Silica particles for coating composition and laminated substrate

Abstract

[Problem] To provide: a coating composition that uses silica particles in which aluminum atoms are bonded to the surfaces of the silica particles at a specific ratio in terms of Al2O3; a laminated substrate that uses the coating composition; and a method for producing the laminated substrate. [Solution] Silica particles to be added to a coating composition contain aluminum atoms forming aluminosilicate sites on the silica particles, wherein the aluminum atoms, which are present in the whole silica particles measured by a dissolution method using a hydrofluoric acid aqueous solution, are bonded to the silica particles at a ratio of 120-50,000 ppm / SiO2 to 1 g of SiO2 of the silica particles in terms of Al2O3. In the silica particles, the ratio of the [specific surface area (C) obtained through the BET method (nitrogen gas adsorption method)] to the [specific surface area (D) converted using a transmission electron microscope] is 1.00-5.00.

Description

Silica particles for coating compositions and laminated substrates

[0001] The present invention relates to a coating composition using silica particles containing aluminum atoms, and a method for producing a laminated substrate.

[0002] Hollow silica particles have a silica shell and a space inside the shell, and due to their characteristics, they have properties such as a low refractive index, low thermal conductivity (thermal insulation), and electrical insulation. Hollow silica particles consist of a core corresponding to the hollow part and an outer shell that forms the outside of the core. An aqueous dispersion of hollow silica particles can be obtained by forming a silica layer on the outside of the core in an aqueous medium and then removing the core. For example, aluminum atoms are added to a dispersion of solid silica particles at a molar ratio of Al ２ O ３ / SiO ２ A method for producing an acidic silica sol has been disclosed in which an aqueous alkali aluminate solution is added at a ratio of 0.0006 to 0.004, and the resulting silica sol is heated at 80 to 250° C. to exchange the cations therein (see Patent Document 1).

[0003] A method for obtaining an aqueous solid silica sol by heating activated silicic acid obtained by cation-exchanging an aqueous alkali silicate solution containing aluminum atoms at 80 to 300°C, or a method for obtaining an aqueous solid silica sol by adding an alkali aluminate to an aqueous silica sol and heating the resulting mixture at 80 to 300°C. The method for obtaining an aqueous solid silica sol by these methods is to disperse aluminum-atom-containing silica particles having aluminosilicate sites on the surface of the silica solid particles in a nitrogen-containing solvent, and measure the aluminum atoms on the surface of the silica particles by a leaching method. ２ O ３ Converted to 800 to 20,000 ppm / SiO ２(See Patent Document 2.) A method for producing hollow silica sol has been disclosed in which a silane compound and an aluminum precursor are reacted with a template core consisting of micelles or reverse micelles of an organic polymer at a Si / Al molar ratio of 7 to 15 to produce core-shell particles having an aluminosilicate shell, which are then reacted with a basic or acidic aqueous solution to form pores in the shell (outer shell) and remove the core, followed by a hydrothermal reaction at 160 to 200°C (See Patent Document 3.)

[0004] Japanese Patent Publication No. 6-199515 International Publication No. 2022 / 097694 Korean Patent No. 10-1659709B1

[0005] Aluminum atoms are attached to the surface of the silica particles. ２ O ３ The present invention provides a coating composition using silica particles bonded at a specific ratio in terms of converted silica particles, a laminated substrate using the coating composition, and a method for producing the laminated substrate.

