have an average primary particle diameter of 1 to 10 nm or 1 to 5 nm as determined by observation with a transmission electron microscope. Examples of the metal oxide particles contained in the coating layer include metal oxide particles containing silicon dioxide, tin oxide, antimony oxide, tungsten oxide, aluminum oxide, and zirconium oxide, respectively, alone, or composite metal oxide particles containing a combination of multiple of the above metal oxides. Examples of the composite metal oxide particles include tin oxide-silicon dioxide composite metal oxide particles, tin oxide-zirconium oxide-silicon dioxide composite metal oxide particles, tin oxide-tungsten oxide-silicon dioxide composite metal oxide particles, and antimony oxide-silicon dioxide composite metal oxide particles. When the metal oxide particles in the coating layer contain silica particles, the ratio of silica particles to other metal oxide particles can be set to a mass ratio of (silicon dioxide) / (other metal oxide) of 0.1 to 5.0.

[0028] When a core-shell structure is used, coating with a coating layer containing metal oxide particles with a metal oxide component or metal oxide content different from that of the metal oxide of the core can include cases where the metal oxide components of the core and the coating layer are different, or cases where the metal oxide components of the core and the coating partially overlap but the compounding ratio of the metal oxides is different.

[0029] In the case of a core-shell structure, the mass ratio of the core metal oxide particle to the coating layer metal oxide particle can be set in the range of (coating metal oxide particle) / (core metal oxide particle) = 0.05 to 0.50. For example, in the case of a tin oxide-silicon dioxide composite oxide contained in the coating layer metal oxide particle, sodium stannate or potassium stannate can be used as the alkali stannate, and preferably sodium stannate can be used.

[0030] As the alkali silicate, sodium silicate and potassium silicate can be used.

[0031] The alkali stannate and alkali silicate can be prepared as an aqueous solution containing silicon dioxide / stannic oxide in a mass ratio of 0.1 to 5, and the cations present in the aqueous solution can then be removed using a cation exchange resin before use. The alkali stannate and alkali silicate can be prepared by dissolving them in water in amounts such that the mass ratio of silicon dioxide / stannic oxide is 0.1 to 5.0. The preferred solids concentration of the aqueous solution is (SnO ２ +SiO ２ ) is 1 to 12 mass %.

[0032] The prepared aqueous solution can be subjected to cation removal using a cation exchange resin. A hydrogen-type strongly acidic cation exchange resin is preferred as the cation exchange resin, and a column packed with, for example, Amberlite (trade name) 120B can be used for cation exchange. By carrying out this cation exchange, the silicic acid component and the stannic acid component polymerize, producing silicon dioxide-stannic oxide composite colloidal particles having a primary particle size of 1 to 4 nm. These silicon dioxide-stannic oxide composite colloidal particles have poor stability and gel within several hours if left standing. Therefore, after cation exchange, an amine compound must be added promptly to stabilize the colloidal particles. Specifically, the silicon dioxide / stannic oxide mass ratio is 0.1 to 5.0, and the M / (SnO ２ +SiO ２ It is necessary to obtain an aqueous sol of silicon dioxide-stannic oxide composite oxide colloidal particles having a primary particle size of 1 to 4 nm stabilized by an amine compound present in a molar ratio of (SnO ２ +SiO ２ ) is 0.1 to 10 mass %.

[0033] To stabilize the silicon dioxide-stannic oxide composite colloidal particles produced by the cation exchange, M / (SnO ２ +SiO ２ It is appropriate to add the amine compound in an amount such that the molar ratio of M / (SnO) (where M represents an amine compound) is 0.1 to 1.0. ２+SiO ２ Addition of an amine compound having a molar ratio of silicon dioxide to stannic oxide of less than 0.1 to 1.0 is not preferred because the mixture loses stability and gels after standing for several hours. Next, an aqueous sol of metal oxide colloid particles (a) used for the core, having a primary particle size of 5 to 60 nm, and an aqueous sol of silicon dioxide to stannic oxide having a mass ratio of silicon dioxide to stannic oxide of 0.1 to 5.0 and an M / (SnO ２ +SiO ２ ) (where M represents an amine compound) in a molar ratio of 0.05 to 0.50, an aqueous sol of modified metal oxide colloid particles (A) in which the metal oxide colloid particles (a) are coated with the silicon dioxide-stannic oxide composite oxide colloid particles (b) can be obtained by mixing the silicon dioxide-stannic oxide composite oxide colloid particles (a) with an aqueous sol of silicon dioxide-stannic oxide composite oxide colloid particles (b) having a primary particle size of 1 to 4 nm stabilized with an amine compound in a molar ratio of 0.5 to 50%, and preferably 5 to 30% by mass.

[0034] The aqueous sol of the metal oxide colloidal particles (a) can have a pH of 5 to 11.5, preferably 7 to 11.5. The pH of the aqueous sol can be adjusted as necessary with an alkaline component. Examples of the alkaline component include hydroxides of alkali metals such as lithium, sodium, and potassium; hydroxides of alkaline earth metals such as calcium, magnesium, and strontium; ammonia; alkylamines such as ethylamine, triethylamine, isopropylamine, and n-propylamine; aralkylamines such as benzylamine; alicyclic amines such as piperidine; alkanolamines such as monoethanolamine and triethanolamine; and quaternary ammonium hydroxides. The aqueous sol of the metal oxide colloidal particles (a) and the aqueous sol of the silicon dioxide-stannic oxide composite oxide colloidal particles (b), which are coated particles, are preferably mixed under stirring.

[0035] The mixing ratio of the silicon dioxide-stannic oxide composite oxide colloid particles (b) to the metal oxide colloid particles (a) is preferably 0.05 to 0.50 in terms of mass ratio (b) / (a). By making the mass ratio 0.05 or more, the metal oxide colloid particles (a) serving as cores can be sufficiently coated with the silicon dioxide-stannic oxide composite oxide colloid particles (b), and a stable hydrophilic organic solvent dispersion sol or a hydrophobic organic solvent dispersion sol having a water solubility of 0.05 to 12% by mass can be obtained. Furthermore, a mass ratio of 0.50 is sufficient and efficient. Next, the obtained aqueous sol of the modified metal oxide colloid particles (A) is subjected to cation exchange. The cation exchange is preferably carried out using a hydrogen-type strongly acidic cation exchange resin. Next, the obtained aqueous sol is mixed with an amine compound in a molar ratio of M / (SnO ２ +SiO ２ The amount of the amine compound to be added is determined so that the ratio M / (SnO ２ +SiO ２ By adjusting the molar ratio of M / (SnO) to 0.001 or more, the dispersion stability of the hydrophilic organic solvent dispersion sol of the present invention becomes sufficient, which is preferable. ２ +SiO ２ By adjusting the molar ratio of the silane compound to be bonded to the particle surfaces of the modified metal oxide colloidal particles (A), it is possible to avoid interference with bonding.

[0036] Next, the aqueous medium of the obtained aqueous sol is replaced with a hydrophilic organic solvent. The method for replacing the dispersion medium from water with a hydrophilic organic solvent can be a known method, such as evaporation replacement under normal or reduced pressure, ultrafiltration membrane method, or solvent extraction method. To efficiently perform the solvent replacement, it is preferable to pre-concentrate the obtained aqueous sol so that the concentration of the modified metal oxide colloidal particles (A) contained therein is in the range of 1 to 70% by mass, or 10 to 50% by mass. Known methods such as thermal evaporation and ultrafiltration can be used to concentrate the sol. The temperature of the sol during solvent replacement is in the range from room temperature to the boiling point of the hydrophilic solvent. The solvent replacement is performed until the water content in the sol is less than 5% by mass. The solids concentration of the obtained sol is 20 to 70% by mass, calculated as the total metal oxide concentration of the modified metal oxide colloidal particles (A). The dispersion medium for the sol can be water or an organic solvent such as an alcohol, ester, ketone, amide, or hydrocarbon.

[0037] Examples of organic solvents include alcohols, esters, ketones, amides, and hydrocarbons having 1 to 10 carbon atoms, which may have an ether bond. Examples of alcohols having 1 to 10 carbon atoms include methanol, ethanol, n-propanol, i-propanol, n-butanol, isobutanol, n-pentanol, ethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether. Examples of ketones include linear or cyclic aliphatic ketones having 3 to 30 carbon atoms, such as methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, methyl amyl ketone, and cyclohexanone.

[0038] Examples of ethers include linear or cyclic aliphatic ethers having 3 to 30 carbon atoms, such as diethyl ether and tetrahydrofuran. Examples of esters include linear or cyclic esters having 2 to 30 carbon atoms, such as ethyl acetate, n-butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, n-propyl acetate, isopropyl acetate, ethyl lactate, butyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, phenyl acetate, phenyl lactate, and phenyl propionate. Examples of amides include aliphatic amides having 3 to 30 carbon atoms, such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and N-ethylpyrrolidone.

[0039] Examples of hydrocarbons include linear or cyclic aliphatic or aromatic hydrocarbons having 6 to 30 carbon atoms, such as hexane, heptane, octane, nonane, decane, benzene, toluene, and xylene. The composition of the present invention can use, as a dispersant, at least one additive a selected from the group consisting of silane compounds other than those represented by formula (1), organic acids and their salts, phosphate esters, amines, and surfactants. The surfaces of the metal oxide particles may be coated with the silane compound represented by formula (1) and additive a. The composition of the present invention can further contain a secondary amine or tertiary amine having a total of 5 to 35 carbon atoms.

