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

Abstract

Provided are a highly dispersible sol containing metal oxide particles and a silane containing a plurality of polymerizable functional groups, and a varnish containing a thermosetting or photocurable resin using the sol and the varnish. The present invention is a metal oxide sol containing a silane compound represented by formula (1) and metal oxide particles, (In formula (1), R1 each independently represents an alkoxy group, an acyloxy group, or a halogen group, R2 each independently represents an alkyl group having 1-10 carbon atoms or an aryl group having 6-30 carbon atoms, R3 is a hydrogen atom or a methyl group, A1 is an alkylene group, A2, A3, and A4 each independently represent a methylene group or an oxygen atom, one of A2, A3, and A4 is an oxygen atom, and n is an integer of 1-3). Also disclosed is a varnish which contains the metal oxide sol and a thermosetting or photocurable resin. The varnish is used for nanoimprint.

Description

Technical Field

[0001] This invention relates to metal oxide sols containing polymeric silane compounds, varnishes using these sols, and methods for manufacturing them. Background Technology

[0002] In the field of coating resins and films, compositions comprising metal oxide particles and silane compounds (especially silane coupling agents) are used. Coating compositions containing silane compounds having polymeric groups, such as acryloyl groups and glycidyl groups, as the silane compound are also available. These compositions have been disclosed as photocurable resin compositions for nanoimprinting (see Patent Document 1).

[0003] Most of the aforementioned silane compounds have one polymerizable functional group in one silane molecule. However, silane compounds with two polymerizable functional groups in one silane molecule (silanes containing multiple polymerizable functional groups) undergo cyclization polymerization with the addition of a polymerization initiator, thus successfully undergoing a curing reaction. Furthermore, it has been disclosed that cyclization improves heat resistance and inhibits the reduction of the thermal weight of the resulting curable resin composition (see Patent Document 2).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2008-266608

[0007] Patent Document 2: International Publication No. 2022 / 158176 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] The purpose of this invention is to provide a highly dispersible sol comprising metal oxide particles and silanes containing multiple polymerizable functional groups, a varnish using the sol, and a method for manufacturing the sol.

[0010] Methods for solving problems

[0011] The present invention, as a first point of view, is the above-mentioned metal oxide sol, which is a metal oxide sol containing silane compounds and metal oxide particles, wherein the silane compounds are represented by formula (1).

[0012]

[0013] (In equation (1), R) 1 Each independently represents an alkoxy, acyloxy, or halogen group, R 2 Each is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms, R 3A is a hydrogen atom or a methyl group. 1 It is an alkylene group, A 2 A 3 and A 4 Each is independently a methylene or oxygen atom, A 2 A 3 and A 4 One of them is an oxygen atom, and n is an integer from 1 to 3.

[0014] As a second viewpoint, it is a metal oxide sol as described in the first viewpoint, wherein the metal oxide particles are coated with a silane compound (1).

[0015] As a third viewpoint, it refers to a metal oxide sol as described in the first or second viewpoint, wherein A 2 and A 4 Methylene, A 3 For oxygen atoms,

[0016] As a fourth point of view, it is a metal oxide sol as described in any one of the first to third points of view, wherein the average primary particle size of the metal oxide particles obtained by nitrogen adsorption is 5–100 nm, and the average particle size obtained by dynamic light scattering is 5–200 nm.

[0017] As a fifth point of view, it refers to a metal oxide sol as described in any one of the first to fourth points of view, wherein the metal oxide particles are oxide particles of one metal or composite oxide particles of two or more metals.

[0018] As a sixth point of view, it is a metal oxide sol as described in any one of points 1 to 5, wherein the metal oxide is a metal oxide selected from at least one of titanium oxide, tin oxide, zirconium oxide, silicon dioxide, zinc oxide, antimony oxide, niobium oxide, and tungsten oxide.

[0019] As a seventh point of view, it is a metal oxide sol as described in any one of the first to sixth points of view, wherein the metal oxide particles are core-shell type metal oxide particles whose surface is coated with a metal oxide particle having a metal oxide composition or metal oxide content different from that of the core metal oxide, and the core metal oxide particle, the coated metal oxide particle, or both contain photoactive metal oxides.

[0020] As the eighth point of view, the metal oxide sol described in the seventh point of view is wherein the aforementioned photoactive metal oxide particles (A) are core-shell type metal oxide particles whose surface is coated with metal oxide particles containing silicon dioxide, and which contain at least 50 mol% titanium oxide in all metal oxides.

[0021] As a ninth point of view, it is a metal oxide sol as described in the seventh or eighth point of view, wherein the metal oxide particles of the core are particles of titanium oxide, zirconium oxide, tin oxide, titanium oxide-tin oxide composite oxide, zirconium oxide-tin oxide composite oxide, titanium oxide-zirconia composite oxide, or titanium oxide-zirconia-tin oxide composite oxide.

[0022] As a tenth point of view, it is a metal oxide sol as described in any one of points 7 to 9, wherein the metal oxide particles of the coating layer are metal oxide particles or composite metal oxide particles selected from at least one of silicon dioxide, tin oxide, antimony oxide, tungsten oxide, aluminum oxide, and zirconium oxide.

[0023] As the 11th point of view, the metal oxide sol as described in any one of the 1st to 10th points of view further comprises an additive a selected from at least one of silane compounds other than formula (1), organic acids and their salts, phosphate esters, amines, and surfactants.

[0024] As the 12th viewpoint, it is a metal oxide sol as described in any of the 1st to 10th viewpoints, wherein the metal oxide particles are coated with a silane compound of formula (1) and additive a.

[0025] As the 13th viewpoint, it is a metal oxide sol as described in the 11th or 12th viewpoint, wherein the silane compound other than formula (1) is a silane compound selected from at least one of formulas (2) to (4).

[0026]

[0027] (In equation (2), R) 11 Each of the following groups is an alkyl, haloalkyl, alkenyl, aryl, or has an organic group having a polyether group, epoxy group, (meth)acryloyl group, mercapto group, amino group, urea group, or cyano group and is bonded to a silicon atom via a Si-C bond: R 12 Each represents an alkoxy, acyloxy, or halogen group, and 'a' represents an integer from 1 to 3.

[0028] In equations (3) and (4), R 13 and R 15Each is an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and is bonded to silicon atoms via Si-C bonds, R 14 and R 16 Each represents an alkoxy, acyloxy, or halogen group; Y represents an alkylene, NH group, or oxygen atom; b is an integer from 1 to 3; c is an integer from 0 to 1; and d is an integer from 1 to 3.

[0029] As the 14th point of view, it is a metal oxide sol as described in the 11th or 12th point of view, wherein the organic acid is an organic acid selected from at least one of divalent aliphatic carboxylic acids, aliphatic hydroxycarboxylic acids, amino acids, and chelating agents; the divalent aliphatic carboxylic acid is selected from oxalic acid, malonic acid, and succinic acid; the aliphatic hydroxycarboxylic acid is selected from glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid; the amino acid is selected from glycine, alanine, valine, leucine, serine, and threonine; and the chelating agent is selected from ethylenediaminetetraacetic acid, L-aspartic-N,N-diacetic acid, and diethylenetriaminepentaacetic acid.

[0030] As the 15th point of view, it is a metal oxide sol as described in the 11th or 12th point of view, wherein the phosphate ester is a phosphate ester selected from at least one of formulas (5) to (7).

[0031]

[0032] (In equations (5) to (7), X) 1 X 2 and X 3 Each represents an alkylene group with 2 to 20 carbon atoms; f, h, and j each represent an integer from 1 to 100; e, g, and i each represent an integer from 1 to 3; Y 1 Y 2 and Y 3 Each represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, or a (meth)acryloyl group.

[0033] As the 16th point of view, it is a metal oxide sol as described in the 11th or 12th point of view, wherein the surfactant is an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or a silicone surfactant.

[0034] As the 17th viewpoint, it is a metal oxide sol as described in viewpoint 11 or 12, wherein the amine is a secondary or tertiary amine having a total carbon number of 5 to 35.

[0035] As the 18th point of view, it is a metal oxide sol as described in any one of points 1 to 17, wherein the dispersion medium of the sol is water, alcohol, ester, ketone, amide, or hydrocarbon.

[0036] As the 19th point, a varnish comprises a metal oxide sol as described in any one of points 1 to 18, and a thermosetting or photocurable resin.

[0037] As the 20th point of view, the varnish described in the 19th point of view is used for nanoimprinting, and

[0038] As the 21st viewpoint, the method for manufacturing a metal oxide sol as described in any one of views 1 to 18 includes the following steps (i) to (iii):

[0039] (i) Process: The aqueous solvent of the aqueous sol of the metal oxide particles is replaced with an alcohol having 1 to 4 carbon atoms and ether bonds.

[0040] (ii) Step: The sol of metal oxide particles obtained in step (i) is mixed with the silane compound of formula (1).

[0041] (iii) Step: The alcohol solvent of the sol of the metal oxide particles obtained in step (ii) is replaced with an organic solvent other than the alcohol mentioned above.

[0042] Invention Effects

[0043] In compositions comprising metal oxide particles and silanes containing multiple polymerizable functional groups, when manufacturing a coating composition, if the dispersion of the metal oxide particles is low, particle composition bias occurs in the film. Furthermore, if the particle composition has functions such as controlling optical properties like refractive index and transparency, or heat resistance, a uniform film cannot be formed. This problem can be solved by combining metal oxide particles with colloidal-level particle sizes and silanes containing multiple polymerizable functional groups, without using metal oxides with powder-level particle sizes.

[0044] In this invention, a highly dispersible sol that makes metal oxide particles colloidal is prepared, and a composition is made by combining these sols with silanes containing multiple polymerizable functional groups. In a film formed by coating and curing these compositions on a substrate, metal oxide particles uniformly exist in colloidal regions. Through cyclization polymerization of the multiple polymerizable functional groups, smooth bonds are formed between the metal oxide particles in the colloidal regions, between these particles and the matrix resin, and between these particles, the matrix resin, and the substrate. This reduces bias in bonding and composition, thereby reducing thermal weight and forming a film with high heat resistance and high uniformity. This allows the inherent properties of the metal oxide particles themselves (e.g., refractive index, particle size, heat resistance) to be fully reflected in the film. Detailed Implementation

[0045] Hereinafter, preferred embodiments of the present invention will be described. However, the following embodiments are merely illustrative examples for illustrating the present invention, and the present invention is not limited to any of the following embodiments.

[0046] One embodiment of the present invention is the above-mentioned metal oxide sol, which is a metal oxide sol containing silane compounds and metal oxide particles, wherein the silane compounds are represented by formula (1).

[0047] In equation (1), R 1 Each independently represents an alkoxy, acyloxy, or halogen group, R 2 Each is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms, R 3 A is a hydrogen atom or a methyl group. 1 It is an alkylene group, A 2 A 3 and A 4 Each is independently a methylene or oxygen atom, A 2 A 3 and A 4 One of them is an oxygen atom, and n is an integer from 1 to 3. As the above-mentioned alkoxy, acyloxy, halogen group, alkyl, alkylene, and aryl groups, the groups exemplified later can be used.

[0048] The silane compound of formula (1) is a silane compound containing multiple polymerizable functional groups and functions as a silane coupling agent.