[0006] In a first aspect, the present invention provides silica particles for addition to a coating composition, the silica particles containing aluminum atoms forming aluminosilicate sites in the silica particles, and the aluminum atoms present in the entire silica particles as measured by dissolving the silica particles in an aqueous hydrofluoric acid solution are Al ２ O ３ Converted to SiO of silica particles ２ 120 to 50,000 ppm / SiO per 1 g ２ as a second aspect, the silica particles according to the first aspect, in which a ratio of [specific surface area (C) measured by the BET method (nitrogen gas adsorption method)] / [specific surface area (D) converted from data obtained by transmission electron microscopy] is 1.00 to 5.00; as a third aspect, the silica particles according to the first aspect, in which a ratio of [specific surface area (C) measured by the BET method (nitrogen gas adsorption method)] / [specific surface area (D) converted from data obtained by transmission electron microscopy] is 1.40 to 5.00; as a fourth aspect, the SiO ２The silica particles according to any one of the first to third aspects, wherein the silica particles have a surface charge amount of 5 to 250 μeq / g calculated per 1 g of the silica particles. As a fifth aspect, the silica particles further comprise a compound represented by formula (1), formula (2), or formula (3): (In formula (1), R １ are each an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxyl group, a protected carboxyl group, a carboxyl group-generating group, or a cyano group, and are bonded to a silicon atom by a Si—C bond, and R ２ represents an alkoxy group, an acyloxy group, a hydroxyl group, or a halogen group, and a represents an integer of 1 to 3. In formulas (2) and (3), R ３ and R ５ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, and R ４ and R ６ each represents an alkoxy group, an acyloxy group, a hydroxyl group, or a halogen group; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer of 1 to 3; c is an integer of 0 or 1; and d is an integer of 1 to 3. as a sixth aspect, the silica particles according to any one of the first to fifth aspects, in which the film formed by the coating composition has a thickness of 1 to 30 μm; as a seventh aspect, the silica particles according to any one of the first to sixth aspects, in which the film formed by the coating composition has a transmittance of 90% or more; as an eighth aspect, the silica particles are derived from a sol in which the silica particles according to any one of the first to seventh aspects are dispersed in a dispersion medium, and have an average particle size of 20 to 150 nm as measured by a dynamic light scattering method; as a ninth aspect, the silica particles according to the eighth aspect, in which the dispersion medium is an alcohol, ketone, ether, amide, or ester having 1 to 10 carbon atoms; as a tenth aspect, the silica particles according to the eighth or ninth aspect, further containing an amine;

[0007] As an eleventh aspect, the silica particles according to the tenth aspect, wherein the amine is at least one amine selected from the group consisting of primary amines, secondary amines, and tertiary amines having 1 to 10 carbon atoms; as a twelfth aspect, the silica particles according to the tenth or eleventh aspect, wherein the amine is a water-soluble amine having a water solubility of 80 g / L or more; as a thirteenth aspect, the silica particles according to the tenth or eleventh aspect, wherein the content of the amine is such that the SiO ２the silica particles according to any one of the tenth to twelfth aspects, which are 0.001 to 10 mass% relative to the total mass of the silica particles; as a fourteenth aspect, the silica particles according to any one of the first to thirteenth aspects, which are redispersible in a developer containing an organic solvent or an alkaline aqueous solution; as a fifteenth aspect, the silica particles according to the fourteenth aspect, in which, when an organic solvent dispersion sol of the silica particles is dried under drying conditions of 60°C and 50 Torr and then redispersed in a developer containing an organic solvent or an alkaline aqueous solution, the average particle size of the silica particles in the developer as measured by a dynamic light scattering method is (particle size of the silica particles in the developer as measured by dynamic light scattering) / (particle size of the silica particles in the organic solvent as measured by dynamic light scattering)=0.5 to 4.0; as a sixteenth aspect, the silica particles according to the fourteenth or fifteenth aspect, in which the alkali component in the developer is an alkali metal hydroxide or a quaternary ammonium; and as a seventeenth aspect, the silica particles according to any one of the fourteenth to sixteenth aspects, in which the organic solvent component in the developer is an alcohol, a ketone, an ester, an amide, or a glycol. According to an eighteenth aspect, the silica particles are solid silica particles having no internal space, hollow silica particles having an internal space in an outer shell, or mixed silica particles of these particles. According to a nineteenth aspect, the silica particles are coating compositions containing the silica particles according to any one of the first to eighteenth aspects and a resin. According to a twentieth aspect, the coating composition is a polysiloxane-based resin, a polyacrylic-based resin, an epoxy-based resin, a thioepoxy resin, a novolac-based resin, a maleimide resin, a polyester-based resin, a polyamide-based resin, a polyimide-based resin, a polyhydroxyimide resin, a polybenzoxazole resin, a polybenzimidazole resin, a polybenzothiazole resin, a polyamic acid resin, a polyhydroxyamide resin, a polyhydroxyazomethine resin, a polyether-based resin, a polybenzoxazine resin, a polystyrene resin, a polyhydroxystyrene resin, a polyurethane resin, a polyurea resin, a condensation-based resin, or a combination thereof.