[0040] For example, when the metal oxide particles (A) contain silica particles, the content of the amine is ２The amount of the secondary amine can be set to 0.01 to 10.0 mmol, or 0.01 to 5.0 mmol, per 100 g of the solvent. Examples of the secondary amine include ethyl n-propylamine, ethylisopropylamine, dipropylamine, diisopropylamine, ethylbutylamine, n-propylbutylamine, dibutylamine, ethylpentylamine, n-propylpentylamine, isopropylpentylamine, dipentylamine, ethyloctylamine, i-propyloctylamine, butyloctylamine, and dioctylamine. Examples of the tertiary amine include triethylamine, ethyldi-n-propylamine, diethyl-n-propylamine, tri-n-propylamine, triisopropylamine, ethyldibutylamine, diethylbutylamine, isopropyldibutylamine, diisopropylethylamine, diisopropylbutylamine, tributylamine, ethyldipentylamine, diethylpentylamine, tripentylamine, methyldioctylamine, dimethyloctylamine, ethyldioctylamine, diethyloctylamine, trioctylamine, benzyldibutylamine, diazabicycloundecene, etc. Among the above amines, secondary amines and tertiary amines having an alkyl group having a total of 6 to 35 carbon atoms are preferred, such as diisopropylamine, tripentylamine, triisopropylamine, dimethyloctylamine, trioctylamine, etc.

[0041] Silane compounds other than those represented by formula (1) include silane coupling agents, and examples of the silane coupling agents include at least one silane compound selected from the group consisting of formulas (2) to (4). In the present invention, photoactive metal oxide particles (A) coated with a hydrolyzate of the above-mentioned silane compound can be used. In formula (2), R １１ are each an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having a polyether group, an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and are bonded to a silicon atom by a Si—C bond, and R ２represents an alkoxy group, an acyloxy group, or a halogen group, and a represents an integer of 1 to 3. In formulas (3) and (4), R １３ and R １５ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, and R １４ and R １６ each represents an alkoxy group, an acyloxy group, or a halogen group; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer of 1 to 3; c is an integer of 0 or 1; and d is an integer of 1 to 3.

[0042] The alkyl group includes alkyl groups having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, an n-pentyl group, a 1-methyln-butyl group, a 2-methyln-butyl group, a 3-methyln-butyl group, a 1,1-dimethyln-propyl group, a 1,2-dimethyln-propyl group, a 2,2-dimethyln-propyl group, a 1-methylcyclopropyl group, a 2 ... Ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group ethyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group cyclobutyl group, 3-ethylcyclobutyl group, 1,2-dimethylcyclobutyl group, 1,3-dimethylcyclobutyl group, 2,2-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,4-dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-n-propylcyclopropyl group, 2-n-propylcyclopropyl group, 1-i-propylcyclopropyl group, 2-i-propylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,Examples of the cyclopropyl group include, but are not limited to, 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl groups, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups.

[0043] The alkylene group may be an alkylene group derived from the alkyl group described above. The aryl group may be an aryl group having 6 to 30 carbon atoms, such as a phenyl group, a naphthyl group, an anthracene group, or a pyrene group. Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, and 2-methyl-3-butenyl. , 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group and the like, but are not limited to these.

[0044] Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, and n-hexyloxy groups, but are not limited to these.

[0045] The acyloxy group includes acyloxy groups having 2 to 10 carbon atoms, such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, an n-butylcarbonyloxy group, an i-butylcarbonyloxy group, an s-butylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, a 1-methyl-n-butylcarbonyloxy group, a 2-methyl-n-butylcarbonyloxy group, a 3-methyl-n-butylcarbonyloxy group, a 1,1-dimethyl-n-propylcarbonyloxy group, a 1,2-dimethyl-n-propylcarbonyloxy group, a 2,2-dimethyl-n-propylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, an n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, and a 2-methyl-n-pentylcarbonyloxy group. Examples of the halogen group include fluorine, chlorine, bromine, and iodine.

[0046] The organic group having a polyether group includes a polyetherpropyl group having an alkoxy group. For example, (CH ３ O) ３ SiC ３ H ６ (OC ２ H ４ ) nOCH ３n can be any number between 1 and 100, or between 1 and 10. Examples of organic groups having an epoxy group include a 2-(3,4-epoxycyclohexyl)ethyl group and a 3-glycidoxypropyl group. The (meth)acryloyl group refers to both an acryloyl group and a methacryloyl group. Examples of organic groups having a (meth)acryloyl group include a 3-methacryloxypropyl group and a 3-acryloxypropyl group.

[0047] An example of an organic group having a mercapto group is a 3-mercaptopropyl group. Examples of organic groups having an amino group are a 2-aminoethyl group, a 3-aminopropyl group, an N-2-(aminoethyl)-3-aminopropyl group, an N-(1,3-dimethyl-butylidene)aminopropyl group, an N-phenyl-3-aminopropyl group, and an N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group. An example of an organic group having a ureido group is a 3-ureidopropyl group. An example of an organic group having a cyano group is a 3-cyanopropyl group. The silane compounds represented by the above formulas (3) and (4) are preferably compounds capable of forming trimethylsilyl groups on the surfaces of silica particles.

[0048] Examples of such compounds include the following.

[0049]

[0050] In the above formula, R ２２ is an alkoxy group, for example, a methoxy group or an ethoxy group. The silane compound may be a silane compound manufactured by Shin-Etsu Chemical Co., Ltd. The silane compound reacts with the hydroxyl groups on the surface of silica particles, for example, the silanol groups in the case of silica particles, to coat the surface of the silica particles with the silane compound through siloxane bonds. The reaction can be carried out at a temperature ranging from 20°C to the boiling point of the dispersion medium, for example, at a temperature ranging from 20°C to 100°C. The reaction can be carried out for about 0.1 to 6 hours.

[0051] The silane compound is used in such a manner that the number of silicon atoms in the silane compound is 0.1 / nm as a coating amount on the surface of the silica particles. ２ ~6.0 pieces / nm ２ The silica particle surfaces can be coated by adding a silane compound equivalent to the coating amount to the silica sol. Water is required for the hydrolysis of the silane compound, but if the sol is an aqueous solvent, the water in the aqueous solvent can be used. Even when the aqueous medium is replaced with an organic solvent, the water remaining in the solvent can be used. For example, water present in the solvent at 0.01 to 5% by mass or 0.01 to 1% by mass can be used. Furthermore, hydrolysis can be carried out with or without a catalyst. When hydrolysis is carried out without a catalyst, the silica particle surfaces are on the acidic side. When hydrolysis is carried out with a catalyst, examples of hydrolysis catalysts include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0052] Examples of metal chelate compounds used as hydrolysis catalysts include triethoxy mono(acetylacetonato)titanium and triethoxy mono(acetylacetonato)zirconium. Examples of organic acids used as hydrolysis catalysts include acetic acid and oxalic acid. Examples of inorganic acids used as hydrolysis catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Examples of organic bases used as hydrolysis catalysts include pyridine, pyrrole, piperazine, and quaternary ammonium salts. Examples of inorganic bases used as hydrolysis catalysts include ammonia, sodium hydroxide, and potassium hydroxide.

[0053] The organic acid is at least one organic acid selected from the group consisting of divalent aliphatic carboxylic acids, aliphatic oxycarboxylic acids, amino acids, and chelating agents. Examples of divalent aliphatic carboxylic acids include oxalic acid, malonic acid, and succinic acid. Examples of aliphatic oxycarboxylic acids include glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid. Examples of amino acids include glycine, alanine, valine, leucine, serine, and threonine. Examples of chelating agents include ethylenediaminetetraacetic acid, L-aspartic acid-N,N-diacetic acid, and diethylenetriaminepentaacetic acid. Examples of organic acid salts include alkali metal salts, ammonium salts, and amine salts of the above organic acids. Examples of alkali metal salts include sodium and potassium.

[0054] The amount of organic acid and its salt added is ２ The amount of the phosphate ester can be set to 0.01 to 10.0 mmol, or 0.01 to 5.0 mmol per 100 g of the aqueous solution. The phosphate ester can be at least one phosphate ester compound selected from the group consisting of formulas (5) to (7).

[0055] In formulas (5) to (7), X １ , X ２ , and X ３ each represents an alkylene group having 2 to 20 carbon atoms; f, h, and j each represent an integer of 1 to 100; e, g, and i each represent an integer of 1 to 3; Y １ , Y ２ , and Y ３ Each of the groups represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a (meth)acrylic group. The phosphate ester is preferably a polyoxyethylene alkyl ether phosphate ester, and for example, the phosphate ester is a phosphate ester in which the terminal alkyl group (Y1) in the above formula (4) represents an alkyl group having 6 to 10 carbon atoms or 12 to 15 carbon atoms. These products include, for example, products manufactured by Toho Chemical Industry Co., Ltd., under the trade names Phosphanol RA-600 and RS-610.

[0056] The amount of phosphate ester added is SiO２ The concentration can be set to 0.01 to 10.0 millimoles or 0.01 to 5.0 millimoles per 100 g of the surfactant. Examples of surfactants that can be used include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and silicone surfactants. Examples of anionic surfactants that can be used in the present invention include sodium and potassium salts of fatty acids, alkylbenzene sulfonates, higher alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfate salts, α-sulfofatty acid esters, α-olefin sulfonates, monoalkyl phosphate ester salts, and alkanesulfonates. For example, examples of alkylbenzene sulfonates include sodium salts, potassium salts, and lithium salts, such as sodium C10-C16 alkylbenzene sulfonate, C10-C16 alkylbenzene sulfonic acid, and sodium alkylnaphthalene sulfonate.