[0049] In formula (1), A is preferred. 2 and A 4 Methylene, A 3 A silane coupling agent consisting of oxygen atoms and n being an integer of 3 can be obtained as a product manufactured by Shin-Etsu Chemical Industry Co., Ltd. under the trade name X-12-1333A, represented by the following formula (1-1).

[0050]

[0051] One embodiment of the present invention is a metal oxide sol containing silane compounds and metal oxide particles, but the metal oxide particles may be coated with silane compounds (1) (also known as surface modification).

[0052] In one embodiment of the present invention, the metal oxide particles preferably have an average primary particle size of 5 to 100 nm obtained by nitrogen adsorption and an average particle size of 5 to 200 nm obtained by dynamic light scattering.

[0053] The aforementioned metal oxide particles can be oxide particles of one metal or composite oxide particles of two or more metals. The term "oxide particles of one metal" refers to the case where the metal oxide contains only one metal, or a metal oxide with a single metal oxide particle as its main component.

[0054] Composite oxide particles containing two or more metals are composite oxide particles containing two or more metal components, indicating the state of the metal oxide particles bonded together at the interface and the way the metal oxides are dissolved in solid solution.

[0055] As a metal oxide, at least one metal oxide selected from titanium oxide, tin oxide, zirconium oxide, silicon dioxide, zinc oxide, antimony oxide, niobium oxide and tungsten oxide can be used.

[0056] The metal oxide particles are core-shell type metal oxide particles whose surfaces are coated with a metal oxide composition or content that is different from that of the core metal oxide particles. The core metal oxide particles, the coated metal oxide particles, or both can contain photoactive metal oxides.

[0057] Regarding the photoactive metal oxide particles (A), the total metal oxides contain at least 50 mol% of at least one photoactive metal oxide selected from titanium oxide, tin oxide and zirconium oxide.

[0058] Core-shell metal oxide particles are metal oxide particles whose surfaces are coated with a metal oxide composition or content that differs from that of the core metal oxide. The core metal oxide particle, the coated metal oxide particle, or both can contain photoactive metal oxides.

[0059] The photoactive metal oxide particle can be defined as a metal oxide particle composed of a photoactive metal oxide particle (i) or a metal oxide particle containing a photoactive metal oxide particle (i). Furthermore, when the photoactive metal oxide particle is a core-shell type metal oxide particle, the core metal oxide particle, the coated metal oxide particle, or both can be defined as a particle containing a photoactive metal oxide particle (i).

[0060] The term "metal oxide particles composed of photoactive metal oxides" refers to a situation where the metal oxide particles contain only photoactive metal oxides (or photoactive metal oxide particles (i)) at a 100 mol% ratio.

[0061] The term "metal oxide particles containing photoactive metal oxide particles" refers to a situation where the metal oxide particles (A) contain photoactive metal oxides (or photoactive metal oxide particles (i)) in a proportion of more than 50 mol% and less than 100 mol% of all metal oxides.

[0062] The term "core-shell type metal oxide particle" refers to a core-shell metal oxide particle whose surface is coated with a metal oxide component or metal oxide content that differs from that of the core metal oxide. This means a case in which the core metal oxide particle, the coated metal oxide particle, or both of them have a proportion of 50 mol% or more and 100 mol% or less in all metal oxides that is photoactive metal oxide (or photoactive metal oxide particle (i)).

[0063] For example, examples of photoactive metal oxide particles include core-shell type metal oxide particles whose surface is covered with metal oxide particles containing silicon dioxide, which are the core of titanium oxide particles, and particles containing more than 50 mol% titanium oxide in all metal oxides.

[0064] Examples of metal oxide particles used for nuclei include those comprising titanium oxide, zirconium oxide, tin oxide, titanium oxide-tin oxide composite oxides, zirconium oxide-tin oxide composite oxides, titanium oxide-zirconia composite oxides, or titanium oxide-zirconia-tin oxide composite oxides. These particles, observed using a transmission electron microscope, have an average primary particle size of 5–100 nm or 5–60 nm.

[0065] Examples of metal oxide particles included in the coating layer include metal oxide particles or composite metal oxide particles selected from at least one of silicon dioxide, tin oxide, antimony oxide, tungsten oxide, aluminum oxide, and zirconium oxide. These particles, observed using a transmission electron microscope, have an average primary particle size of 1–10 nm or 1–5 nm. Examples of metal oxide particles included in the coating layer include individual metal oxide particles of silicon dioxide, tin oxide, antimony oxide, tungsten oxide, aluminum oxide, and zirconium oxide, or composite metal oxide particles formed by combining multiple of the above metal oxides. Examples of composite metal oxide particles include tin oxide-silica composite metal oxide particles, tin oxide-zirconia-silica composite metal oxide particles, tin oxide-tungsten oxide-silica composite metal oxide particles, and antimony oxide-silica composite metal oxide particles. When the coating layer contains silicon dioxide particles, the ratio of silicon dioxide particles to other metal oxide particles, expressed as a (silicon dioxide) / (other metal oxide) mass ratio, can be set to a ratio of 0.1 to 5.0.

[0066] When using a core-shell structure, the coating can include cases where the metal oxide composition or content of the core is different from that of the metal oxide in the core, or cases where the metal oxide composition of the core and the coating is different, or cases where the composition of the core and the coating is partially the same, but the proportions of the metal oxides are different.

[0067] In the case of a core-shell structure, the mass ratio of the metal oxide particles in the core to the metal oxide particles in the coating can be set to a range of (coating metal oxide particles) / (core metal oxide particles) = 0.05 to 0.50.

[0068] For example, in the case of a tin oxide-silicon dioxide composite oxide contained in the coated metal oxide particles, sodium stannate or potassium stannate can be used as the alkali metal of stannate, and sodium stannate is preferred.

[0069] Sodium silicate and potassium silicate can be used as alkali metals of silicates.

[0070] In the case of alkali metal stannate and alkali metal silicate, a substance can be obtained by preparing an aqueous solution containing silicon dioxide / tin oxide in a mass ratio of 0.1 to 5, and then removing the cations present in the aqueous solution by passing it through a cation exchange resin.

[0071] For alkali metal stannate and alkali metal silicate, they can be prepared by dissolving in water at a mass ratio of silicon dioxide to tin oxide of 0.1 to 5.0. The preferred aqueous solution has a solid content concentration of 1 to 12% by mass, calculated as (SnO2 + SiO2).

[0072] The prepared aqueous solution can be used to remove cations using a cation exchange resin. A hydrogen-form, strongly acidic cation exchange resin is preferred as the cation exchange resin. During the cation exchange, a column packed with, for example, Amberlite (trade name) 120B can be used. Through this cation exchange, the silicic acid component polymerizes with the stannic acid component, generating silica-tin oxide composite colloidal particles with a primary particle size of 1 to 4 nm.

[0073] The silica-tin oxide composite colloidal particles lack stability and gel within hours of standing. Therefore, amine compounds need to be rapidly added after cation exchange to stabilize them. Specifically, an aqueous sol containing silica-tin oxide composite oxide colloidal particles with a primary particle size of 1 to 4 nm needs to be prepared, stabilized with an amine compound present in a silica / tin oxide mass ratio of 0.1 to 5.0 and at a molar ratio of M / (SnO2+SiO2) of 0.1 to 1.0 (where M represents the amine compound). The concentration of the resulting aqueous sol is 0.1 to 10% by mass (SnO2+SiO2).

[0074] In the stabilization of the silica-tin oxide composite colloidal particles generated by the cation exchange, it is suitable to add an amount of amine compound in the form of a molar ratio of M / (SnO2+SiO2) of 0.1 to 1.0. When the molar ratio of M / (SnO2+SiO2) is less than 0.1 to 1.0, the amine compound will lose stability and gel after being left for several hours, which is therefore undesirable.

[0075] Next, by mixing an aqueous sol of colloidal metal oxide particles (a) with a primary particle size of 5 to 60 nm as the core, and an aqueous sol of silica-tin oxide composite oxide colloidal particles (b) with a primary particle size of 1 to 4 nm stabilized with an amine compound having a silica / tin oxide mass ratio of 0.1 to 5.0 and a molar ratio of M / (SnO2+SiO2) of 0.1 to 1.0 (where M represents an amine compound), with the mass ratio of the silica-tin oxide composite oxide colloidal particles to the metal oxide colloidal particles being (b) to (a) being 0.05 to 0.50, it is possible to obtain an aqueous sol of modified metal oxide colloidal particles (A) formed by coating the metal oxide colloidal particles (a) with the silica-tin oxide composite oxide colloidal particles (b).

[0076] The concentration of the solid component in the aqueous sol of the metal oxide colloidal particles (a) is 0.5 to 50% by mass, preferably 5 to 30% by mass.

[0077] The aqueous sol of the metal oxide colloidal particles (a) can be used with a pH of 5 to 11.5, preferably 7 to 11.5. The pH of the aqueous sol can be adjusted as needed using an alkaline component. Examples of alkaline components used include alkali metal hydroxides such as lithium, sodium, and potassium; alkaline earth metal hydroxides such as calcium, magnesium, and strontium; alkylamines such as ammonia, 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.

[0078] The mixing of the aqueous sol of the metal oxide colloidal particles (a) and the aqueous sol of the silica-tin oxide composite oxide colloidal particles (b) as coating particles is preferably carried out under stirring.

[0079] The mixing ratio of the silica-tin oxide composite oxide colloidal particles (b) to the metal oxide colloidal particles (a) is expressed as a mass ratio (b) / (a), and is preferably 0.05 to 0.50. By setting it to 0.05 or higher, sufficient coating of the metal oxide colloidal particles (a) with the silica-tin oxide composite oxide colloidal particles (b) as nuclei can be achieved, resulting in a stable hydrophilic organic solvent dispersion or a hydrophobic organic solvent dispersion having a water solubility of 0.05 to 12% by mass. Furthermore, a mass ratio of 0.50 is sufficient for high efficiency.

[0080] Next, cation exchange is performed on the aqueous sol of the resulting modified metal oxide colloidal particles (A). The cation exchange is preferably performed using a hydrogen-form strongly acidic cation exchange resin.

[0081] Next, an amine compound is added to the resulting aqueous sol in an amount where the molar ratio of the amine compound to the silica-tin oxide composite colloidal particles (b) is M / (SnO2+SiO2) (where M represents the amine compound) is 0.001 to 0.08. By setting the amount of added amine compound such that the molar ratio of M / (SnO2+SiO2) is 0.001 or more, the dispersion stability of the hydrophilic organic solvent dispersion sol of the present invention becomes sufficiently good, which is therefore preferable. Furthermore, by setting the molar ratio of M / (SnO2+SiO2) to 0.08 or less, obstacles to bonding of silane compounds bonded to the particle surface of the modified metal oxide colloidal particles (A) can be avoided.

[0082] Next, the aqueous medium of the resulting aqueous sol is replaced with a hydrophilic organic solvent. Known methods can be used to replace the dispersion medium from water with a hydrophilic organic solvent, such as evaporation displacement under normal or reduced pressure, ultrafiltration membrane method, and solvent extraction method.