[0008] as a 21st aspect, a coating composition according to the 19th or 20th aspect, which contains a radical generator or an acid generator; as a 22nd aspect, a coating composition according to the 21st aspect, in which the coating composition is a resist composition; as a 23rd aspect, a method for producing a layered substrate, which includes step (i) of applying the coating composition according to any one of the 19th to 22nd aspects onto a substrate and drying it to form a coating film, and step (ii) of curing the coating film; as a 24th aspect, a method for producing a layered substrate according to the 23rd aspect, in which the curing in step (ii) is thermal curing, photocuring, or a combination thereof; as a 25th aspect, a method for producing a layered substrate according to the 23rd or 24th aspect, in which the curing in step (ii) is exposure performed on the coating film through a mask; as a 26th aspect, a method for producing a layered substrate according to any one of the 22nd to 25th aspects, further comprising a step (iii) of developing or planarizing after curing; as a 27th aspect, a method for producing a layered substrate according to the 26th aspect, in which the development or planarization is performed with an organic solvent or an alkaline aqueous solution; and According to a twenty-eighth aspect, there is provided a method for producing a laminated substrate including a multilayer film in which an upper layer film, a lower layer film, or a film is formed on both the coating film according to any one of the twenty-third to twenty-seventh aspects.

[0009] It is known that aluminosilicate sites generated by the reaction of aluminate ions with silanol groups on the surface of silica particles impart a negative charge to the silica particles in silica sol. Increasing the negative zeta potential of aluminosilicate sites improves their stability in the dispersion medium. This improves compatibility with organic solvents and charged resins in particular. Furthermore, by incorporating aluminum compounds into an acidic silicic acid solution and growing the particles, the aluminum compounds are encapsulated within the silica particles, and the alkali metals present within the silica particles are trapped within the silica particles, resulting in a stable silica sol. The alkali metals encapsulated within the silica particles are released outside the system over time, causing instability. Furthermore, because aluminosilicates are generated inside the silica particles, even in areas not required for stabilization, the amount of aluminum present in the aluminosilicate of the silica particles increases, and the amount of alkali metals bound to the aluminosilicate also increases, eventually leaching out of the silica particles over time. In solid silica particles without cavities within the silica particles, it is possible to form aluminosilicate sites near the surface by impregnating the silica particles with an aluminum compound from the surface after formation. Even if the aluminum compound penetrates to the center of the silica particle, sodium remains inside. In hollow silica particles with cavities inside the outer shell, the aluminum compound penetrates the outer shell when impregnated from the outside. However, the aluminum compound impregnated on the outside of the outer shell and the aluminum compound impregnated to the inside of the outer shell each form aluminosilicate sites, and alkali metals also exist that bond to them. While the alkali metals present in the aluminosilicate sites present on the outside of the outer shell can be removed during production, the alkali metals present in the aluminosilicate sites present on the inside of the outer shell are difficult to remove during production and may leak through the pores of the outer shell over time.The present invention aims to provide hollow silica particles that have aluminum atoms present on the outside of the outer shell of hollow silica particles, which can be measured by a leaching method, and aluminum atoms present inside the outer shell, which cannot be measured by a leaching method but are measured by a dissolution method using a hydrofluoric acid solution, but which have high dispersion stability in a medium and are free from concerns about alkali metal leakage, etc. When impregnating an aluminum compound from the outside after formation of the hollow silica particles, the hollow silica particles may be hydrothermally treated before impregnation to improve the density of the outer shell, and then the aluminum compound may be impregnated by heat treatment, or hollow silica particles that have not been hydrothermally treated beforehand may be impregnated by heat treatment with the aluminum compound. In both the former and latter cases, it is preferable that the aluminum atoms be present in a specific ratio relative to the silica. The silica particles of the present invention are contained in a coating composition, and after application to a substrate and drying, the silica particles are present in a coating film. The coating film is exposed to light through a mask and developed with a developer to form a pattern, and the substrate is then processed by etching with a chemical solution or gas. Furthermore, the above-mentioned coating film is itself a cured film after exposure without a mask, but in order to improve planarization, the surface layer of the cured film can be peeled off with a developer to achieve planarization. The present invention provides a coating composition that has good film performance when aluminum-containing silica particles are coated on a substrate as a coating composition to form a film.