[0057] Examples of higher alcohol sulfates include sodium dodecyl sulfate (sodium lauryl sulfate), triethanolamine lauryl sulfate, and triethanolammonium lauryl sulfate, each of which has 12 carbon atoms. Examples of polyoxyethylene alkyl ether sulfates include sodium polyoxyethylene styrenated phenyl ether sulfate, ammonium polyoxyethylene styrenated phenyl ether sulfate, sodium polyoxyethylene decyl ether sulfate, ammonium polyoxyethylene decyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, and sodium polyoxyethylene oleyl cetyl ether sulfate. Examples of α-olefin sulfonates include sodium α-olefin sulfonate. Examples of alkane sulfonates include sodium 2-ethylhexyl sulfate. Examples of cationic surfactants used in the present invention include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, and amine salts.

[0058] Alkyltrimethylammonium salts are quaternary ammonium salts that have chloride ions or bromide ions as counterions. Examples include dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, coconut alkyltrimethylammonium chloride, and alkyl(C16-18)trimethylammonium chloride. Dialkyldimethylammonium salts have two lipophilic main chains and two methyl groups. Examples include bis(hydrogenated tallow)dimethylammonium chloride. Examples include didecyldimethylammonium chloride, dicocoalkyldimethylammonium chloride, dihydrogenated tallow alkyldimethylammonium chloride, and dialkyl(C14-18)dimethylammonium chloride.

[0059] Alkyldimethylbenzylammonium salts are quaternary ammonium salts having one lipophilic main chain, two methyl groups, and one benzyl group, and examples thereof include benzalkonium chloride. Examples include alkyl(C8-18)dimethylbenzylammonium chloride. Amine salt agents include those in which the hydrogen atoms of ammonia are substituted with one or more hydrocarbon groups, and examples thereof include N-methylbishydroxyethylamine fatty acid ester hydrochloride. Examples of amphoteric surfactants that can be used in the present invention include N-alkyl-β-alanine-type alkylamino fatty acid salts, alkylcarboxybetaine-type alkylbetaines, and N,N-dimethyldodecylamine oxide-type alkylamine oxides. Examples of these include lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, and lauryldimethylamine oxide.

[0060] Nonionic surfactants for use in the present invention include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, alkyl glucosides, polyoxyethylene fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and fatty acid alkanolamides. For example, examples of polyoxyethylene alkyl ethers include polyoxyethylene dodecyl ether (polyoxyethylene lauryl ether), polyoxyalkylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyalkylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene behenyl ether, polyoxyethylene-2-ethylhexyl ether, and polyoxyethylene isodecyl ether.

[0061] Examples of polyoxyethylene alkylphenol ethers include polyoxyethylene styrenated phenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene distyrenated phenyl ether, and polyoxyethylene tribenzyl phenyl ether. Examples of alkyl glucosides include decyl glucoside and lauryl glucoside. Examples of polyoxyethylene fatty acid esters include polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyethylene glycol distearate, polyethylene glycol dioleate, and polypropylene glycol dioleate.

[0062] Examples of sorbitan fatty acid esters include sorbitan monocaprylate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monosesquioleate, and ethylene oxide adducts thereof. Examples of polyoxyethylene sorbitan fatty acid esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan triisostearate.

[0063] Examples of fatty acid alkanolamides include coconut oil fatty acid diethanolamide, beef tallow fatty acid diethanolamide, lauric acid diethanolamide, and oleic acid diethanolamide.

[0064] Further examples of surfactants include polyoxyalkyl ethers or polyoxyalkyl glycols such as polyoxyethylene polyoxypropylene glycol and polyoxyethylene fatty acid esters, polyoxyethylene hydrogenated castor oil ether, sorbitan fatty acid ester alkyl ethers, alkyl polyglucosides, sorbitan monooleate, and sucrose fatty acid esters. Silicone surfactants can also be used as surfactants. Silicone surfactants are compounds having repeating units containing siloxane bonds in their main chains. The weight-average molecular weight of the silicone surfactants can range from 500 to 50,000. These surfactants may also be modified silicone surfactants, and examples include structures in which organic groups are introduced into the side chains and / or terminals of polysiloxanes. Examples of organic groups include amino groups, epoxy groups, alicyclic epoxy groups, carbinol groups, mercapto groups, carboxyl groups, aliphatic ester groups, aliphatic amide groups, and polyether groups.

[0065] Examples of silicone surfactants include trade names such as Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), Silwet 1-77, L-7280, L-7001, L-7002, L-7200, L-7210, L-7220, L-7230, L7500, L-7600, L-7602, L-7604, L-7605, L-7622, ​​and L-765. Examples of suitable polyether-modified silicones include L-7001 (manufactured by Dowsil Industries, Inc.), L-8500, and L-8610 (all manufactured by Momentive Performance Materials, Inc.), KP-341, KF-6001, and KF-6002 (manufactured by Shin-Etsu Silicones Co., Ltd.), and BYK307, BYK323, and BYK330 (manufactured by BYK-Chemie). For example, a polyether-modified silicone under the trade name of L-7001 (manufactured by Dowsil Industries, Inc.) can be suitably used.

[0066] The method for producing the metal oxide sol can include the following steps (i) to (iii): step (i): solvent-substituting the aqueous solvent of the aqueous sol of metal oxide particles with an alcohol having 1 to 4 carbon atoms which may have an ether bond, step (ii): mixing the alcohol sol of metal oxide particles obtained in step (i) with a silane compound of formula (1), and step (iii): solvent-substituting the alcohol solvent of the alcohol sol of metal oxide particles obtained in step (ii) with an organic solvent other than the alcohol. The composition obtained through the production method has a solids content of 0.1 to 70% by mass, and the photoactive metal oxide particles (A) can account for 80 to 99% by mass and the dispersant for 1 to 20% by mass of the total solids content.

[0067] Here, the term "solid content" refers to the components of the composition excluding the solvent component, and the term "solid concentration" refers to the concentration of solids in the composition. The composition of the present invention can be further mixed with a thermosetting or photocurable resin to produce a varnish. A varnish containing a curing agent such as an amine-based curing agent, an acid anhydride-based curing agent, or an acid generator-based curing agent (thermal acid generator or photoacid generator) can be cured. A varnish containing the composition, a resin, and a curing agent can be applied to or filled on a substrate and then heated, irradiated with light, or a combination thereof to form a cured product. Examples of curable resins include resins having functional groups such as epoxy groups or (meth)acryloyl groups. Examples of epoxy group-containing resins include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, novolac-type epoxy resins, aliphatic-type epoxy resins, and glycidylamine-type epoxy resins.

[0068] Examples of the (meth)acryloyl group-containing resin include polymerizable (meth)acrylate monomers, and examples of the monofunctional acrylate monomer include β-carboxyethyl acrylate, isobornyl acrylate, phenoxydiethylene glycol acrylate, phenoxyethyl acrylate, etc. Examples of the bifunctional acrylate monomer include dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, PO-modified neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, PEG 200 diacrylate, PEG 400 diacrylate, PEG 600 diacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol diacrylate, etc. Examples of trifunctional acrylate monomers include trimethylolpropane triacrylate, trimethylolpropane ethoxy triacrylate, glycerin propoxy triacrylate, pentaerythritol (tri / tetra)acrylate, and pentaerythritol (tri / tetra)acrylate. Examples of tetrafunctional or higher acrylate monomers include pentaerythritol alkoxytetraacrylate, pentaerythritol ethoxytetraacrylate, pentaerythritol (tri / tetra)acrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexaacrylate. Examples of methacrylate monomers include isobornyl methacrylate, polyethylene glycol dimethacrylate, and trimethylpropane trimethacrylate. These polymerizable (meth)acrylate monomers can be used alone or in combination of two or more.

[0069] In the case of a thermosetting varnish, the thermosetting agent can be contained in a ratio of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, relative to the functional groups, such as epoxy groups or (meth)acryloyl groups, of the resin. The equivalent of the thermosetting agent relative to the curable resin is expressed as the equivalent ratio of the thermosetting agent to the functional groups. Examples of thermosetting agents include phenolic resins, amine-based curing agents, polyamide resins, imidazoles, polymercaptans, acid anhydrides, and thermal acid generators. Acid anhydride-based curing agents and amine-based curing agents are particularly preferred.

[0070] Although these thermosetting agents can be used by dissolving them in a solvent even if they are solid, evaporation of the solvent reduces the density of the cured product and creates pores, which reduces the strength and water resistance of the cured product. Therefore, it is preferable that the curing agent itself is liquid at room temperature and normal pressure. Examples of phenolic resins include phenol novolac resins and cresol novolac resins.

[0071] Examples of amine curing agents include piperidine, N,N-dimethylpiperazine, triethylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthenediamine, isophoronediamine, diaminodicyclohexylmethane, 1,3-diaminomethylcyclohexane, xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and diethyltoluenediamine. Among these, liquid diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthenediamine, isophoronediamine, diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, diethyltoluenediamine, etc. can be preferably used.

[0072] Examples of polyamide resins include polyamidoamines, which are produced by condensation of dimer acid and polyamine and have a primary amine and a secondary amine in the molecule. Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and epoxyimidazole adduct.

[0073] Examples of polymercaptans include those in which a mercaptan group is present at the end of a polypropylene glycol chain and those in which a mercaptan group is present at the end of a polyethylene glycol chain, and liquid polymers are preferred.