[0083] To ensure efficient solvent exchange, the resulting aqueous sol is preferably pre-concentrated to a concentration of 1 to 70% by mass or 10 to 50% by mass of the modified metal oxide colloidal particles (A). Known methods such as heating evaporation and ultrafiltration can be used for sol concentration. The temperature of the sol during solvent exchange is ranged from room temperature to the boiling point of the hydrophilic solvent. Solvent exchange is performed until the water content in the sol is less than 5% by mass. The solids concentration of the resulting sol, based on the total metal oxide concentration of the modified metal oxide colloidal particles (A), is 20 to 70% by mass.

[0084] As a dispersion medium for sols, water or organic solvents such as alcohols, esters, ketones, amides, or hydrocarbons can be used.

[0085] Examples of organic solvents include alcohols, esters, ketones, amides, or hydrocarbons with 1 to 10 carbon atoms that may have ether bonds.

[0086] Examples of alcohols with 1 to 10 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, ethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether.

[0087] As ketones, examples include straight-chain or cyclic aliphatic ketones with 3 to 30 carbon atoms, such as methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, methyl pentyl ketone, cyclohexanone, etc.

[0088] As ethers, examples include straight-chain or cyclic aliphatic ethers with 3 to 30 carbon atoms, such as diethyl ether and tetrahydrofuran.

[0089] As esters, examples include straight-chain or cyclic esters with 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.

[0090] Amides are aliphatic amides with 3 to 30 carbon atoms, such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and N-ethylpyrrolidone.

[0091] As hydrocarbons, examples include straight-chain or cyclic aliphatic or aromatic hydrocarbons with 6 to 30 carbon atoms, such as hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, etc.

[0092] In relation to the compositions of the present invention, as a dispersant, an additive a selected from at least one of silane compounds other than formula (1), organic acids and their salts, phosphate esters, amines and surfactants can be used.

[0093] The surface of the metal oxide particles can be coated with a silane compound of formula (1) and an additive a.

[0094] The compositions of the present invention may further comprise secondary or tertiary amines having a total carbon number of 5 to 35.

[0095] For example, when the metal oxide particles (A) contain silicon dioxide particles, the content of the amine can be set to 0.01 to 10.0 mmol or 0.01 to 5.0 mmol relative to 100 g of SiO2 in the silicon dioxide particles.

[0096] Examples of secondary amines mentioned above include ethyl n-propylamine, ethyl isopropylamine, dipropylamine, diisopropylamine, ethyl butylamine, n-propyl butylamine, dibutylamine, ethyl pentylamine, n-propyl pentylamine, isopropyl pentylamine, dipentylamine, ethyl octylamine, isopropyl octylamine, butyl octylamine, and dioctylamine.

[0097] Examples of the aforementioned tertiary amines include triethylamine, ethyl di-n-propylamine, diethyl-n-propylamine, tri-n-propylamine, triisopropylamine, ethyl dibutylamine, diethylbutylamine, isopropyl dibutylamine, diisopropyl ethylamine, diisopropyl butylamine, tributylamine, ethyl dipentylamine, diethylpentylamine, tripentylamine, methyl dioctylamine, dimethyl octylamine, ethyl dioctylamine, diethyl octylamine, trioctylamine, benzyl dibutylamine, and diazabicycloundecene.

[0098] Among the above-mentioned amines, secondary and tertiary amines having alkyl groups having a total number of carbon atoms of 6 to 35 are preferred, such as diisopropylamine, tripentylamine, triisopropylamine, dimethyloctylamine, trioctylamine, etc.

[0099] As a silane compound other than formula (1), silane coupling agents can be listed, for example, silane compounds selected from at least one of formulas (2) to (4). In the present invention, photoactive metal oxide particles (A) coated with hydrolysate of the above-mentioned silane compounds can be used.

[0100] In equation (2), R 11Each of the following groups is an alkyl, haloalkyl, alkenyl, aryl, or has an organic group having a polyether group, epoxy group, (meth)acryloyl group, mercapto group, amino group, urea group, or cyano group and is bonded to a silicon atom via a Si-C bond: R 12 Each represents an alkoxy, acyloxy, or halogen group, and 'a' represents an integer from 1 to 3.

[0101] In equations (3) and (4), R 13 and R 15 Each is an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and is bonded to silicon atoms via Si-C bonds, R 14 and R 16 Each represents an alkoxy, acyloxy, or halogen group; Y represents an alkylene, NH group, or oxygen atom; b is an integer from 1 to 3; c is an integer from 0 to 1; and d is an integer from 1 to 3.

[0102] Examples of alkyl groups with 1 to 18 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl 1,2-Dimethyl-cyclopropyl, 2,3-Dimethyl-cyclopropyl, 1-Ethyl-cyclopropyl, 2-Ethyl-cyclopropyl, n-Hexyl, 1-Methyl-n-pentyl, 2-Methyl-n-pentyl, 3-Methyl-n-pentyl, 4-Methyl-n-pentyl, 1,1-Dimethyl-n-butyl, 1,2-Dimethyl-n-butyl, 1,3-Dimethyl-n-butyl, 2,2-Dimethyl-n-butyl, 2,3-Dimethyl-n-butyl, 3,3-Dimethyl-n-butyl, 1-Ethyl-n-butyl, 2-Ethyl-n-butyl, 1,1,2-Trimethyl-n-propyl, 1,2,2-Trimethyl-n-propyl Methyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl 1-Isopropyl-cyclopropyl, 2-Isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, etc., but not limited to these.

[0103] In addition, alkylene groups can be listed as those derived from the alkyl groups mentioned above.

[0104] Examples of aryl groups with 6 to 30 carbon atoms include phenyl, naphthyl, anthraceneyl, and pyrene.

[0105] Examples of alkenyl groups include those with 2 to 10 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, etc. -Butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, etc., but not limited to these.

[0106] Examples of alkoxy groups with 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 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, but these are not limited to these.

[0107] Examples of acyloxy groups with 2 to 10 carbon atoms include methyl carbonyloxy, ethyl carbonyloxy, n-propyl carbonyloxy, isopropyl carbonyloxy, n-butyl carbonyloxy, isobutyl carbonyloxy, sec-butyl carbonyloxy, tert-butyl carbonyloxy, n-pentyl carbonyloxy, 1-methyl n-butyl carbonyloxy, 2-methyl n-butyl carbonyloxy, 3-methyl n-butyl carbonyloxy, 1,1-dimethyl n-propyl carbonyloxy, 1,2-dimethyl n-propyl carbonyloxy, 2,2-dimethyl n-propyl carbonyloxy, 1-ethyl n-propyl carbonyloxy, n-hexyl carbonyloxy, 1-methyl n-pentyl carbonyloxy, 2-methyl n-pentyl carbonyloxy, etc., but are not limited to these.

[0108] Examples of halogen groups include fluorine, chlorine, bromine, and iodine.

[0109] As an organic group containing a polyether group, polyetherpropyl groups containing an alkoxy group can be listed as examples. For example, (CH3O)3SiC3H6(OC2H4)nOCH3 can be listed. n can be used in the range of 1 to 100 or 1 to 10.

[0110] Examples of organic groups with epoxy groups include 2-(3,4-epoxycyclohexyl)ethyl and 3-epoxypropoxypropyl.

[0111] The term "(meth)acryloyl" refers to both acryloyl and methacryloyl groups. Examples of organic groups containing a (meth)acryloyl group include 3-methacryloyloxypropyl and 3-acryloyloxypropyl.

[0112] Examples of organic groups containing a thiol group include 3-mercaptopropyl.

[0113] Examples of organic groups containing amino groups include 2-aminoethyl, 3-aminopropyl, N-2-(aminoethyl)-3-aminopropyl, N-(1,3-dimethyl-butylene)aminopropyl, N-phenyl-3-aminopropyl, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl.

[0114] Examples of organic groups containing a urea group include 3-ureopropyl.

[0115] Examples of organic groups containing a cyano group include 3-cyanopropyl.

[0116] The silane compounds represented by the above formulas (3) and (4) are preferably compounds that can form trimethylsilyl groups on the surface of silica particles.

[0117] Examples of these compounds are shown below.

[0118]

[0119] In the above formula, R 22 The alkoxy group can be an alkoxy group, such as methoxy or ethoxy. The silane compounds described above can be silane compounds manufactured by Shin-Etsu Chemical Co., Ltd.

[0120] The hydroxyl groups on the surface of the silica particles, or, in the case of silica particles, silanol groups, can react with the aforementioned silane compounds to coat the silica particles with the siloxane compounds via siloxane bonds. The reaction can be carried out at temperatures ranging from 20°C to the boiling point of the dispersion medium, but can also be carried out at temperatures ranging from, for example, 20°C to 100°C. The reaction can proceed for approximately 0.1 to 6 hours.

[0121] Regarding the aforementioned silane compounds, the coating amount on the surface of silica particles is equivalent to 0.1 silicon atoms / nm in the silane compound. 2 ~6.0 units / nm 2 A certain amount of silane compound is added to the silica sol to coat the surface of the silica particles.

[0122] The hydrolysis of the aforementioned silane compounds requires water, but if the sol is in an aqueous solvent, the water content in that aqueous solvent can be used. Even when the aqueous medium solvent is replaced with an organic solvent, the water remaining in the solvent can be used. For example, water present in the solvent at 0.01–5% by mass or 0.01–1% by mass can be used. Furthermore, hydrolysis can be carried out using a catalyst or without a catalyst.

[0123] In the absence of a catalyst, the surface of silica particles sometimes exists on an acidic side. When a catalyst is used, examples of hydrolysis catalysts include metal chelates, organic acids, inorganic acids, organic bases, and inorganic bases.

[0124] Examples of metal chelates used as hydrolysis catalysts include triethoxy-mono(acetylacetone)titanium and triethoxy-mono(acetylacetone)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.

[0125] The organic acid is selected from at least one of divalent aliphatic carboxylic acids, aliphatic hydroxycarboxylic acids, amino acids, and chelating agents. Examples of divalent aliphatic carboxylic acids include oxalic acid, malonic acid, and succinic acid. Examples of aliphatic hydroxycarboxylic 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-N,N-diacetic acid, and diethylenetriaminepentaacetic acid. Examples of organic acid salts include alkali metal salts, ammonium salts, and amine salts of the above-mentioned organic acids. Examples of alkali metals include sodium and potassium.

[0126] The amount of organic acid and its salt added relative to 100g of SiO2 can be set from 0.01 to 10.0 mmol or from 0.01 to 5.0 mmol.

[0127] As phosphate esters, at least one phosphate ester compound selected from formulas (5) to (7) can be listed.

[0128] In equations (5) to (7), X 1 X 2 and X 3 Each represents an alkylene group with 2 to 20 carbon atoms; f, h, and j each represent an integer from 1 to 100; e, g, and i each represent an integer from 1 to 3; Y 1 Y 2 and Y 3 Each represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, or a (meth)acryloyl group.

[0129] As a phosphate ester, polyoxyethylene alkyl ether phosphate esters are preferred. For example, the phosphate esters mentioned above can be phosphate esters in which the terminal alkyl group (Y1) in the above formula (4) represents an alkyl group with 6 to 10 or 12 to 15 carbon atoms. These products can be manufactured, for example, by Toho Chemical Industry Co., Ltd., under the trade names Phosphhanol RA-600 and RS-610.

[0130] The amount of phosphate ester added relative to 100g of SiO2 can be set to 0.01–10.0 mmol or 0.01–5.0 mmol.

[0131] As surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and silicone surfactants can be used.