[0010] 1 is a photograph of the membrane obtained in Example 10. FIG. 2 is a photograph of the membrane obtained in Comparative Example 1.

[0011] The present invention relates to silica particles to be added to a coating composition, the silica particles containing aluminum atoms forming aluminosilicate sites in the silica particles, and the aluminum atoms present in the entire silica particles are measured by dissolving the silica particles in a hydrofluoric acid aqueous solution, and the aluminum atoms are determined to be Al. ２ O ３ Converted to SiO of silica particles ２ 120 to 50,000 ppm / SiO per 1 g ２In the present invention, the silica particles may be solid silica particles with no internal space, hollow silica particles with internal space in the shell, or a mixture of these particles. In the present invention, the term "silica particles" used in the specification refers to solid silica particles, hollow silica particles, or a mixture of these particles.

[0012] Hollow silica particles have a silica shell and a space inside the shell. Hollow silica can be obtained by forming a shell mainly composed of silica on the surface of a part corresponding to the core, called a template, in a dispersion medium, and then removing the part corresponding to the core. In the present invention, aluminum atoms are measured by measuring aluminum present on the surface of silica particles by leaching silica particles with an aqueous solution of at least one mineral acid selected from the group consisting of sulfuric acid, nitric acid, and hydrochloric acid. ２ O ３ That is, the aluminum atoms measured by the leaching method are ２ O ３ Converted to SiO of silica particles ２ 100 to 20,000 ppm / SiO per 1 g ２ , or 100 to 15,000 ppm / SiO ２ , or 100 to 10,000 ppm / SiO ２ , or 100 to 3000 ppm / SiO ２ , or 200 to 5000 ppm / SiO ２ , or 400 to 5000 ppm / SiO ２ , or 800 to 3000 ppm / SiO ２ It is important for the silica particles to be dispersed in a solvent or resin that the aluminosilicate is present on the surface of the silica particles and forms aluminosilicate sites. When producing an acidic silica sol, it is desirable to increase the absolute value of the zeta potential of the silica particles in the acidic region. ２ Less than Al ２ O ３ The stability of silica particles tends to decrease when the ratio (A) is 3000 ppm / SiO２ When the content is more than this amount, there is a tendency for the particle size after doping to increase over time compared to the particle size measured by dynamic light scattering (DLS particle size) before doping with aluminum atoms by the aluminum compound at the stage of the aluminum-containing hollow silica aqueous sol.