[0074] As the acid anhydride curing agent, anhydrides of compounds having multiple carboxyl groups in one molecule are preferred.These acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methylendomethylene tetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, chlorendic anhydride, etc.As the thermal acid generator, sulfonium salts and phosphonium salts are mentioned, and sulfonium salts are preferably used.For example, the following compounds can be mentioned:

[0075]

[0076] In the formula, R represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, with an alkyl group having 1 to 12 carbon atoms being particularly preferred. Among these, methyltetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride (methylnadic anhydride, methylhimic anhydride), hydrogenated methylnadic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methylhexahydrophthalic anhydride, and a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, which are liquid at room temperature and normal pressure, are preferred. The viscosity of these liquid acid anhydrides is approximately 10 mPas to 1,000 mPas when measured at 25°C. Furthermore, when obtaining the above-mentioned cured product, a curing aid may be used in combination, as appropriate. Examples of the curing aid include organic phosphorus compounds such as triphenylphosphine and tributylphosphine, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and methyltriphenylphosphonium diethyl phosphate, and quaternary ammonium salts such as 1,8-diazabicyclo(5,4,0)undecane-7-ene, salts of 1,8-diazabicyclo(5,4,0)undecane-7-ene and octylic acid, zinc octylate, and tetrabutylammonium bromide. These curing aids can be contained in a ratio of 0.001 to 0.1 parts by mass per part by mass of the curing agent.

[0077] A thermosetting varnish is obtained by mixing a composition, a resin, a curing agent, and optionally, a curing aid. This mixing can be performed in a reaction vessel using a stirring blade or kneader. Mixing is performed by a heated mixing method at a temperature of 60°C to 100°C for 0.5 to 1 hour. The resulting curable resin varnish (thermosetting composition) is a thermosetting coating composition with an appropriate viscosity for use, for example, as a liquid encapsulant. Liquid thermosetting varnishes can be prepared to any viscosity and can be used as transparent encapsulants for LEDs and other devices by casting, potting, dispensing, printing, or other methods, allowing for partial encapsulation at any desired location. The liquid thermosetting composition is directly mounted on an LED or other device in its liquid state using the method described above, followed by drying and curing to obtain a cured epoxy resin product. The thermosetting varnish (thermosetting coating composition) can be applied to a substrate and cured at a temperature of 80°C to 200°C.

[0078] In the case of a photocurable varnish, a photocuring agent (photoacid generator or photoradical generator) can be contained in an amount of 0.5 to 20% by mass, preferably 0.8 to 10% by mass, relative to the functional groups in the resin, such as epoxy groups or (meth)acryloyl groups. The photoacid generator is not particularly limited as long as it generates an acid directly or indirectly upon irradiation with light.

[0079] Specific examples of the photoacid generator that can be used include triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivative compounds, onium salts such as iodonium salts, sulfonium salts, phosphonium salts, and selenium salts, metallocene complexes, and iron arene complexes. Among the onium salts used as the photoacid generator, examples of iodonium salts include diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium mesylate, bis(p-tert-butylphenyl)iodonium tosylate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium )iodonium tetrafluoroborate, bis(p-tert-butylphenyl)iodonium chloride, bis(p-chlorophenyl)iodonium chloride, bis(p-chlorophenyl)iodonium tetrafluoroborate, and further bis(4-t-butylphenyl)iodonium hexafluorophosphate and other bis(alkylphenyl)iodonium salts; alkoxycarbonylalkoxy-trialkylaryl iodonium salts (for example, 4-[(1-ethoxycarbonyl-ethoxy)phenyl]-(2,4,6-trimethylphenyl)-iodonium hexafluorophosphate, etc.); and bis(alkoxyaryl)iodonium salts (for example, bis(alkoxyphenyl)iodonium salts such as (4-methoxyphenyl)phenyliodonium hexafluoroantimonate).

[0080] Examples of sulfonium salts include triphenylsulfonium salts such as triphenylsulfonium chloride, triphenylsulfonium bromide, tri(p-methoxyphenyl)sulfonium tetrafluoroborate, tri(p-methoxyphenyl)sulfonium hexafluorophosphonate, tri(p-ethoxyphenyl)sulfonium tetrafluoroborate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, and triphenylsulfonium hexafluorophosphate; and sulfonium salts such as (4-phenylthiophenyl)diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl)diphenylsulfonium hexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluorophosphate, and (4-methoxyphenyl)diphenylsulfonium hexafluoroantimonate.

[0081] Examples of phosphonium salts include triphenylphosphonium chloride, triphenylphosphonium bromide, tri(p-methoxyphenyl)phosphonium tetrafluoroborate, tri(p-methoxyphenyl)phosphonium hexafluorophosphonate, tri(p-ethoxyphenyl)phosphonium tetrafluoroborate, 4-chlorobenzenediazonium hexafluorophosphate, and benzyltriphenylphosphonium hexafluoroantimonate. Other examples include selenium salts such as triphenylselenium hexafluorophosphate, and metallocene complexes such as (η5 or η6-isopropylbenzene)(η5-cyclopentadienyl)iron(II) hexafluorophosphate. The following compounds can also be used as photoacid generators.

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091] As the photoacid generator, sulfonium salt compounds and iodonium salt compounds are preferred. The anion species thereof is CF ３ SO ３ － , C ４ F ９ SO ３ － , C ８ F １７ SO ３ － , camphorsulfonate anion, tosylate anion, BF ４ － , P.F. ６ － , AsF ６ － and SbF ６ － In particular, anion species such as phosphorus hexafluoride and antimony hexafluoride, which exhibit strong acidity, are preferred.

[0092] Examples of photoradical generators include acetophenones, benzoins, benzophenones, thioxanthones, and acylphosphine oxides.

[0093] Examples of acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer.

[0094] Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0095] Examples of benzophenones include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, and (4-benzoylbenzyl)trimethylammonium chloride.

[0096] Examples of thioxanthones include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride.

[0097] Examples of acylphosphine oxides include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. The composition and varnish of the present invention may contain conventional additives as needed. Examples of such additives include pigments, colorants, thickeners, sensitizers, antifoaming agents, leveling agents, coatability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light resistance stabilizers, etc.), plasticizers, dissolution promoters, fillers, and antistatic agents. These additives may be used alone or in combination of two or more.

[0098] Examples of methods for applying the composition and varnish of the present invention include flow coating, spin coating, spray coating, screen printing, casting, bar coating, curtain coating, roll coating, gravure coating, dipping, slit coating, and nanoimprinting.

[0099] The nanoimprinting method is a method for producing a microstructure by applying nanoimprint processing to a resin composition to obtain a microstructure, and can include, for example, the steps of (1) applying the resin composition to form a coating, (2) transferring a pattern to the coating using a nanostamper, and (3) curing the coating to which the pattern has been transferred to obtain a microstructure.

[0100] In the above step (1), a coating made of a resin composition may be formed on a transparent support, and in the step (2), a nanostamper made of at least one material selected from silicone, glass, and silica glass may be used. Furthermore, steps (2) and (3) may involve pressing the nanostamper against the coating at a pressure of 0.1 to 10 MPa for 0.1 to 300 seconds or 5 to 50 seconds to transfer the pattern, while simultaneously applying heat or UV irradiation to harden the coating to obtain a microstructure. The manufacturing method of the present invention may further include a step (4) of etching the cured coating. The present invention can provide a microstructure. Examples of microstructures include semiconductor materials, diffractive light-condensing films, polarizing films, optical waveguides, and holograms.

[0101] Nanoimprinting can be used to refer to not only conventional nanoimprinting (nanoimprinting in the narrow sense), in which a pattern is transferred by pressing a nanostamper onto a coating provided on a support, but also to a mold-based fine pattern transfer technology (nanoimprinting in the broad sense), in which a mold on which a fine pattern is formed is used instead of a nanostamper, a resin composition is poured onto the mold, a support is placed on top of it, and the mold is pressed from the top surface. Because a resin composition that is resistant to cure shrinkage is used, nanoimprinting can efficiently produce microstructures with nanometer-order fine patterns with excellent precision. This method of nanoimprinting a resin composition is suitable for mass production of microstructures, and can economically and efficiently produce microstructures such as semiconductor materials, optical waveguides, and holograms.

[0102] In the present invention, the photo-coating composition can be applied to a substrate and cured by light irradiation. Heating can also be performed before or after light irradiation. The thickness of the coating film can be selected from a range of about 0.01 μm to 10 mm depending on the intended use of the cured product. For example, when used as a photoresist, the thickness can be about 0.05 to 10 μm (particularly 0.1 to 5 μm), when used as a printed wiring board, the thickness can be about 5 μm to 5 mm (particularly 100 μm to 1 mm), and when used as an optical thin film, the thickness can be about 0.1 to 100 μm (particularly 0.3 to 50 μm).

[0103] When a photoacid generator is used, the light to be irradiated or exposed may be, for example, gamma rays, X-rays, ultraviolet light, or visible light, and is usually visible light or ultraviolet light, particularly ultraviolet light. The wavelength of the light is, for example, about 150 to 800 nm, preferably about 150 to 600 nm, more preferably about 200 to 400 nm, and particularly about 300 to 400 nm. The amount of irradiation light varies depending on the thickness of the coating film, but is, for example, about 2 to 20,000 mJ / cm. ２ , preferably 5 to 5000 mJ / cm ２ The light source can be selected depending on the type of light to be exposed, and for example, in the case of ultraviolet light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a deuterium lamp, a halogen lamp, or laser light (helium-cadmium laser, excimer laser, etc.) can be used. Such light irradiation causes the curing reaction of the composition to proceed.

[0104] When a thermal acid generator is used, or when a photoacid generator is used, heating of the coating film, which is optionally performed after light irradiation, is carried out at, for example, 60 to 250°C, preferably about 100 to 200°C. The heating time can be selected from the range of 3 seconds or more (e.g., about 3 seconds to 5 hours), for example, 5 seconds to 2 hours, preferably about 20 seconds to 30 minutes, and typically about 1 minute to 3 hours (e.g., about 5 minutes to 2.5 hours). Furthermore, when forming a pattern or image (e.g., when producing a printed wiring board, etc.), the coating film formed on the substrate may be subjected to pattern exposure. This pattern exposure may be carried out by scanning with laser light or by irradiating with light through a photomask. A pattern or image can be formed by developing (or dissolving) the non-irradiated areas (unexposed areas) generated by such pattern exposure with a developer.