[0132] Examples of anionic surfactants used in this invention include sodium and potassium salts of fatty acids, alkylbenzene sulfonates, higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, α-sulfonyl fatty acid esters, α-olefin sulfonates, monoalkyl phosphates, and alkane sulfonates.

[0133] For example, sodium salts, potassium salts, and lithium salts can be listed as alkylbenzene sulfonates, such as C10-C16 sodium alkylbenzene sulfonate, C10-C16 alkylbenzene sulfonic acid, and sodium alkylnaphthalene sulfonate.

[0134] Examples of higher alcohol sulfate salts include sodium dodecyl sulfate (sodium lauryl sulfate), triethanolamine lauryl sulfate, and triethanolamine lauryl sulfate, which have 12 carbon atoms.

[0135] Examples of polyoxyethylene alkyl ether sulfates include sodium polyoxyethylene styrene phenyl ether sulfate, sodium polyoxyethylene styrene phenyl ether sulfate, sodium polyoxyethylene decyl ether sulfate, sodium polyoxyethylene decyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, and sodium polyoxyethylene oleyl cetyl ether sulfate.

[0136] Examples of α-olefin sulfonates include sodium α-olefin sulfonate.

[0137] Examples of alkane sulfonates include sodium 2-ethylhexyl sulfate.

[0138] Examples of cationic surfactants used in this invention include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, and amine salts.

[0139] Alkyltrimethylammonium salts are quaternary ammonium salts with chloride and bromide ions as counterions. Examples include dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, cocoyltrimethylammonium chloride, and alkyl (C16-18)trimethylammonium chloride.

[0140] Dialkyl dimethyl ammonium salts are substances with two lipophilic main chains and two methyl groups. Examples include bis(hydrogenated tallow) dimethyl ammonium chloride, decyl dimethyl ammonium chloride, dicosyl dimethyl ammonium chloride, dihydrogenated tallow alkyl dimethyl ammonium chloride, and dialkyl (C14-18) dimethyl ammonium chloride.

[0141] Alkyl dimethyl benzyl ammonium salts are quaternary ammonium salts having one lipophilic main chain, two methyl groups, and one benzyl group, such as benzalkonium chloride. Alkyl (C8-18) dimethyl benzyl ammonium chloride is another example.

[0142] As an amine salt agent, it is a substance formed by replacing one or more hydrocarbon groups with hydrogen atoms of ammonia, such as N-methyldihydroxyethylamine fatty acid ester hydrochloride.

[0143] Examples of amphoteric surfactants used in this invention include N-alkyl-β-alanine type alkylamino fatty acid salts, alkyl carboxybetaine type alkyl betaines, and N,N-dimethyldodecylamine oxide type alkylamine oxides. Examples of these include lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazoline betaine, and lauryl dimethylamine oxide.

[0144] Examples of nonionic surfactants used in this 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), polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene oil-based ether, polyoxyethylene stearyl ether, polyoxyethylene docosyl ether, polyoxyethylene-2-ethylhexyl ether, and polyoxyethylene isodecyl ether.

[0145] Examples of polyoxyethylene alkylphenol ethers include polyoxyethylene styrene phenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene styrene phenyl ether, and polyoxyethylene tribenzylphenyl ether.

[0146] Examples of alkyl glucosides include decyl glucoside and lauryl glucoside.

[0147] Examples of polyoxyethylene fatty acid esters include polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyethylene glycol distearate, polyethylene glycol dioleate, and polypropylene glycol dioleate.

[0148] 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 sesquioleate, and their ethylene oxide adducts.

[0149] 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.

[0150] In addition, examples of fatty acid alkanolamides include coconut oil fatty acid diethanolamide, tallow fatty acid diethanolamide, lauric acid diethanolamide, and oleic acid diethanolamide.

[0151] Furthermore, examples of surfactants include polyoxyethylene polyoxypropylene glycol, polyoxyethylene fatty acid esters and other polyoxyalkyl ethers or polyoxyalkyl glycols, polyoxyethylene hydrogenated castor oil ether, sorbitan fatty acid ester alkyl ether, alkyl polyglucoside, sorbitan monooleate, sucrose fatty acid ester, etc.

[0152] In addition, silicone surfactants can be used as surfactants. Silicone surfactants are compounds having repeating units containing siloxane bonds in their main chain. The weight-average molecular weight of silicone surfactants can be used in the range of 500 to 50,000. These can be modified silicone surfactants, and examples include structures in which organic groups are introduced into the side chains and / or ends of polysiloxanes. Examples of organic groups include amino, epoxy, alicyclic epoxy, carbinol, mercapto, carboxyl, aliphatic ester, aliphatic amide, and polyether groups.

[0153] As organosilicon surfactants, the following trade names can be listed: Tore Silicone DC3PA, Tore Silicone SH7PA, Tore Silicone DC11PA, Tore Silicone SH21PA, Tore Silicone SH28PA, ToreSilicone SH29PA, Tore Silicone SH30PA, Tore Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), Silwet l-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, ​​L-7657, L-8500, L-8610 (all Momentive Performance). Materials Corporation), KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Silicone Corporation), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie Corporation), etc. For example, as a polyether-modified silicone, the trade name L-7001 (manufactured by DOWSIL Corporation) can be preferred.

[0154] The method for manufacturing the above-mentioned metal oxide sol can include the following steps (i) to (iii):

[0155] (i) Process: The aqueous solvent of the aqueous sol of the metal oxide particles is replaced with an alcohol having 1 to 4 carbon atoms and ether bonds.

[0156] (ii) Step: The sol of metal oxide particles obtained in step (i) is mixed with the silane compound of formula (1).

[0157] (iii) Step: The alcohol solvent of the sol of the metal oxide particles obtained in step (ii) is replaced with an organic solvent other than the alcohol mentioned above.

[0158] The composition obtained by the above manufacturing method can be set to have a solid content of 0.1 to 70% by mass, a photoactive metal oxide particle (A) content of 80 to 99% by mass in the total solid content, and a dispersant content of 1 to 20% by mass.

[0159] Here, "solid component" refers to the component from which the solvent component has been removed from the composition, and "solid component concentration" refers to the concentration of solid components in the composition.

[0160] The compositions of the present invention can be further mixed with thermosetting or photocurable resins to produce varnishes.

[0161] Furthermore, varnishes containing curing agents such as amine-based curing agents, anhydride-based curing agents, or acid-generating curing agents (thermal acid-generating agents or photo-acid-generating agents) can be cured. A varnish containing this composition, resin, and curing agent can be applied to or filled onto a substrate, and cured by heating, light irradiation, or a combination thereof. Examples of curable resins include resins having functional groups such as epoxy groups or (meth)acryloyl groups.

[0162] Examples of epoxy resins containing epoxy groups include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenolic varnish type epoxy resin, aliphatic type epoxy resin, and glycidylamine type epoxy resin.

[0163] Resins containing (meth)acryloyl groups include polymerizable (meth)acrylate monomers. Monofunctional acrylate monomers include β-carboxyethyl acrylate, isobornyl acrylate, phenoxy diethylene glycol acrylate, and phenoxy ethyl acrylate. Difunctional acrylate monomers include dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, PO-modified neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, PEG200 diacrylate, PEG400 diacrylate, PEG600 diacrylate, tricyclodecanediethanol diacrylate, and tricyclodecanediethanol diacrylate. Trifunctional acrylate monomers include trimethylolpropane triacrylate, trimethylolpropane ethoxy triacrylate, glycerol propoxy triacrylate, pentaerythritol (tri / tetra) acrylate, and pentaerythritol (tri / tetra) acrylate. Examples of acrylate monomers with four or more functionalities include pentaerythritol alkoxytetraacrylate, pentaerythritol ethoxytetraacrylate, pentaerythritol (tri / tetra)acrylate, di(trimethylolpropane)tetraacrylate, di(trimethylolpropane)tetraacrylate, di(trimethylolpropane)tetraacrylate, di(trimethylolpropane)tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexaacrylate. Additionally, examples include isobornyl methacrylate, polyethylene glycol dimethacrylate, and trimethylpropane trimethacrylate. These polymerizable (meth)acrylate monomers can be used as one or a mixture of two or more.

[0164] In the case of thermosetting varnishes, a thermosetting agent may be contained in a proportion 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 group.

[0165] Examples of thermosetting agents include phenolic resins, amine curing agents, polyamide resins, imidazoles, polythiols, acid anhydrides, and heat-generating acid agents. Acid anhydride curing agents and amine curing agents are particularly preferred.

[0166] Even if these thermosetting agents are solid, they can be used by dissolving them in a solvent. However, due to the evaporation of the solvent, the density of the cured product decreases and pores are formed, which in turn 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 pressure.

[0167] Examples of phenolic resins include phenolic varnish resin and cresol varnish resin.

[0168] Examples of amine-based 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, isophorone diamine, diaminodicyclohexylmethane, 1,3-diaminomethylcyclohexane, xylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and diethyltoluenediamine. Among these, liquid forms of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthenediamine, isophorone diamine, diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and diethyltoluenediamine are preferred.

[0169] Polyamide resins include polyamide amines, which are formed by the condensation of dimer acids and polyamines and have primary and secondary amines in their molecules.

[0170] Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole ontyl trimellitate, and epoxide imidazole adducts (Adduct).

[0171] Examples of polythiols include substances having thiol groups at the ends of polypropylene glycol chains and substances having thiol groups at the ends of polyethylene glycol chains, with liquid substances being preferred.

[0172] As an anhydride-based curing agent, anhydrides containing multiple carboxyl groups in one molecule are preferred. Examples of such anhydride-based curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic tetracarboxylic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol dipreptyltrimethacrylate, glycerol trimellitic trimethacrylate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, inner methylenetetrahydrophthalic anhydride, methyl inner methylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, and chlorhexidine anhydride.

[0173] Examples of thermally generated acid agents include sulfonium salts and phosphonium salts, but sulfonium salts are preferred. For example, the following compounds can be cited.

[0174]

[0175] In the formula, R represents an alkyl group with 1 to 12 carbon atoms or an aryl group with 6 to 20 carbon atoms, with alkyl groups with 1 to 12 carbon atoms being particularly preferred.

[0176] Among these, the preferred options are methyltetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride (methylnadic anhydride, methyl humic anhydride), hydrogenated methylnadic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methylhexahydrophthalic anhydride, and mixtures of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, which are liquids at room temperature and pressure. The viscosity of these liquid anhydrides is approximately 10 mPas to 1000 mPas when measured at 25°C.

[0177] In addition, when obtaining the above-mentioned cured product, curing aids may be used in combination as appropriate. Examples of curing aids include organophosphorus compounds such as triphenylphosphine and tributylphosphine, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and diethyl methyltriphenylphosphonium phosphate, quaternary ammonium salts such as 1,8-diazabicyclo(5,4,0)undecane-7-ene, 1,8-diazabicyclo(5,4,0)undecane-7-ene and octanoic acid salts, zinc octanoate, and tetrabutylammonium bromide. These curing aids can be contained in a ratio of 0.001 to 0.1 parts by mass relative to 1 part by mass of the curing agent.

[0178] Thermosetting varnishes are obtained by mixing the composition, resin, curing agent, and curing aids as needed. These mixtures can be carried out in a reaction vessel using stirring blades or a kneader.