[0013] The aluminum atoms present on the surface of silica particles as aluminosilicate can be leached (eluted) in a structure similar to aluminum salt, aluminum oxide, or aluminum hydroxide by leaching (eluting) the silica particles with an aqueous solution of at least one mineral acid selected from the group consisting of sulfuric acid, nitric acid, and hydrochloric acid, and the aluminum atoms can be measured from the solution using an ICP emission spectrometer. ２ O ３ The pH can be expressed in terms of the total amount of aluminum compound dissolved in the silica particle. In particular, a method of leaching (elution) using an aqueous nitric acid solution is used. The aqueous nitric acid solution used for leaching can be used at a pH in the range of 0.5 to 4.0, 0.5 to 3.0, 0.5 to 2.0, or 1.0 to 1.5, and typically, an aqueous nitric acid solution with a pH of 1.0 can be used. For example, 100 mL of the above aqueous nitric acid solution is added to 1 g of silica, and the solution is kept at a temperature of 20 to 70°C or 40 to 60°C for 10 to 24 hours to elute the aluminum compound from the surface of the silica particles, which can then be used as an analytical sample.

[0014] In the present invention, the silica particle surface can be defined as the region where the aluminum compound can be eluted by the above-mentioned leaching. This can be done by evaporating the solvent from the silica sol, and then grinding the silica gel dried at 250°C to obtain silica powder. 20 mL of a nitric acid solution at pH 1.0 was added to 0.2 g of the silica powder, and the mixture was thoroughly shaken, kept in a thermostatic chamber at 50°C for 17 hours, and then centrifuged and filtered. The aluminum content in the filtrate was measured using an ICP emission spectrometer. ２ O ３ The aluminum content converted to 1000 ppm was divided by the mass of the silica powder to determine the amount of aluminum bound to the silica particle surface (Al ２ O ３ / SiO ２ ) (ppm).

[0015] Furthermore, even when aluminosilicate is formed on the surface of silica particles, depending on the manufacturing method, aluminosilicate may be selectively formed not only on the surface but also inside the silica particles. ２ O ３ Converted into SiO of hollow silica particles ２ (B) 120 to 50,000 ppm / SiO ２ , or 400 to 20,000 ppm / SiO ２ , or 400 to 10,000 ppm / SiO ２ , or 1000 to 5000 ppm / SiO ２ , or 1000 to 4000 ppm / SiO ２ , or 120 to 4000 ppm / SiO ２ When producing an acidic silica sol, it is desirable to increase the absolute value of the zeta potential of the silica particles in the acidic region. ２ Less than Al ２ O ３ The stability of silica particles tends to decrease when the ratio (B) is 4000 ppm / SiO ２ When the content is more than this amount, there is a tendency for the particle size after doping to increase over time compared to the particle size measured by dynamic light scattering (DLS particle size) before doping with aluminum atoms by the aluminum compound at the stage of the aluminum-containing hollow silica aqueous sol.

[0016] The ratio of aluminum present on the surface of the silica particle to the entire silica particle, that is, the ratio (A) / (B), can be set in the range of 0.001 to 1.0, or 0.01 to 1.0, or 0.1 to 1.0, or 0.3 to 1.0, or 0.4 to 1.0. The aluminum atoms present in the entire silica particle can be measured by dissolving the silica particle in a hydrofluoric acid aqueous solution, and the aluminum content can be determined. ２ O ３That is, the aluminum atoms present as aluminosilicate throughout the silica particles can be measured by dissolving them in a hydrofluoric acid solution using an ICP emission spectrometer. ２ O ３ The amount of aluminum atoms present on the silica particle surface can be calculated by converting the amount of aluminum atoms present on the silica particle surface into the amount of aluminum atoms present on the silica particle surface. The hydrofluoric acid solution can be used at a concentration of, for example, 48% by mass, and the amount of the hydrofluoric acid solution can be used as long as it is sufficient to dissolve the silica particles. In this way, aluminosilicate sites are formed on the silica particle surface, and the SiO ２ The amount of negative charge calculated per gram of the polymer is measured in the range of 5 to 250 μeq / g, or 5 to 150 μeq / g, or 5 to 100 μeq / g, or 25 to 150 μeq / g, or 25 to 100 μeq / g.