[0105] As the developer, an alkaline aqueous solution or an organic solvent can be used. Examples of alkaline aqueous solutions include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine. The alkaline developer is generally an aqueous solution of 10% by mass or less, and preferably an aqueous solution of 0.1 to 3.0% by mass. Furthermore, alcohols and surfactants can be added to the developer, and these are each preferably present in an amount of 0.05 to 10 parts by mass per 100 parts by mass of the developer.

[0106] Among these, a 0.1 to 2.38 mass % aqueous solution of tetramethylammonium hydroxide can be used. Furthermore, the organic solvent used as the developer can be a common organic solvent, such as acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, ethyl lactate, cyclohexanone, etc., and these can be used alone or in combination. Propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, etc. are particularly preferred.

[0107] In the present invention, an adhesion promoter can be added to the varnish for the purpose of improving adhesion to the substrate after development. Examples of such adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; vinyltrichlorosilane; and γ-chloropropyltrimethoxysilane. Examples of adhesion promoters include silanes such as γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-(N-piperidinyl)propyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. One or more of the above adhesion promoters can be used alone or in combination. The amount of these adhesion promoters added is typically 18% by mass or less, preferably 0.0008 to 9% by mass, and more preferably 0.04 to 9% by mass, based on the solid content.

[0108] The composition and varnish of the present invention may contain a sensitizer. Usable sensitizers include anthracene, phenothiazene, perylene, thioxanthone, and benzophenone thioxanthone. Furthermore, examples of sensitizing dyes include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, and pyrylium salt dyes. Anthracene sensitizers are particularly preferred. When used in combination with a cationic curing catalyst (radiation-sensitive cationic polymerization initiator), they dramatically improve sensitivity and also possess radical polymerization initiation capabilities. In hybrid systems that combine the cationic curing system of the present invention with a radical curing system, the catalyst species can be simplified. Specific anthracene compounds that are effective include dibutoxyanthracene and dipropoxyanthraquinone. The amount of the sensitizer added is 0.01 to 20% by weight, preferably 0.01 to 10% by weight, based on the solid content.

[0109] Thermosetting and photocuring materials using varnishes containing the epoxy compound of the present invention are characterized by rapid curing, transparency, and minimal cure shrinkage, and can be used to coat and bond electronic components, optical components, and precision mechanical components. For example, they can be used to bond mobile phone and camera lenses, optical elements such as light-emitting diodes (LEDs) and semiconductor lasers (LDs), liquid crystal panels, biochips, camera lenses and prisms, magnetic components in hard disks of personal computers, CD and DVD player pickups (the part that captures optical information reflected from the disc), speaker cones and coils, motor magnets, circuit boards, electronic components, and internal engine components of automobiles. As hard coating materials for surface protection of automobile bodies, lamps and electrical appliances, building materials, and plastics, they can be used for, for example, automobile and motorcycle bodies, headlight lenses and mirrors, plastic eyeglass lenses, mobile phones, game consoles, optical films, ID cards, and the like. Examples of ink materials for printing on metals such as aluminum and plastics include inks for printing on cards such as credit cards and membership cards, switches on electrical appliances and office equipment, and keyboards, as well as inks for inkjet printers for CDs, DVDs, etc.

[0110] Other applications include a technique for curing resins in combination with 3D CAD to create complex three-dimensional objects, application to stereolithography such as the production of models for industrial products, and application to optical fiber coatings, adhesion, optical waveguides, thick-film resists, etc. Furthermore, a cured body-forming composition containing the composition of the present invention can be suitably used as an insulating resin for electronic materials such as semiconductor encapsulation materials, adhesives for electronic materials, printed wiring board materials, interlayer insulating film materials, and encapsulants for power modules, as well as an insulating resin used in high-voltage equipment such as generator coils, transformer coils, and gas-insulated switchgear.

[0111] [Total Metal Oxide Concentration] The sol was weighed in a crucible and pre-dried by heating at 110° C. for 30 minutes to remove the solvent, and then calcined at 600° C. for 30 minutes. The crucible was weighed, and the total metal oxide concentration was calculated from the weight of the residue.

[0112] [Average particle size by dynamic light scattering (particle size by dynamic light scattering)] The sol was diluted with a dispersion solvent, and the particle size was measured using the parameters of the solvent with a dynamic light scattering measuring device (manufactured by Malvern Instruments Ltd, trade name: Zetasizer).

[0113] [Dispersion Stability] After storing the dispersion liquid under the conditions of 50°C for 1 week, samples in which the particle size measured by dynamic light scattering was less than 1.2 times that before the storage test were evaluated as unchanged and were marked with "○", whereas samples in which the particle size measured by dynamic light scattering was changed by 1.2 times or more than that before the storage test, or samples in which the sol state could not be maintained and sedimentation and separation into two layers occurred were evaluated with "×".

[0114] [Surface Modification Ratio] From the molecular formula of the surface modifier (silane compound), the ratio of the molecular weight derived from carbon to the molecular weight of the surface modifier (M Ａ Next, the ratio of the weight of the surface modifier added to the weight of the metal oxide particles when preparing the metal oxide sol containing the surface-modified metal oxide particles (W Ａ ) was used to calculate the carbon content (C Ａ ) was calculated. Ａ = M Ａ ×W Ａ Next, 10 mL of n-hexane was added to 2 mL of metal oxide sol containing surface-modified metal oxide particles, and the mixture was centrifuged (centrifugal force: 2770 G), after which the supernatant was discarded and the sediment was separated. Next, 20 mL of n-hexane was added, and the sediment was separated by centrifugation (centrifugal force: 2770 G). This operation was repeated twice. The obtained sediment was vacuum dried at 150°C to obtain a dry powder. The carbon content (C) of this dry powder was measured using an elemental analyzer (manufactured by PerkinElmer, trade name 2400II). Ｂ ) and nitrogen content (N Ｂ The carbon content (C Ｂ ) is derived from the surface modifier used to modify the surface of the metal oxide particles and the amine compound added when preparing the metal oxide particles, and the nitrogen content (N Ｂ) is derived from the amine compound added when preparing the metal oxide particles. From the molecular formula of the amine compound added when preparing the metal oxide particles, the ratio of the molecular weight derived from carbon (M Ｂ ) and the nitrogen-derived molecular weight ratio (M Ｃ ) was calculated, and the carbon content (C Ｂ ) of the carbon content derived from the surface modifier (C Ｃ ) was calculated. Ｃ =C Ｂ -N Ｂ ×M Ｂ / M Ｃ Next, the weight ratio of the metal oxide component in the dry powder obtained by vacuum drying at 150°C (P Ａ ) was calculated using the following formula: Ａ = 1 - C Ｃ / M Ａ -N Ｂ / M Ｃ Finally, the surface modification rate of the particles bound to the surface was determined by the following formula: Surface modification rate = (C Ｃ / P Ａ ) / C Ａ In the present invention, the surface modification rate is preferably 30 to 100%, more preferably 40 to 100%, and by setting the surface modification rate within the above-mentioned range, the dispersion stability in organic solvents and resins becomes good, and a cured film with high transparency can be obtained.

[0115] The cured films obtained in the examples and comparative examples were formed and evaluated by the methods described below. (1) Film Thickness The reflectance of the cured film formed on a glass substrate was measured using a reflectance measuring device (manufactured by Olympus Corporation, trade name USPM-RU). The film thickness of the cured film was calculated from the measured reflectance using optical simulation.

[0116] (2) Transparency The presence or absence of haze in the cured film formed on the glass substrate was examined using a spectroscopic haze meter (SH7000, manufactured by Nippon Denshoku Industries Co., Ltd.). The evaluation criteria are as follows: ○: Haze value less than 0.1%. △: Haze value 0.1% or more but less than 0.3%. ×: Haze value 0.3% or more.

[0117] (3) UV resistance: UV resistance was measured using an ultraviolet fluorescent lamp accelerated weathering tester (manufactured by Q-Lab, product name QUV) equipped with a UV-A lamp at 0.89 W / m ２ A cured film formed on a glass substrate was irradiated with ultraviolet light for 3 hours under conditions of (340 nm). The evaluation criteria are as follows: When the initial film thickness is d0 and the film thickness after light resistance evaluation is d, Film thickness change rate = (d0 - d) / d0 x 100. Good: Film thickness change rate is less than 5%. Bad: Film thickness change rate is 5% or more.

[0118] (4) Imprintability A coating liquid containing a colloidal particle organic solvent dispersion sol was spin-coated onto a quartz substrate and heated on a hot plate at 100°C for 1 minute to produce a film from which the solvent had been removed. The resulting film was irradiated with ultraviolet light using a nanoimprinter (manufactured by Meisho Kiko Co., Ltd., product name NM-0801HB) while a release-treated quartz mold (manufactured by Kyodo International Co., Ltd., product name DTM-2-1) was pressed against it, and the film was cured while transferring a concave-convex pattern. The mold was peeled from the resulting cured film, and the formed pattern was observed with an SEM (manufactured by JEOL Ltd., product name JSM-6010LV). The evaluation criteria were as follows: ○: The pattern was transferred, and the imprintability was good. ×: The pattern was not transferred, and the imprintability was poor.