[0179] Mixing is carried out by heating at a temperature of 60℃ to 100℃ for 0.5 to 1 hour.

[0180] The resulting curable resin varnish (thermosetting composition) is a thermosetting coating composition with a suitable viscosity, for example, for use as a liquid sealing material. The liquid thermosetting varnish can be prepared to any viscosity, and since it can be used as a transparent sealing material for LEDs, etc., by methods such as casting, pouring, dispensing, and printing, it can be partially sealed at any location. By directly applying the liquid thermosetting composition to LEDs, etc., in liquid form using the methods described above, followed by drying and curing, a cured epoxy resin body is obtained.

[0181] A cured product is obtained by applying a thermosetting varnish (thermosetting coating composition) to a substrate and heating it at a temperature of 80–200°C.

[0182] In the case of a photocurable varnish, a photocuring agent (photoacid generator or photoradioactive agent) may be contained in a proportion of 0.5 to 20% by mass, preferably 0.8 to 10% by mass, relative to functional groups such as epoxy groups or (meth)acryloyl groups in the resin.

[0183] There are no particular limitations on photoacid-producing agents, as long as they are substances that produce acid directly or indirectly due to light irradiation.

[0184] Specific examples of photoacid generators include triazine compounds, acetophenone derivatives, disulfone compounds, diazomethane compounds, sulfonic acid derivatives, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, metallocene complexes, and iron aromatic hydrocarbon complexes.

[0185] Among the ononium salts used as the aforementioned photoacid-generating agents, examples of iodonium salts include diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium methanesulfonate, diphenyliodonium toluenesulfonate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium methanesulfonate, bis(p-tert-butylphenyl)iodonium toluenesulfonate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, and bis(p-tert-butylphenyl)iodonium. Tetrafluoroborate, bis(p-tert-butylphenyl)iodonium chloride, bis(p-chlorophenyl)iodonium chloride, bis(p-chlorophenyl)iodonium tetrafluoroborate, and further examples include bis(alkylphenyl)iodonium salts such as bis(4-tert-butylphenyl)iodonium hexafluorophosphate, alkoxycarbonylalkoxy-trialkylaryl iodonium salts (e.g., 4-[(1-ethoxycarbonyl-ethoxy)phenyl]-(2,4,6-trimethylphenyl)-iodonium hexafluorophosphate), and bis(alkoxyaryl)iodonium salts (e.g., (4-methoxyphenyl)phenyliodonium hexafluoroantimonate, etc.).

[0186] Examples of sulfonium salts include triphenylsulfonium chloride, triphenylsulfonium bromide, tri(p-methoxyphenyl)sulfonium tetrafluoroborate, tri(p-methoxyphenyl)sulfonium hexafluorophosphonate, tri(p-ethoxyphenyl)sulfonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, etc.; (4-phenylthiophenyl)diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl)diphenylsulfonium hexafluorophosphate, bis[4-(diphenylsulfonium)phenyl]sulfide-bis-hexafluoroantimonate, bis[4-(diphenylsulfonium)phenyl]sulfide-bis-hexafluorophosphate, (4-methoxyphenyl)diphenylsulfonium hexafluoroantimonate, etc.

[0187] 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-chlorobenzyldiazoium hexafluorophosphate, and benzyltriphenylphosphonium hexafluoroantimonate.

[0188] In addition, examples include selenomonium salts such as triphenylselenomonium hexafluorophosphate and metallocene complexes such as (η5 or η6-isopropylbenzene) (η5-cyclopentadienyl)iron(II) hexafluorophosphate.

[0189] In addition, the following compounds can also be used as photoacid generators.

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199] As photoacid-generating agents, sulfonium salt compounds and iodonium salt compounds are preferred. Examples of their anions include CF3SO3. - C4F9SO3 - C8F 17 SO3 - Camphor sulfonic acid anion, toluene sulfonic acid anion, BF4- PF6 - AsF6 - and SbF6 - Etc. Particularly preferred are anionic species such as phosphorus hexafluoride and antimony hexafluoride, which exhibit strong acidity.

[0200] In addition, examples of photoradical generators include acetophenones, benzoins, benzophenones, thioxanones, and acylphosphine oxides.

[0201] Examples of acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexylphenylone, 2-methyl-2-morpholino(4-thiomethylphenyl)propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone.

[0202] Examples of benzoin derivatives include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0203] Examples of benzophenones include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenoxy)ethyl]benzenemethylammonium bromide, and (4-benzoylbenzyl)trimethylammonium chloride.

[0204] 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 methyl chloride.

[0205] 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.

[0206] The compositions and varnishes of the present invention may include conventional additives as needed. Examples of such additives include pigments, colorants, thickeners, sensitizers, defoamers, leveling agents, coatability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), plasticizers, solubilizers, fillers, and antistatic agents. These additives may be used alone or in combination of two or more.

[0207] Examples of coating methods for the compositions and varnishes of the present invention include flow coating, spin coating, spray coating, screen printing, casting, rod coating, curtain coating, roller coating, gravure coating, immersion coating, slot coating, and nanoimprinting.

[0208] Nanoimprinting is a method for manufacturing microstructures by performing nanoimprinting processing on a resin composition. For example, it can include a step of (1) coating the above-mentioned resin composition to form a film, (2) transferring a pattern onto the film using a nanoimprinting process, and (3) curing the film with the transferred pattern to obtain a microstructure.

[0209] In step (1) above, a film formed from a resin composition can be formed on a transparent support. In step (2), a nano-molding material selected from at least one of silicone, glass, and silica glass can be used as a raw material. Furthermore, steps (2) and (3) can involve pressing the nano-molding material with a pressure of 0.1–10 MPa for 0.1–300 seconds or 5–50 seconds to transfer a pattern, while simultaneously heating or UV irradiating the film to cure it, thereby obtaining a microstructure. The manufacturing method of the present invention may further include a step (4) of etching the cured film.

[0210] In this invention, microstructures can be provided. Microstructures include, for example, semiconductor materials, diffractive light-collecting films, polarizing films, optical waveguides, or holograms.

[0211] In the case of nanoimprinting, in addition to the usual nanoimprinting (narrowly defined) in which a pattern is transferred by pressing a nanomold onto a film set on a support, it is also possible to use a micro-pattern transfer technique using a mold (broadly defined) that uses a mold with a fine pattern instead of a nanomold, pours a resin composition onto the mold, overlaps a support on it, and presses it from the top.

[0212] Because of the use of resin compositions that are difficult to cure and shrink, nanoimprinting allows for the efficient and precise fabrication of microstructures with nanoscale patterns. This method of nanoimprinting with such resin compositions is suitable for the mass production of microstructures, enabling the economical and efficient manufacture of microstructures such as semiconductor materials, optical waveguides, and holograms.

[0213] In this invention, a photocoating composition can be coated onto a substrate and cured by light irradiation. Additionally, heating can be performed before and after light irradiation.

[0214] The thickness of the coating can be selected from approximately 0.01 μm to 10 mm depending on the intended use of the cured material. For example, when used as a photoresist, it can be set to approximately 0.05 to 10 μm (especially 0.1 to 5 μm); when used as a printed wiring substrate, it can be set to approximately 5 μm to 5 mm (especially 100 μm to 1 mm); and when used as an optical thin film, it can be set to approximately 0.1 to 100 μm (especially 0.3 to 50 μm).

[0215] The light used for irradiation or exposure when using photoacid-generating agents can be, for example, gamma rays, X-rays, ultraviolet light, or visible light, usually visible light or ultraviolet light, especially ultraviolet light. The wavelength of the light is, for example, 150–800 nm, preferably 150–600 nm, more preferably 200–400 nm, and particularly around 300–400 nm. The amount of irradiated light varies depending on the thickness of the coating, but can be set to, for example, 2–20000 mJ / cm². 2 Preferred concentration: 5–5000 mJ / cm 2 The light source can be selected according to the type of light being exposed; for example, in the case of ultraviolet light, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, deuterium lamps, halogen lamps, lasers (helium-cadmium lasers, excimer lasers, etc.) can be used. The curing reaction of the composition is carried out by such light irradiation.

[0216] When using a heat-generating acid agent, or a photo-generating acid agent, the coating film is heated as needed after light irradiation, for example, at 60–250°C, preferably around 100–200°C. The heating time can be selected from a range of more than 3 seconds (e.g., 3 seconds to about 5 hours), for example, 5 seconds to 2 hours, preferably around 20 seconds to 30 minutes, and usually around 1 minute to 3 hours (e.g., 5 minutes to 2.5 hours).

[0217] Furthermore, when forming patterns or images (e.g., when manufacturing printed wiring boards), the coating formed on the substrate can be pattern-exposed. This pattern exposure can be performed by scanning with a laser or by irradiating with light through a photomask. The unexposed areas (unexposed portions) generated by such pattern exposure can be developed (or dissolved) with a developer to form patterns or images.

[0218] As a developer, it can be used in alkaline aqueous solutions and organic solvents.

[0219] 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 solutions of amines such as ethanolamine, propylamine, and ethylenediamine.

[0220] The alkaline developer is typically an aqueous solution of 10% by mass or less, preferably an aqueous solution of 0.1% to 3.0% by mass. Furthermore, alcohols and surfactants can also be added to the developer, preferably in amounts of 0.05 to 10 parts by mass relative to 100 parts by mass of the developer.

[0221] Among them, a 0.1–2.38% (w / w) aqueous solution of tetramethylammonium hydroxide can be used.

[0222] Furthermore, common organic solvents can be used as the developing solution, 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 can be used as one or a mixture of two or more. In particular, propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, etc., are preferred.

[0223] In this invention, to improve adhesion to the developed substrate, an adhesion promoter can be added to the varnish. 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 trimethylsilylimidazolium; vinyltrichlorosilane; and γ-chlorosilane. The adhesive accelerators include silanes such as propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, and γ-(N-piperidinyl)propyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urea, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. One or more of these adhesive accelerators can be used in combination. The amount of these adhesive accelerators added in the solids component is typically less than 18% by mass, preferably 0.0008 to 9% by mass, and more preferably 0.04 to 9% by mass.

[0224] The compositions and varnishes of the present invention may contain sensitizers. Examples of usable sensitizers include anthracene, phenothiazine, perylene, thioxanthone, and benzophenone-thioxanthone. Furthermore, examples of sensitizing pigments include thiopyranonium salt pigments, anthocyanin pigments, quinoline pigments, styrylquinoline pigments, coumarinone pigments, thioxanthone pigments, xanthanthone pigments, oxonol pigments, anthocyanin pigments, rhodamine pigments, and pyranonium salt pigments. Anthracene-based sensitizers are particularly preferred, as their sensitivity is dramatically improved when used in conjunction with a cationic curing catalyst (a radiosensitive cationic polymerization initiator), and they also possess free radical polymerization initiation capabilities. The hybrid type of the present invention, which combines a cationic curing system and a free radical curing system, simplifies the selection of catalysts. Specifically, dibutoxyanthracene and dipropoxyanthraquinone are effective anthracene compounds. Regarding the amount of sensitizer added, it is used in the solid component at a ratio of 0.01 to 20% by mass, preferably 0.01 to 10% by mass.

[0225] The thermosetting and photocuring materials using the epoxy compound-containing varnishes of this invention possess characteristics such as rapid curing, transparency, and low curing shrinkage, and can be used for coating and bonding electronic components, optical components, and precision mechanical components. For example, they can be used for bonding optical components such as lenses for mobile phones and cameras, light-emitting diodes (LEDs) and semiconductor lasers (LDs), liquid crystal panels, biochips, camera lenses, prisms, magnetic components of hard drives in personal computers, pickups (the part that acquires light information reflected from optical discs) in CD and DVD players, cones and coils of speakers, magnets in electric motors, circuit boards, electronic components, and internal components of automobile engines.

[0226] As a hard coating material used for surface protection of automobile bodies, lamps, electrical products, building materials, plastics, etc., it can be applied to automobile and motorcycle bodies, headlamp lenses, mirrors, plastic lenses for eyeglasses, mobile phones, game consoles, optical films, ID cards, etc.

[0227] As an ink material used in printing on metals such as aluminum and plastics, its applications include credit cards, membership cards and other cards, electrical products, switches for OA equipment, ink for printing on keyboards, and ink for inkjet printers for CDs, DVDs and other products.

[0228] In addition, examples include the technology of combining with 3D CAD to create complex three-dimensional objects by curing resin, its application in stereolithography such as the model making of industrial products, and its application in the coating, bonding, optical waveguides, and thick film resists of optical fibers.

[0229] Furthermore, the cured composition containing the composition of the present invention is suitable for use as an insulating resin for electronic materials such as semiconductor sealing materials, adhesives for electronic materials, printed wiring board materials, interlayer insulating film materials, sealing materials for power modules, and insulating resins for high-voltage equipment such as generator coils, transformer coils, and gas-insulated switching devices.

[0230] Example

[0231] [Total metal oxide concentration]

[0232] Weigh the sol using a crucible, heat it at 110°C for 30 minutes to remove the solvent, and perform pre-drying. Then calcine it at 600°C for 30 minutes. Weigh the crucible and calculate the total metal oxide concentration from the weight of the residue.

[0233] [Average Particle Size Based on Dynamic Light Scattering (Dynamic Light Scattering Method for Particle Size)]

[0234] The sol was diluted with a dispersing solvent, and the parameters of the solvent were measured using a dynamic light scattering method. The apparatus was manufactured by Malvern Instruments Ltd and traded under the name Zetasizer.

[0235] [Dispersion Stability]

[0236] After storing the dispersion at 50°C for 1 week, samples with no change in particle size less than 1.2 times compared to before the storage test were marked as "○", while samples with a change in particle size of more than 1.2 times or that could not maintain the sol state and precipitated into two layers were marked as "×".

[0237] [Surface modification rate]

[0238] Based on the molecular formula of the surface modifier (silane compound), calculate the percentage of carbon-derived molecular weight in the surface modifier's molecular weight (M). A Next, when preparing a metal oxide sol containing surface-modified metal oxide particles, a ratio (W / W) of surface modifier added relative to the weight of the metal oxide particles is used. A The amount of carbon (C) in the surface modifier added relative to the weight of the metal oxide particles is calculated using the following formula. A ).

[0239]

[0240] Next, 2 mL of a metal oxide sol containing surface-modified metal oxide particles was added to 10 mL of n-hexane. After centrifugation (centrifugal force: 2770 G), the supernatant was discarded, and the precipitate was separated. This process was then repeated twice, adding 20 mL of n-hexane and centrifuging (centrifugal force: 2770 G) to separate the precipitate. The resulting precipitate was vacuum dried at 150 °C to obtain a dry powder. The carbon content (C) of this dry powder was determined using an elemental analysis apparatus (PerkinElmer, trade name 2400II). B ) and nitrogen content (N B The obtained carbon content (C) B The nitrogen content (N) originates from surface modifiers used to modify the surface of metal oxide particles and amine compounds added during the production of metal oxide particles. B The amine compound is derived from the amine compound added during the production of metal oxide particles. Based on the molecular formula of the amine compound added during the production of metal oxide particles, the percentage of carbon-derived molecular weight in the added amine compound's molecular weight (M) is calculated. B ) and the ratio of molecular weight derived from nitrogen (M C The carbon content (C) obtained from elemental analysis is calculated using the following formula. B The carbon content (C) derived from surface modifiers in the ) C ).

[0241]

[0242] Next, the weight ratio (P) of the metal oxide component in the dried powder obtained by vacuum drying at 150°C is calculated according to the following formula. A ).

[0243]

[0244] Finally, the surface modification rate bonded to the particle surface is quantified according to the following formula.

[0245]

[0246] In this invention, the surface modification rate is preferably 30-100%, more preferably 40-100%. By keeping the surface modification rate within the above-mentioned range, the dispersion stability in organic solvents and resins becomes better, and a highly transparent cured film can be obtained.

[0247] In addition, the cured films obtained in the examples and comparative examples were formed and evaluated using the methods shown below.

[0248] (1) Film thickness

[0249] The reflectance of the cured film formed on a glass substrate was measured using a reflectance meter (manufactured by Olympus Corporation, trade name USPM-RU). The thickness of the cured film was calculated using optical simulation based on the measured reflectance.

[0250] (2) Transparency

[0251] The presence or absence of turbidity in the cured film formed on the glass substrate was examined using a spectrophotometer (NHK Denshoku Kogyo Co., Ltd. SH7000). The judgment criteria are as follows.

[0252] ○: Haze value is less than 0.1%.

[0253] △: Haze value is above 0.1% but less than 0.3%.

[0254] ×: Haze value is above 0.3%.

[0255] (3) UV resistance

[0256] Using a UV-A fluorescent lamp-type accelerated weathering tester (manufactured by Q-Lab, trade name QUV), at 0.89 W / m 2 Under conditions of (340nm), the cured film formed on the glass substrate was irradiated with ultraviolet light for 3 hours. The judgment criteria are as follows.

[0257] When the initial film thickness is set as d0, and the film thickness after lightfastness evaluation is set as d,

[0258] Film thickness change rate = (d0 - d) / d0 × 100

[0259] ○: The film thickness change rate is less than 5%.

[0260] ×: The film thickness change rate is above 5%.

[0261] (4) Imprintability

[0262] A solvent-free film was prepared by spin-coating a sol containing colloidal particles and an organic solvent dispersion onto a quartz substrate and heating it at 100°C for 1 minute using a hot plate. The resulting film was then cured by irradiating it with ultraviolet light while being pressed against a quartz mold (manufactured by Kyodo International Co., Ltd., trade name NM-0801HB) that had undergone a mold release treatment. The cured film was then peeled off from the mold, and the resulting pattern was observed using a SEM (Japan Electronics Co., Ltd., trade name JSM-6010LV). The evaluation criteria are as follows.

[0263] ○: The pattern is transferred and has good imprintability.

[0264] ×: The pattern was not transferred, resulting in poor imprintability.

[0265] (Refer to Example 1): Preparation of titanium dioxide-tin oxide composite oxide colloidal particles (A1) that form the nucleus

[0266] 319.5 g of a 25% (w / w) tetramethylammonium hydroxide aqueous solution was dissolved in 947.1 g of pure water. Then, under stirring, 7.4 g of metastannic acid (containing 6.3 g of SnO2), 236.6 g of titanium tetraisopropoxide (containing 66.6 g of TiO2), and 82.0 g of oxalic acid dihydrate (containing 58.5 g of oxalic acid) were added. The mixture was kept at 80°C for 2 hours, then the pressure was reduced to 580 Torr and maintained for 2 hours to prepare a new solution. This solution was then placed in a glass-lined autoclave and subjected to hydrothermal treatment at 140°C for 5 hours. After cooling to room temperature, the solution was removed. The resulting sol was desalted and washed by ultrafiltration, and then 41.6 g of 35% tetraethylammonium hydroxide was added. The resulting sol was an alkaline aqueous dispersion of titanium dioxide-tin oxide composite colloidal particles (Al), with a pH of 11.2 and a total metal oxide concentration (TiO2 and SnO2) of 5.0% by mass. The primary particle size observed using a transmission electron microscope was 5–15 nm. X-ray diffraction analysis of the powder obtained by drying the sol at 110 °C confirmed it to be rutile crystals.

[0267] (Refer to Example 2): Preparation of titanium dioxide-tin oxide composite oxide colloidal particles (A2) that form the nucleus

[0268] 319.5 g of a 25% (w / w) tetramethylammonium hydroxide aqueous solution was dissolved in 947.1 g of pure water. Then, under stirring, 14.8 g of metastannic acid (containing 12.5 g of SnO2), 236.6 g of titanium tetraisopropoxide (containing 66.6 g of TiO2), and 82.0 g of oxalic acid dihydrate (containing 58.5 g of oxalic acid) were added. The mixture was kept at 80°C for 2 hours, then the pressure was reduced to 580 Torr and kept for 2 hours to prepare a new solution. This solution was then placed in a glass-lined autoclave and subjected to hydrothermal treatment at 140°C for 5 hours. After cooling to room temperature, the solution was removed. The resulting sol was desalted and washed by ultrafiltration, and then 45.2 g of 35% tetraethylammonium hydroxide was added. The resulting sol was an alkaline aqueous dispersion of titanium oxide-tin oxide composite colloidal particles (A2), with a pH of 11.5 and a total metal oxide concentration (TiO2 and SnO2) of 5.0% by mass. The primary particle size observed using a transmission electron microscope was 5–15 nm. X-ray diffraction analysis of the powder obtained by drying the sol at 110 °C confirmed it to be rutile crystals.

[0269] (Refer to Example 3): Preparation of silica-tin oxide composite oxide colloidal particles (B1) as coatings

[0270] 77.2 g of JIS No. 3 sodium silicate (containing 29.8% by mass, converted to SiO2) was dissolved in 668.8 g of pure water. Then, 20.9 g of sodium stannate (NaSnO3·H2O, containing 55.1% by mass, converted to SnO2) was dissolved. The resulting aqueous solution was passed through a column packed with hydrogen-form cation exchange resin (Amberlite (trade name) IR-120B). Next, 7.2 g of diisopropylamine was added to the resulting aqueous dispersion. The resulting sol was an alkaline aqueous dispersion of silica-tin oxide composite colloidal particles (B1), with a pH of 8.0, a total metal oxide concentration (SnO2 and SnO2) of 1.7% by mass, and a primary particle size of 1–4 nm as observed by transmission electron microscopy.

[0271] (Refer to Example 4): Preparation of Zirconia-Tin Oxide Composite Oxide Colloidal Particles (A3) that form the nucleus

[0272] 293.7 g of a tetramethylammonium bicarbonate aqueous solution (containing 42.4% by mass, converted from tetramethylammonium hydroxide) was diluted with 111.5 g of pure water. While stirring the aqueous solution, 168.4 g of zirconium oxycarbonate powder (containing 40.1% by mass, converted from ZrO2) was slowly added. After the addition was complete, the solution was heated to 85°C, and 9.6 g of metastannic acid (containing 86.0% by mass, calculated as SnO2) was slowly added. The solution was then heated at 105°C for 5 hours to mature, followed by hydrothermal treatment at 145°C for 5 hours. Next, the sol was washed and concentrated using an ultrafiltration device while adding pure water. The resulting sol was an alkaline aqueous dispersion of zirconium oxide-tin oxide composite oxide colloidal particles (A3), with a pH of 9.4, a total metal oxide concentration (combined ZrO2 and SnO2) of 10.0% by mass, and a primary particle size of 3–20 nm as observed by transmission electron microscopy.