[0119] Reference Example 1: Preparation of titanium oxide-stannic oxide composite oxide colloidal particles (A1) as cores 319.5 g of a 25 mass % aqueous solution of tetramethylammonium hydroxide was dissolved in 947.1 g of pure water, and then 7.4 g of metastannic acid (SnO ２ 6.3 g in terms of titanium tetraisopropoxide), 236.6 g (TiO ２To the resulting mixture, 82.0 g of oxalic acid dihydrate (containing 66.6 g in terms of oxalic acid equivalent) and 82.0 g of oxalic acid dihydrate (58.5 g in terms of oxalic acid equivalent) were added under stirring. The mixed solution was maintained at 80°C for 2 hours, and then the pressure was reduced to 580 Torr and maintained for 2 hours to prepare a mixed solution. The mixed solution was placed in a glass-lined autoclave vessel, subjected to hydrothermal treatment at 140°C for 5 hours, cooled to room temperature, and then removed. The resulting sol was desalted and washed by ultrafiltration, and 41.6 g of 35% tetraethylammonium hydroxide was added. The resulting sol was an aqueous dispersion sol of alkaline titanium oxide-stannic oxide composite oxide colloidal particles (A1), and had a pH of 11.2 and a total metal oxide concentration (TiO ２ , and SnO ２ The sol was dried at 110°C and the powder was subjected to X-ray diffraction analysis, which confirmed that the powder was a rutile crystal.

[0120] Reference Example 2: Preparation of titanium oxide-stannic oxide composite oxide colloidal particles (A2) as cores 319.5 g of a 25 mass % aqueous solution of tetramethylammonium hydroxide was dissolved in 947.1 g of pure water, and then 14.8 g of metastannic acid (SnO ２ 12.5g in terms of titanium tetraisopropoxide), 236.6g (TiO ２ To the resulting mixture, 82.0 g of oxalic acid dihydrate (containing 66.6 g in terms of oxalic acid equivalent) and 82.0 g of oxalic acid dihydrate (containing 58.5 g in terms of oxalic acid equivalent) were added under stirring. The mixed solution was maintained at 80°C for 2 hours, and then the pressure was reduced to 580 Torr and maintained for 2 hours to prepare a mixed solution. The mixed solution was placed in a glass-lined autoclave vessel, subjected to hydrothermal treatment at 140°C for 5 hours, cooled to room temperature, and then removed. The resulting sol was desalted and washed by ultrafiltration, and 45.2 g of 35% tetraethylammonium hydroxide was added. The resulting sol was an aqueous dispersion sol of alkaline titanium oxide-stannic oxide composite oxide colloidal particles (A2), and had a pH of 11.5 and a total metal oxide concentration (TiO ２ , and SnO ２ The sol was dried at 110°C and the powder was subjected to X-ray diffraction analysis, which confirmed that the sol was a rutile crystal.

[0121] (Reference Example 3): Preparation of silicon dioxide-stannic oxide composite oxide colloidal particles (B1) to be coated. ２ 77.2 g of sodium stannate (containing 29.8% by mass of sodium stannate in terms of sodium stannate content) was dissolved in 668.8 g of pure water, and then sodium stannate NaSnO ３ ・H ２ O(SnO ２ Into the aqueous solution was dissolved 20.9 g of silicon dioxide-stannic oxide composite oxide colloidal particles (B1), which contained 55.1% by mass of silicon dioxide. The resulting aqueous solution was passed through a column packed with a hydrogen-type cation exchange resin (Amberlite (trade name) IR-120B). Next, 7.2 g of diisopropylamine was added to the resulting aqueous dispersion sol. The resulting sol was an aqueous dispersion sol of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (B1), and had a pH of 8.0 and a total metal oxide concentration (SnO ２ , and SnO ２ ) 1.7% by mass, and the primary particle diameter was 1 to 4 nm when observed with a transmission electron microscope.

[0122] Reference Example 4: Preparation of Zirconium Oxide-Stannic Oxide Composite Oxide Colloidal Particles (A3) as Cores 293.7 g of an aqueous solution of tetramethylammonium hydrogen carbonate (containing 42.4% by mass in terms of tetramethylammonium hydroxide) was diluted with 111.5 g of pure water, and zirconium oxycarbonate powder (ZrO ２ After the addition was completed, the mixture was heated to 85°C and 9.6 g of metastannic acid (SnO ２ To the resulting solution, a solution containing 86.0% by mass of zirconium oxide (as a stannic oxide composite oxide colloidal particle) was gradually added, and the solution was heated and aged at 105°C for 5 hours, followed by a hydrothermal treatment at 145°C for 5 hours. The sol was then washed and concentrated in an ultrafiltration device while adding pure water. The resulting sol was an aqueous dispersion sol of alkaline zirconium oxide-stannic oxide composite oxide colloidal particles (A3), with a pH of 9.4 and a total metal oxide concentration (ZrO ２ , and SnO ２ The primary particle size was 3 to 20 nm as determined by observation with a transmission electron microscope.

[0123] (Reference Example 5): Preparation of stannic oxide colloidal particles (A4) serving as cores 64.0 g of oxalic acid dihydrate (45.7 g in terms of oxalic acid) was dissolved in 723.3 g of pure water, and the solution was heated to 70°C with stirring. Then, 290.3 g of 35% hydrogen peroxide water and metallic tin powder (SnO ２ To the reaction mixture, 128.1 g of 35% hydrogen peroxide (99.7% content in terms of tin) was added. The addition of hydrogen peroxide and metallic tin was alternately performed in 10 divided portions. First, 29.0 g of 35% hydrogen peroxide was added, followed by 12.8 g of metallic tin. This operation was repeated after waiting for the reaction to complete (10 to 15 minutes). The addition took 2 hours, and after the addition was completed, the reaction was terminated by heating for 2 hours while maintaining the liquid temperature at 90°C. Next, 394.5 g of 35% hydrogen peroxide was added, and the mixture was kept at 90°C for 5 hours. Next, 5.1 g of isopropylamine was added, and the mixture was kept at 50°C for 3 hours, after which the mixture was passed through a column packed with 500 ml of anion exchange resin (Amberlite (trade name) IRA-410). The resulting sol was an aqueous dispersion sol of alkaline stannic oxide colloidal particles (A4), with a pH of 11.0 and SnO ２ The concentration was 4.0% by mass, and the primary particle diameter was 2 to 24 nm as determined by observation with a transmission electron microscope.

[0124] (Production Example 1): Preparation of titanium oxide-stannic oxide composite oxide colloidal particles (C1) modified with silicon dioxide-stannic oxide composite oxide. 1500.0 g of the aqueous dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (A1) prepared in Reference Example 1 was added with stirring to 661.8 g of the aqueous dispersion sol of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (B1) prepared in Reference Example 4. The mixture was heated at 95°C for 3 hours and then passed through a column packed with a cation exchange resin (Amberlite (trade name) IR-120B, manufactured by Organo Corporation). 2.5 g of tri-n-pentylamine was added to the obtained aqueous dispersion sol, which was then concentrated by ultrafiltration membrane method to obtain an aqueous dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (C1) modified with silicon dioxide-stannic oxide composite oxide. This aqueous dispersion sol had a pH of 5.2, a total metal oxide (TiO ２ , SnO ２ , and SiO ２The concentration was 30.5% by mass, the viscosity was 5.0 mPa·s, and the average particle size measured by dynamic light scattering (DLS) (dynamic light scattering particle size) was 15 nm.

[0125] (Production Example 2): Preparation of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C2) modified with silicon dioxide-stannic oxide composite oxide Zirconium oxychloride (ZrO ２ 82.7 g of a zirconium oxychloride solution (containing 21.2% by mass in terms of ZrO) was diluted with 501.1 g of pure water to obtain 583.8 g of an aqueous solution of zirconium oxychloride (ZrO ２ A 1000 ml aqueous dispersion of titanium dioxide-stannic oxide composite oxide colloidal particles (A2) (containing 3.0% by mass, calculated as 1000 ml of stannic oxide) was prepared, and 1750.0 g of the aqueous dispersion sol of titanium dioxide-stannic oxide composite oxide colloidal particles (A2) prepared in Reference Example 2 was added under stirring. Hydrolysis was then carried out by heating at 95°C for 5 hours, yielding an aqueous dispersion sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles having a thin film layer of zirconium oxide formed on the surface. 2330.0 g of the obtained aqueous dispersion sol was added under stirring to 1852.9 g of the aqueous dispersion sol of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (B1) prepared in Reference Example 4, and the mixture was passed through a column packed with 500 ml of anion exchange resin (Amberlite (trade name) IRA-410, manufactured by Organo Corporation). The aqueous dispersion sol after passing through was then heated at 95°C for 5 hours, and then passed through a column packed with cation exchange resin (Amberlite (trade name) IR-120B, manufactured by Organo Corporation). To the obtained water-dispersed sol, 3.5 g of tri-n-pentylamine was added, and the mixture was concentrated by an ultrafiltration membrane method to obtain a water-dispersed sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C2) modified with silicon dioxide-stannic oxide composite oxide. This water-dispersed sol had a pH of 5.2, a total metal oxide (TiO ２ , ZrO ２ , SnO ２ , and SiO ２ The concentration was 30.5% by mass, the viscosity was 5.0 mPa·s, and the average particle size measured by dynamic light scattering (DLS) (dynamic light scattering particle size) was 20 nm.