[0273] (Refer to Example 5): Preparation of tin oxide colloidal particles (A4) that form a nucleus

[0274] 64.0 g of oxalic acid dihydrate (equivalent to 45.7 g of oxalic acid) was dissolved in 723.3 g of pure water. While stirring, the solution was heated to 70°C. Then, 290.3 g of 35% hydrogen peroxide solution and 128.1 g of metallic tin powder (containing 99.7% SnO2) were added. The hydrogen peroxide solution and metallic tin were added alternately in 10 batches. First, 29.0 g of 35% hydrogen peroxide solution was added, followed by 12.8 g of metallic tin. The reaction was allowed to complete (10–15 minutes), and this process was repeated. The total addition time was 2 hours. After the addition was complete, the solution temperature was maintained at 90°C while heating for 2 hours to complete the reaction. Next, 394.5 g of 35% hydrogen peroxide solution was added, and the solution was maintained at 90°C for 5 hours. Next, 5.1 g of isopropylamine was added, and after maintaining the solution at 50°C for 3 hours, the solution 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 of basic tin oxide colloidal particles (A4), with a pH of 11.0 and a SnO2 concentration of 4.0% by mass. The primary particle size observed using a transmission electron microscope was 2–24 nm.

[0275] (Manufacturing Example 1): Preparation of titanium dioxide-tin oxide composite oxide colloidal particles (C1) modified with silica-tin oxide composite oxide

[0276] 1500.0 g of the aqueous dispersion of titanium dioxide-tin oxide composite oxide colloidal particles (A1) prepared in Reference Example 1 was added to 661.8 g of the alkaline silica-tin oxide composite oxide colloidal particles (B1) prepared in Reference Example 4 under stirring. After heating at 95°C for 3 hours, the solution was passed through a column packed with cation exchange resin (Amberlite IR-120B, manufactured by ORGANO Co., Ltd.). 2.5 g of tri-n-pentylamine was added to the resulting aqueous dispersion, and the solution was concentrated by ultrafiltration to obtain an aqueous dispersion of titanium dioxide-tin oxide composite oxide colloidal particles (C1) modified with silica-tin oxide composite oxide. The aqueous dispersion has a pH of 5.2, a total metal oxide (TiO2, SnO2 and SiO2) concentration of 30.5% by mass, a viscosity of 5.0 mPa·s, and an average particle size (dynamic light scattering particle size) of 15 nm obtained by dynamic light scattering (DLS).

[0277] (Manufacturing Example 2): Preparation of titanium dioxide-tin oxide-zirconia composite oxide colloidal particles (C2) modified with silica-tin oxide composite oxide

[0278] 82.7 g of zirconium oxychloride (containing 21.2% by mass, converted from ZrO2) was diluted with 501.1 g of pure water to prepare 583.8 g of zirconium oxychloride aqueous solution (containing 3.0% by mass, converted from ZrO2). 1750.0 g of an aqueous dispersion sol of titanium oxide-tin oxide composite oxide colloidal particles (A2) prepared in Reference Example 2 was added under stirring. Hydrolysis was then performed by heating at 95°C for 5 hours to obtain an aqueous dispersion sol of titanium oxide-tin oxide-zirconia composite oxide colloidal particles with a zirconium oxide film layer formed on the surface. 2330.0 g of the obtained aqueous dispersion sol was added under stirring to 1852.9 g of an alkaline silica-tin oxide composite oxide colloidal particle (B1) aqueous dispersion sol prepared in Reference Example 4, and the solution was passed through a column filled with 500 mL of anion exchange resin (Amberlite IRA-410, manufactured by ORGANO Co., Ltd.). Next, the aqueous dispersion sol after liquid percolation was heated at 95°C for 5 hours, and then passed through a column packed with cation exchange resin (Amberlite IR-120B, manufactured by ORGANO Co., Ltd.). 3.5 g of tri-n-pentylamine was added to the resulting aqueous dispersion sol, and the mixture was concentrated using ultrafiltration to obtain an aqueous dispersion sol of titanium dioxide-tin oxide-zirconia composite oxide colloidal particles (C2) modified with silica-tin oxide composite oxide. This aqueous dispersion sol had a pH of 5.2, a total metal oxide (TiO2, ZrO2, SnO2, and SiO2) concentration of 30.5% by mass, a viscosity of 5.0 mPa·s, and an average particle size (dynamic light scattering particle size) of 20 nm obtained by dynamic light scattering (DLS).

[0279] (Manufacturing Example 3): Preparation of Zirconia-Tin Oxide Composite Oxide Colloidal Particles (C3) Modified with Silica-Tin Oxide Composite Oxide

[0280] To 700.0 g of the alkaline zirconium oxide-tin oxide composite oxide colloidal particles (A3) obtained in Reference Example 4, 800.0 g of the alkaline silica-tin oxide composite oxide colloidal particles (B1) prepared in Reference Example 2 were added under stirring. The mixture was then heated to 95°C and held for 2 hours, followed by bubbling through a column packed with hydrogen-form cation exchange resin (Amberlite (trade name) IR-120B). 3.4 g of tri-n-pentylamine was added to the resulting aqueous dispersion, and the mixture was concentrated using ultrafiltration to obtain an aqueous dispersion of zirconium oxide-tin oxide composite oxide colloidal particles (C3) modified with silica-tin oxide composite oxide. The aqueous dispersion has a pH of 5.0, a total metal oxide (ZrO2, SnO2 and SiO2) concentration of 30.0% by mass, a viscosity of 5.3 mPa·s, and an average particle size (dynamic light scattering particle size) of 23 nm obtained by dynamic light scattering (DLS).

[0281] (Manufacturing Example 4): Preparation of tin oxide colloidal particles (C4) modified with silica-tin oxide composite oxide

[0282] To 1400.0 g of the aqueous dispersion of tin oxide colloidal particles (A4) obtained in Reference Example 5, 500.0 g of the alkaline silica-tin oxide composite oxide colloidal particles (B1) prepared in Reference Example 2 was added under stirring. The mixture was then heated to 95°C and held for 2 hours, followed by bubbling through a column packed with hydrogen-form cation exchange resin (Amberlite (trade name) IR-120B). 1.5 g of tri-n-pentylamine was added to the resulting aqueous dispersion, and the mixture was concentrated using ultrafiltration to obtain an aqueous dispersion of tin oxide colloidal particles (C4) modified with silica-tin oxide composite oxide. This aqueous dispersion had a total metal oxide (SnO2 and SiO2) concentration of 30.5% by mass, a viscosity of 4.8 mPa·s, and an average particle size (DLS particle size) of 18 nm.

[0283] (Example 1)

[0284] 100g of an aqueous dispersion sol of silica-tin oxide-titanium oxide composite oxide colloidal particles (C1) modified with silica-tin oxide composite oxide obtained in Manufacturing Example 1 was used to replace the dispersion medium with methanol using a rotary evaporator, resulting in a methanol dispersion sol of silica-tin oxide-titanium oxide composite oxide colloidal particles (C1) modified with silica-tin oxide composite oxide. To the obtained sol, 6.1g of a product called X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a surface modifier under stirring, and the mixture was refluxed at 65°C for 5 hours to modify the particle surface. Next, the dispersion medium was replaced with propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) using a rotary evaporator to prepare a PGMEA dispersion sol. The total metal oxide (TiO2, SnO2 and SiO2) concentration of the surface-modified PGMEA dispersion sol was 20.5% by mass, the average particle size (dynamic light scattering particle size) obtained by dynamic light scattering (DLS) was 16 nm, the dispersion stability was "○", and the surface modification rate was 40%.

[0285] (Membrane evaluation A-1)

[0286] Using the PGMEA dispersion sol obtained in Example 1, a cured film was prepared according to the following steps.

[0287] In a brown bottle equipped with a magnetic stirrer, 1.3 g of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) and 3.0 g of PGME were added, and 25.3 g of the PGMEA dispersion sol from Example 1 was added while stirring. Next, 0.013 g of a photoradical polymerization initiator (manufactured by BASF Co., Ltd., 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 Chemical Co., Ltd., trade name DOWSIL L-7001) were added, and the mixture was stirred for 0.5 hours to prepare the coating solution. Prepare glass substrates and apply a coating solution (1 μm thickness) to them using a spin coating method. After allowing the solvent to evaporate at 100°C for 2 minutes, the cumulative light intensity is calculated to be 1000 mJ / cm². 2 The coating is cured using ultraviolet light from a high-pressure mercury lamp to form a cured film. The resulting cured film has a transparency rating of "○" and a UV resistance rating of "○". Furthermore, when evaluating the imprintability using this coating solution, it received a rating of "○".

[0288] (Membrane evaluation A-2)

[0289] Using the PGMEA dispersion sol obtained in Example 1, a cured film was prepared following the same steps as in film evaluation A-1, except that the resin binder was changed to polyethylene glycol #400 acrylate (manufactured by Resonac Co., Ltd., trade name FA-240A). The resulting cured film had a transparency rating of "○" and a UV resistance rating of "○". Furthermore, when evaluating imprintability using this coating solution, the rating was "○".

[0290] (Membrane evaluation A-3)

[0291] Using the PGMEA dispersion sol obtained in Example 1, a cured film was prepared following the same steps as in film evaluation A-1, except that the resin binder was changed to a flexural silicone oligomer containing acryloyl groups (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name X-40-2761). The resulting cured film had a transparency rating of "○" and a UV resistance rating of "○". Furthermore, when evaluating imprintability using this coating solution, the rating was "○".

[0292] (Example 2)

[0293] Except that, in Example 1, the colloidal particles were changed to (C2) obtained in Manufacturing Example 2, the amount of surface modifier added was 3.1 g, and the displacement solvent was propylene glycol monomethyl ether (hereinafter referred to as PGME), the sol was prepared in the same manner as in Example 1. At this time, the total metal oxide (TiO2, SnO2, ZrO2, and SiO2) concentration of the PGME dispersion sol was 30.5% by mass, the average particle size obtained by dynamic light scattering (DLS) was 13 nm, the dispersion stability was "○", and the surface modification rate was 40%.

[0294] (Example 3)

[0295] Except that, in Example 1, the colloidal particles were changed to (C3) obtained in Manufacturing Example 3, the amount of surface modifier X-12-1333A added was 3.1 g, and PGME was used as the displacement solvent, the sol was prepared in the same manner as in Example 1. At this time, the total metal oxide (ZrO2, SnO2, and SiO2) concentration of the PGME-dispersed sol was 20.5% by mass, the average particle size (dynamic light scattering particle size) obtained by dynamic light scattering (DLS) was 16 nm, the dispersion stability was "○", and the surface modification rate was 40%.

[0296] Next, using the sol, a cured film was prepared following the same steps as in film evaluation A-1.

[0297] The resulting cured film had a transparency rating of "○" and a UV resistance rating of "○". Additionally, when evaluating the imprintability using this coating solution, it was rated as "○".

[0298] (Example 4)

[0299] Except that in Example 1, the colloidal particles were changed to (C4) obtained in Manufacturing Example 4, the amount of surface modifier X-12-1333A added was 1.5 g, and PGME was used as the displacement solvent, the sol was prepared in the same manner as in Example 1. At this time, the total metal oxide (SnO2 and SiO2) concentration of the PGME dispersion sol was 20.5% by mass%, the average particle size (dynamic light scattering particle size) obtained by dynamic light scattering (DLS) was 18 nm, the dispersion stability was "○", and the surface modification rate was 50%.