[0126] (Production Example 3): Preparation of zirconium oxide-stannic oxide composite oxide colloidal particles (C3) modified with silicon dioxide-stannic oxide composite oxide. 800.0 g of the aqueous dispersion sol of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (B1) prepared in Reference Example 2 was added to 700.0 g of the aqueous dispersion sol of alkaline zirconium oxide-stannic oxide composite oxide colloidal particles (A3) obtained in Reference Example 4 under stirring. The mixture was then heated to 95°C and maintained for 2 hours, after which the mixture was passed through a column packed with a hydrogen-type cation exchange resin (Amberlite (trade name) IR-120B). 3.4 g of tri-n-pentylamine was added to the obtained aqueous dispersion sol, which was then concentrated by ultrafiltration membrane method to obtain an aqueous dispersion sol of zirconium oxide-stannic oxide composite oxide colloidal particles (C3) modified with silicon dioxide-stannic oxide composite oxide. This aqueous dispersion sol had a pH of 5.0, a total metal oxide (ZrO ２ , SnO ２ , and SiO ２ The concentration was 30.0% by mass, the viscosity was 5.3 mPa·s, and the average particle size measured by dynamic light scattering (DLS) (dynamic light scattering particle size) was 23 nm.

[0127] (Production Example 4): Preparation of stannic oxide colloidal particles (C4) modified with silicon dioxide-stannic oxide composite oxide To 1,400.0 g of the aqueous dispersion sol of stannic oxide colloidal particles (A4) obtained in Reference Example 5, 500.0 g of the aqueous dispersion sol of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (B1) prepared in Reference Example 2 was added under stirring. The mixture was then heated to 95°C and maintained for 2 hours, after which the mixture was passed through a column packed with a hydrogen-type cation exchange resin (Amberlite (trade name) IR-120B). 1.5 g of tri-n-pentylamine was added to the obtained aqueous dispersion sol, and the mixture was concentrated by ultrafiltration membrane method to obtain an aqueous dispersion sol of stannic oxide colloidal particles (C4) modified with silicon dioxide-stannic oxide composite oxide. This aqueous dispersion sol was a sol containing 1,400.0 g of the aqueous dispersion sol of stannic oxide colloidal particles (A4) obtained in Reference Example 5. The total metal oxides (SnO ２ , and SiO ２ The concentration was 30.5% by mass, the viscosity was 4.8 mPa·s, and the average particle size measured by dynamic light scattering (DLS) (dynamic light scattering particle size) was 18 nm.

[0128] Example 1 The dispersion medium of 100 g of the aqueous dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (C1) modified with silicon dioxide-stannic oxide composite oxide obtained in Production Example 1 was replaced with methanol using a rotary evaporator to obtain a methanol dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (C1) modified with silicon dioxide-stannic oxide composite oxide. 6.1 g of a surface modifier (trade name: X-12-1333A, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the obtained sol under stirring, and the particles were surface-modified by heating under reflux at 65°C for 5 hours. Next, the dispersion medium was replaced with propylene glycol monomethyl ether acetate (hereinafter, PGMEA) using a rotary evaporator to prepare a PGMEA dispersion sol. This surface-modified PGMEA dispersion sol contained a total metal oxide (TiO ２ , SnO ２ , and SiO ２ ) concentration was 20.5% by mass, the average particle size measured by dynamic light scattering (DLS) (dynamic light scattering particle size) was 16 nm, the dispersion stability was "○", and the surface modification rate was 40%.

[0129] (Film Evaluation A-1) A cured film was prepared using the PGMEA dispersion sol obtained in Example 1 by the following procedure. 1.3 g of a mixture of dipentaerythritol hexaacrylate and pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a resin binder and 3.0 g of PGME were added to a brown bottle equipped with a magnetic stirrer, and 25.3 g of the PGMEA dispersion sol of Example 1 was added while stirring. Next, 0.013 g of a photoradical polymerization initiator (manufactured by BASF Corporation, trade name Irgacure OXE01) and 0.3 g of a PGME solution (L-7001 concentration 10.0% by mass) of a polyether-modified silicone surface modifier (manufactured by Dow-Toray Co., Ltd., trade name DOWSIL™ L-7001) were added, and the mixture was stirred for 0.5 hours to prepare a coating liquid. Glass substrates were prepared, and the coating liquid was applied to them by spin coating (film thickness 1 μm). After volatilizing the solvent at 100° C. for 2 minutes, the coating liquid was applied to the glass substrates with an integrated light intensity of 1000 mJ / cm 2 ２The coating solution was then cured with ultraviolet light using a high-pressure mercury lamp until the cured film reached a transparency of "○" and a UV resistance of "○". The coating solution was also used to evaluate imprintability, which was also evaluated as "○".

[0130] (Film Evaluation A-2) A cured film was produced using the PGMEA dispersion sol obtained in Example 1 in the same manner as in Film Evaluation A-1, except that the resin binder was changed to polyethylene glycol #400 acrylate (manufactured by Resonac Corporation, product name FA-240A). The obtained cured film was rated as "○" for transparency and "○" for UV resistance. The same coating liquid was also used to evaluate imprintability, which was rated as "○".

[0131] (Film Evaluation A-3) A cured film was produced using the PGMEA-dispersed sol obtained in Example 1, in the same manner as in Film Evaluation A-1, except that the resin binder was changed to an acrylic group-containing, flexible silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., product name X-40-2761). The obtained cured film was rated as "○" for transparency and "○" for UV resistance. The same coating liquid was also used to evaluate imprintability, which was rated as "○".

[0132] (Example 2) A sol was prepared in the same manner as in Example 1, except that the colloidal particles were changed to (C2) obtained in Production Example 2, the amount of surface modifier added was changed to 3.1 g, and the substitution solvent was changed to propylene glycol monomethyl ether (hereinafter, PGME). In this case, the PGME-dispersed sol was prepared by dispersing the total metal oxides (TiO ２ , SnO ２ , ZrO ２ and SiO ２ ) concentration was 30.5% by mass, the average particle size measured by dynamic light scattering (DLS) (dynamic light scattering particle size) was 13 nm, the dispersion stability was "○", and the surface modification rate was 40%.

[0133] (Example 3) A sol was prepared in the same manner as in Example 1, except that the colloidal particles were changed to (C3) obtained in Production Example 3, the amount of surface modifier X-12-1333A added was changed to 3.1 g, and the substitution solvent was changed to PGME. In this case, the PGME-dispersed sol was prepared by dispersing all metal oxides (ZrO ２ , SnO ２and SiO ２ The sol had a concentration of 20.5% by mass, an average particle size (dynamic light scattering particle size) of 16 nm as determined by dynamic light scattering (DLS), a dispersion stability of "○", and a surface modification rate of 40%. Next, a cured film was produced using this sol in the same manner as in Film Evaluation A-1. The obtained cured film had a transparency of "○" and a UV resistance of "○". Furthermore, when the same coating liquid was used to evaluate imprintability, it was rated as "○".

[0134] Example 4 A sol was prepared in the same manner as in Example 1, except that the colloidal particles were changed to (C4) obtained in Production Example 4, the amount of surface modifier X-12-1333A added was changed to 1.5 g, and the substitution solvent was changed to PGME. In this case, the PGME-dispersed sol was prepared by dispersing all metal oxides (SnO ２ and SiO ２ The sol had a concentration of 20.5% by mass, an average particle size (dynamic light scattering particle size) of 18 nm as determined by dynamic light scattering (DLS), a dispersion stability rating of "○", and a surface modification rate of 50%. Next, a cured film was produced using this sol in the same manner as in Film Evaluation A-1. The obtained cured film had a transparency rating of "○" and a UV resistance rating of "○". Furthermore, when the same coating liquid was used to evaluate imprintability, it was rated as "○".

[0135] Example 5 A sol was prepared in the same manner as in Example 1, except that the colloidal particles were changed to an aqueous silica sol, trade name Snowtex O-33 (silica concentration 33.5% by mass, pH 2.6, manufactured by Nissan Chemical Industries, Ltd.), the amount of surface modifier X-12-1333A added was changed to 6.7 g, and the substitution solvent was changed to PGME. In this case, the PGME-dispersed sol was prepared by dispersing all metal oxides (SiO ２ The sol had a sol concentration of 20.6% by mass, an average particle size (dynamic light scattering particle size) of 24 nm as determined by dynamic light scattering (DLS), a dispersion stability rating of "○", and a surface modification rate of 80%. Next, a cured film was produced using this sol in the same manner as in Film Evaluation A-1. The obtained cured film had a transparency rating of "○" and a UV resistance rating of "○". Furthermore, when the same coating liquid was used to evaluate imprintability, it was rated as "○".

[0136] Example 6 To 100 g of the aqueous dispersion sol of the zirconium oxide-stannic oxide composite oxide colloidal particles (A3) obtained in Reference Example 4, 200 g of methanol and 2.0 g of a surface modifier, X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.), were added under stirring, and the particles were surface-modified by reflux heating at 65°C for 5 hours. Next, a PGME-dispersed sol was prepared by replacing the dispersion medium with PGME using a rotary evaporator. This surface-modified PGME-dispersed sol was prepared by dissolving all metal oxides (ZrO ２ , SnO ２ , and SiO ２ The sol had a concentration of 20.5% by mass, an average particle size (dynamic light scattering particle size) of 12 nm as determined by dynamic light scattering (DLS), dispersion stability of "○", and a surface modification rate of 70%. Next, a cured film was produced using this sol in the same manner as in Film Evaluation A-1. The obtained cured film had a transparency of "○" and a UV resistance of "○". Furthermore, when the same coating liquid was used to evaluate imprintability, it was rated as "○".

[0137] (Example 7) A sol was prepared in the same manner as in Example 1, except that the colloidal particles were changed to (C2) obtained in Production Example 2, the amount of surface modifier X-12-1333A added was changed to 3.1 g, and the substitution solvent was changed to methyl ethyl ketone (hereinafter, MEK). In this case, the MEK dispersion sol was prepared by dispersing all metal oxides (TiO ２ , SnO ２ , ZrO ２ and SiO ２ ) concentration was 30.5% by mass, the average particle size measured by dynamic light scattering (DLS) (dynamic light scattering particle size) was 14 nm, the dispersion stability was "○", and the surface modification rate was 70%.