[0300] Next, using this sol, a cured film was prepared following the same steps as in film evaluation A-1.

[0301] The resulting cured film had a transparency rating of "○" and a UV resistance rating of "○". Additionally, when evaluating the imprintability using this coating solution, it was rated as "○".

[0302] (Example 5)

[0303] Except that in Example 1, the colloidal particles were changed to an aqueous silica sol, the trade name SNOWTEX O-33 (silica concentration 33.5% by mass, pH 2.6, manufactured by Nissan Chemical Co., Ltd.), the amount of surface modifier X-12-1333A added was 6.7 g, and PGME was used as the displacement solvent, the sol was prepared in the same manner as in Example 1. At this time, the total metal oxide (SiO2) concentration of the PGME dispersion sol was 20.6% by mass, the average particle size obtained by dynamic light scattering (DLS) was 24 nm, the dispersion stability was "○", and the surface modification rate was 80%.

[0304] Next, using this sol, a cured film was prepared following the same steps as in film evaluation A-1.

[0305] The resulting cured film had a transparency rating of "○" and a UV resistance rating of "○". Additionally, when evaluating the imprintability using this coating solution, it was rated as "○".

[0306] (Example 6)

[0307] In 100 g of the aqueous dispersion sol of zirconium oxide-tin oxide composite oxide colloidal particles (A3) obtained in Reference Example 4, 200 g of methanol and 2.0 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a surface modifier were added under stirring, and the mixture was refluxed at 65°C for 5 hours to modify the particle surface. Next, the dispersion medium was replaced with PGME using a rotary evaporator to prepare a PGME dispersion sol. The total metal oxide (ZrO2, SnO2, and SiO2) concentration of this surface-modified PGME dispersion sol was 20.5% by mass, the average particle size (dynamic light scattering particle size) obtained by dynamic light scattering (DLS) was 12 nm, the dispersion stability was "○", and the surface modification rate was 70%.

[0308] Next, using this sol, a cured film was prepared following the same steps as in film evaluation A-1.

[0309] The resulting cured film had a transparency rating of "○" and a UV resistance rating of "○". Additionally, when evaluating the imprintability using this coating solution, it was rated as "○".

[0310] (Example 7)

[0311] Except that, in Example 1, the colloidal particles were changed to (C2) obtained in Manufacturing Example 2, the amount of surface modifier X-12-1333A added was 3.1 g, and the displacement solvent was methyl ethyl ketone (hereinafter referred to as MEK), the sol was prepared in the same manner as in Example 1. At this time, the total metal oxide (TiO2, SnO2, ZrO2, and SiO2) concentration of the MEK dispersion sol was 30.5% by mass, the average particle size obtained by dynamic light scattering (DLS) was 14 nm, the dispersion stability was "○", and the surface modification rate was 70%.

[0312] (Comparative Example 1)

[0313] 10.0 g of TiO2 nanopowder (trade name Titanium(IV) oxide, rutile, <100 nm particle size, 99.5% trace metals basis) manufactured by Sigma-Aldrich Co., Ltd. was added to 23.3 g of methanol. Next, 2.0 g of product X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.4 g of pure water were added. The TiO2 nanopowder was surface modified by reflux heating at 65°C for 5 hours. Then, a PGMEA dispersion was prepared by replacing the dispersion medium with PGMEA using a rotary evaporator. The total metal oxide concentration of this surface-modified PGMEA dispersion was 20.5% by mass, the average particle size (dynamic light scattering particle size) obtained by DLS was 683 nm, the dispersion stability was "×", and the surface modification rate was 3%.

[0314] Next, using this dispersion, a cured membrane was prepared following the same steps as in membrane evaluation A-1.

[0315] The transparency of the resulting cured film is "×", and its UV resistance and imprintability cannot be evaluated.

[0316] (Comparative Example 2)

[0317] In Example 1, surface modification under the trade name X-12-1333A was not performed, and the methanol solvent was replaced with PGME. At this point, the total metal oxide (TiO2, SnO2, and SiO2) concentration of the PGME dispersion sol was 30.5% by mass, the average particle size obtained by dynamic light scattering (DLS) was 55 nm, the dispersion stability was "○", and the surface modification rate was 0%.

[0318] Next, using this sol, a cured film was prepared following the same steps as in film evaluation A-1.

[0319] The resulting cured film has a transparency rating of "○" and a UV resistance rating of "○". Furthermore, when evaluating the imprintability using this coating solution, it received a rating of "×".

[0320] (Comparative Example 3)

[0321] Except that in Example 1, the surface modifier was 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503) g, and the displacement solvent was PGME, the sol was prepared in the same manner as in Example 1. At this time, the total metal oxide (TiO2, SnO2, and SiO2) concentration of the PGME-dispersed sol was 30.5% by mass, the average particle size obtained by dynamic light scattering (DLS) was 19 nm, the dispersion stability was "○", and the surface modification rate was 20%.

[0322] Next, using this sol, a cured film was prepared following the same steps as in film evaluation A-1.

[0323] The transparency of the resulting cured film is "×", and its UV resistance and imprintability cannot be evaluated.

[0324] (Comparative Example 4)

[0325] Except that, in Comparative Example 1, 10.0 g of SiO2 powder (trade name AEROSIL 130) manufactured by Aerosil Co., Ltd. of Japan was used instead of the particles, a dispersion was prepared in the same manner as in Comparative Example 1. The total metal oxide concentration of this surface-modified PGMEA dispersion was 20.5% by mass, the average particle size (dynamic light scattering particle size) obtained by dynamic light scattering (DLS) was 355 nm, the dispersion stability was "×", and the surface modification rate was 5%.

[0326] The results above show that instead of using powdered metal oxides, a combination of colloidal metal oxide particles and silanes containing multiple polymeric functional groups is used to create a composition with excellent preservation stability. The resulting film, when coated onto a substrate and cured, exhibits excellent transparency, UV resistance, and imprintability.

[0327] Industrial availability

[0328] A highly dispersible sol containing metal oxide particles and silanes containing multiple polymerizable functional groups is obtained, and varnishes containing thermosetting or photocurable resins using these are used in compositions applicable to nanoimprinting processes.

Claims

1. A metal oxide sol, comprising a silane compound and metal oxide particles, wherein, Silane compounds are represented by formula (1), In equation (1), R 1 Each independently represents an alkoxy, acyloxy, or halogen group, R 2 Each is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms, R 3 A is a hydrogen atom or a methyl group. 1 It is an alkylene group, A 2 A 3 and A 4 Each is independently a methylene or oxygen atom, A 2 A 3 and A 4 One of them is an oxygen atom, and n is an integer from 1 to 3.

2. The metal oxide sol as described in claim 1, wherein, Metal oxide particles are coated with silane compound (1).

3. The metal oxide sol as described in claim 1 or 2, wherein, A 2 and A 4 Methylene, A 3 It is an oxygen atom.

4. The metal oxide sol according to any one of claims 1 to 3, wherein, The average primary particle size of the metal oxide particles obtained by nitrogen adsorption is 5–100 nm, and the average particle size obtained by dynamic light scattering is 5–200 nm.

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

6. The metal oxide sol according to any one of claims 1 to 5, wherein, The metal oxide is selected from at least one 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 whose surfaces are coated with a metal oxide composition or content that is different from that of the core metal oxide particles. The core metal oxide particles, the coated metal oxide particles, or both contain photoactive metal oxides.

8. The metal oxide sol as described in claim 7, wherein, The aforementioned photoactive metal oxide particles (A) are core-shell type metal oxide particles whose surface is covered with metal oxide particles containing silicon dioxide, and contain more than 50 mol% titanium oxide in all metal oxides.

9. The metal oxide sol as described in claim 7 or 8, wherein, The metal oxide particles of the aforementioned core are particles of titanium oxide, zirconium oxide, tin oxide, titanium oxide-tin oxide composite oxide, zirconium oxide-tin oxide composite oxide, titanium oxide-zirconia composite oxide, or titanium oxide-zirconia-tin oxide composite oxide.

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

11. The metal oxide sol according to any one of claims 1 to 10, further comprising an additive a selected from at least one of silane compounds other than formula (1), organic acids and their salts, phosphate 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 a silane compound of formula (1) and an additive a.

13. The metal oxide sol as described in claim 11 or 12, wherein, Silane compounds other than those in formula (1) are silane compounds selected from at least one of formulas (2) to (4). In equation (2), R 11 Each of the following groups is an alkyl, haloalkyl, alkenyl, aryl, or has an organic group having a polyether group, epoxy group, (meth)acryloyl group, mercapto group, amino group, urea group, or cyano group and is bonded to a silicon atom via a Si-C bond: R 12 Each represents an alkoxy, acyloxy, or halogen group, and 'a' represents an integer from 1 to 3. In equations (3) and (4), R 13 and R 15 Each is an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and is bonded to silicon atoms via Si-C bonds, R 14 and R 16 Each represents an alkoxy, acyloxy, or halogen group; Y represents an alkylene, NH group, or oxygen atom; b is an integer from 1 to 3; c is an integer from 0 to 1; and d is an integer from 1 to 3.

14. The metal oxide sol of claim 11, wherein, The organic acid mentioned above is an organic acid selected from at least one of divalent aliphatic carboxylic acids, aliphatic hydroxycarboxylic acids, amino acids, and chelating agents. The divalent aliphatic carboxylic acid is selected from oxalic acid, malonic acid, and succinic acid. The aliphatic hydroxycarboxylic acid is selected from glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid. The amino acid is selected from glycine, alanine, valine, leucine, serine, and threonine. The chelating agent is selected from ethylenediaminetetraacetic acid, L-aspartic-N,N-diacetic acid, and diethylenetriaminepentaacetic acid.

15. The metal oxide sol of claim 11, wherein, The aforementioned phosphate ester is selected from at least one of formulas (5) to (7). In equations (5) to (7), X 1 X 2 and X 3 Each represents an alkylene group with 2 to 20 carbon atoms; f, h, and j each represent an integer from 1 to 100; e, g, and i each represent an integer from 1 to 3; Y 1 Y 2 and Y 3 Each represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, or a (meth)acryloyl group.

16. The metal oxide sol of claim 11, wherein, The surfactants mentioned above are anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, or silicone surfactants.

17. The metal oxide sol of claim 11 or 12, wherein, Amines are secondary or tertiary amines with a total number of carbon atoms ranging from 5 to 35.

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

19. A varnish comprising a metal oxide sol as claimed in any one of claims 1 to 18, and a thermosetting or photocurable resin.

20. The varnish as described in claim 19, used for nanoimprinting.

21. A method for manufacturing a metal oxide sol as described in any one of claims 1 to 18, comprising the following steps (i) to (iii): (i) Process: The aqueous solvent of the aqueous sol of the metal oxide particles is replaced with an alcohol having 1 to 4 carbon atoms and ether bonds. (ii) Step: The sol of metal oxide particles obtained in step (i) is mixed with the silane compound of formula (1). (iii) Step: The alcohol solvent of the sol of the metal oxide particles obtained in step (ii) is replaced with an organic solvent other than the alcohol mentioned above.

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