[0138] (Comparative Example 1) TiO manufactured by Sigma-Aldrich Co., Ltd. ２ 10.0 g of nanopowder (trade name: Titanium (IV) oxide, rutile, <100 nm particle size, 99.5% trace metals basis) was added to 23.3 g of methanol. Next, 2.0 g of X-12-1333A (trade name: Shin-Etsu Chemical Co., Ltd.) and 0.4 g of pure water were added. This was refluxed at 65°C for 5 hours to obtain TiO ２The nanopowder was surface-modified. Next, a PGMEA dispersion was produced by replacing the dispersion medium with PGMEA using a rotary evaporator. This surface-modified PGMEA dispersion had a total metal oxide concentration of 20.5% by mass, an average particle size (dynamic light scattering particle size) of 683 nm as determined by dynamic light scattering (DLS), a dispersion stability of "x", and a surface modification rate of 3%. Next, a cured film was produced using this dispersion using the same procedure as in Film Evaluation A-1. The resulting cured film was rated "x" for transparency, and its UV resistance and imprintability were not evaluated.

[0139] Comparative Example 2 In Example 1, the solvent was replaced from methanol to PGME without carrying out the surface modification using the product name X-12-1333A. At this time, the PGME dispersion sol was a total of 100% of the total metal oxides (TiO ２ , SnO ２ and SiO ２ The sol had a sol concentration of 30.5% by mass, an average particle size (dynamic light scattering particle size) of 55 nm as determined by dynamic light scattering (DLS), a dispersion stability of "○", and a surface modification rate of 0%. Next, a cured film was produced using this sol in the same manner as in Film Evaluation A-1. The obtained cured film had a transparency of "○" and a UV resistance of "○". Furthermore, when the same coating liquid was used to evaluate imprintability, it was rated as "×".

[0140] Comparative Example 3 A sol was prepared in the same manner as in Example 1, except that the surface modifier was changed to 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) g and the substitution solvent was changed to PGME. At this time, the PGME-dispersed sol was a total metal oxide (TiO ２ , SnO ２ and SiO ２ The sol had a concentration of 30.5% by mass, an average particle size (dynamic light scattering particle size) of 19 nm as determined by dynamic light scattering (DLS), a dispersion stability rating of "○", and a surface modification rate of 20%. Next, a cured film was produced using this sol in the same manner as in Film Evaluation A-1. The resulting cured film was rated "x" for transparency, and was not suitable for evaluation of UV resistance and imprintability.

[0141] Comparative Example 4 In Comparative Example 1, the particles were replaced with SiO ２A dispersion was prepared in the same manner as in Comparative Example 1, except that the amount of powder (product name AEROSIL (registered trademark) 130) was changed to 10.0 g. This surface-modified PGMEA dispersion had a total metal oxide concentration of 20.5 mass%, an average particle size (dynamic light scattering particle size) of 355 nm as determined by dynamic light scattering (DLS), dispersion stability of "x", and a surface modification rate of 5%.

[0142] From the above results, it became clear that by combining colloidal metal oxide particles, rather than powdered metal oxide, with a silane containing multiple polymerizable functional groups, a composition with excellent storage stability was obtained, and that the coating formed by applying this to a substrate and curing it was excellent in all of transparency, UV resistance, and imprintability.

[0143] A highly dispersible sol containing metal oxide particles and a silane containing multiple polymerizable functional groups, and a varnish containing a thermosetting or photocurable resin using the sol are obtained, and these can be used in compositions for nanoimprint processes.

Claims

1. A metal oxide sol containing a silane compound and metal oxide particles, wherein the silane compound is represented by the formula (1): (In formula (1), R １ each independently represents an alkoxy group, an acyloxy group, or a halogen group; R ２ are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms; R ３ is a hydrogen atom or a methyl group, A １ is an alkylene group; A ２ , A ３ , and A ４ are each independently a methylene group or an oxygen atom; A ２ , A ３ , and A ４ wherein one of the atoms is an oxygen atom, and n is an integer of 1 to 3.

2. The metal oxide sol according to claim 1, wherein the metal oxide particles are coated with the silane compound (1).

3. A ２ and A ４ is a methylene group, and A ３ The metal oxide sol according to claim 1 or 2, wherein is an oxygen atom.

4. The metal oxide sol according to any one of claims 1 to 3, wherein the metal oxide particles have an average primary particle size of 5 to 100 nm as measured by a nitrogen gas adsorption method and an average particle size of 5 to 200 nm as measured by a dynamic light scattering method.

5. The metal oxide sol according to any one of claims 1 to 4, wherein the metal oxide particles are oxide particles of one kind of metal or composite oxide particles of two or more kinds of metals.

6. The metal oxide sol according to any one of claims 1 to 5, wherein the metal oxide is at least one metal oxide selected from the group consisting of titanium oxide, tin oxide, zirconium oxide, silicon dioxide, zinc oxide, antimony oxide, niobium oxide, and tungsten oxide.

7. The metal oxide sol according to any one of claims 1 to 6, wherein the metal oxide particles are core-shell type metal oxide particles in which the surface of a core metal oxide particle is coated with a coating layer of metal oxide particles having a metal oxide component or metal oxide content different from that of the core metal oxide, and the core metal oxide particle, the metal oxide particle of the coating layer, or both, contain a metal oxide having photoactivity.

8. The metal oxide sol according to claim 7, wherein the photoactive metal oxide particles (A) are core-shell type metal oxide particles in which the surfaces of metal oxide particles containing titanium oxide as cores are covered with metal oxide particles containing silica, and the total metal oxide contains 50 mol % or more of titanium oxide.

9. The metal oxide sol according to claim 7 or 8, wherein the metal oxide particles of the core are particles of titanium oxide, zirconium oxide, tin oxide, a composite oxide of titanium oxide and tin oxide, a composite oxide of zirconium oxide and tin oxide, a composite oxide of titanium oxide and zirconium oxide, or a composite oxide of titanium oxide, zirconium oxide and tin oxide.

10. The metal oxide sol according to any one of claims 7 to 9, wherein the metal oxide particles of the coating layer are particles of at least one metal oxide or composite metal oxide selected from the group consisting of silicon dioxide, tin oxide, antimony oxide, tungsten oxide, aluminum oxide, and zirconium oxide.

11. The metal oxide sol according to any one of claims 1 to 10, further comprising at least one additive a selected from the group consisting of silane compounds other than those represented by formula (1), organic acids and their salts, phosphoric esters, amines, and surfactants.

12. The metal oxide sol according to any one of claims 1 to 10, wherein the metal oxide particles are coated with the silane compound of formula (1) and the additive a.

13. The silane compound other than the formula (1) is a silane compound represented by the formulas (2) to (4): (In formula (2), R １１ each represents an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having a polyether group, an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and is bonded to a silicon atom by a Si-C bond; R １２ Each represents an alkoxy group, an acyloxy group, or a halogen group, a represents an integer of 1 to 3, and in formula (3) and formula (4), R １３ and R １５ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, R １４ and R １６ each represents an alkoxy group, an acyloxy group, or a halogen group, Y represents an alkylene group, an NH group, or an oxygen atom, b is an integer of 1 to 3, c is an integer of 0 or 1, and d is an integer of 1 to 3. The metal oxide sol according to claim 11 or 12, 14. The metal oxide sol according to claim 11, wherein the organic acid is at least one organic acid selected from the group consisting of a divalent aliphatic carboxylic acid, an aliphatic oxycarboxylic acid, an amino acid, and a chelating agent, the divalent aliphatic carboxylic acid being selected from the group consisting of oxalic acid, malonic acid, and succinic acid, the aliphatic oxycarboxylic acid being selected from the group consisting of glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid, the amino acid being selected from the group consisting of glycine, alanine, valine, leucine, serine, and threonine, and the chelating agent being selected from the group consisting of ethylenediaminetetraacetic acid, L-aspartic acid-N,N-diacetic acid, and diethylenetriaminepentaacetic acid.

15. The phosphate ester is represented by the formula (5) to (7): (In formulas (5) to (7), X １ , X ２ , and X ３ each represents an alkylene group having 2 to 20 carbon atoms; f, h, and j each represent an integer of 1 to 100; e, g, and i each represent an integer of 1 to 3; Y １ , Y ２ , and Y ３ each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a (meth)acrylic group.

16. The metal oxide sol according to claim 11, wherein the surfactant is an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or a silicon-based surfactant.

17. The metal oxide sol according to claim 11 or 12, wherein the amine is a secondary or tertiary amine having a total of 5 to 35 carbon atoms.

18. The metal oxide sol according to any one of claims 1 to 17, wherein the dispersion medium of the sol is water, an alcohol, an ester, a ketone, an amide, or a hydrocarbon.

19. A varnish comprising the metal oxide sol according to any one of claims 1 to 18 and a thermosetting or photosetting resin.

20. The varnish according to claim 19, which is used for nanoimprinting.

21. A method for producing a metal oxide sol according to any one of claims 1 to 18, comprising the following steps (i) to (iii): step (i): a step (i) of solvent-substituting an aqueous solvent of an aqueous sol of metal oxide particles with an alcohol having 1 to 4 carbon atoms which may have an ether bond; step (ii): a step (ii) of mixing the alcohol sol of metal oxide particles obtained in step (i) with a silane compound of formula (1); and step (iii): a step (iii) of solvent-substituting the alcohol solvent of the alcohol sol of metal oxide particles obtained in step (ii) with an organic solvent other than the alcohol.

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