[0017] The silica particles can be obtained as a silica sol dispersed in a dispersion medium. A hollow silica sol can be obtained by dispersing silica particles in a dispersion medium, and the average particle diameter measured by dynamic light scattering is 20 to 150 nm. Hollow silica is obtained by forming a silica-based shell on the surface of a portion corresponding to the core, known as a template, in the dispersion medium, and then removing the portion corresponding to the core. In this state, the hollow silica aqueous sol is a hollow silica aqueous sol. The hollow silica aqueous sol obtained in this manner can be subjected to solvent substitution with an alcoholic solvent as an organic solvent. The alcoholic solvent is preferably an alcohol having 1 to 5 carbon atoms, which may have an ether bond, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, propylene glycol monomethyl ether, or propylene glycol monoethyl ether. Subsequently, the resulting particles can be coated with a silane compound, if desired, and then subjected to solvent substitution with another organic solvent.

[0018] In the present invention, examples of organic solvents include alcohols, ketones, ethers, esters, and amides having 1 to 10 carbon atoms. Alcohols having 1 to 10 carbon atoms are aliphatic alcohols, including primary alcohols, secondary alcohols, and tertiary alcohols. These alcohols can also be polyhydric alcohols, such as dihydric alcohols and trihydric alcohols. Examples of monohydric primary alcohols include methanol, ethanol, 1-propanol, 1-butanol, and 1-hexanol. Examples of monohydric secondary alcohols include 2-propanol, 2-butanol, cyclohexanol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Examples of monohydric tertiary alcohols include tert-butyl alcohol.

[0019] Examples of dihydric alcohols include methanediol, ethylene glycol, and propylene glycol. Examples of trihydric alcohols include glycerin. As the ketone having 1 to 10 carbon atoms, an aliphatic ketone can be preferably used. Examples include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, and methyl cyclopentanone.

[0020] As the ether having 1 to 10 carbon atoms, an aliphatic ether can be preferably used. Examples include dimethyl ether, ethyl methyl ether, diethyl ether, tetrahydrofuran, and 1,4-dioxane. As the ester having 1 to 10 carbon atoms, an aliphatic ester can be preferably used. Examples include methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl acrylate, ethyl acrylate, propyl acrylate, dimethyl maleate, diethyl maleate, dipropyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, and γ-butyrolactone.

[0021] Examples of the amide include N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, dimethylacrylamide, acryloylmorpholine, diethylacrylamide, N-methylpyrrolidone, N-ethylpyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, etc. In the aqueous silica sol and organic solvent silica sol, which are the raw materials, the hollow silica particles can have an average particle size, as measured by dynamic light scattering (DLS), in the range of 5 to 150 nm, 20 to 150 nm, 30 to 150 nm, 40 to 150 nm, 50 to 150 nm, 50 to 120 nm, or 50 to 100 nm. The average primary particle size as determined by observation with a transmission electron microscope can be in the range of 5 to 150 nm, or 20 to 150 nm, or 30 to 150 nm, or 40 to 150 nm, or 50 to 150 nm, or 50 to 120 nm, or 50 to 100 nm.

[0022] The specific surface area (C) measured by the BET method (nitrogen gas adsorption method) is 18 to 550 m ２ / g, or 18 to 200 m ２ / g, or 50 to 160 m２ / g, or 60 to 160 m ２ / g, or 70 to 160 m ２ / g, or 80 to 150 m ２ The specific surface area (D) calculated from the data obtained by a transmission electron microscope can be set to 5 to 150 nm or 18 to 136 m ２ / g, or 18 to 90 m ２ / g, or 18 to 68 m ２ / g, or 18 to 54 m ２ / g, or 18-27m ２ / g, or 18-23m ２ / g. The ratio of [specific surface area (C) measured by the BET method (nitrogen gas adsorption method)] to [specific surface area (D) converted from data obtained by transmission electron microscopy] can be set within the range of 1.00 to 5.00, or 1.40 to 5.00, or 1.40 to 3.50, or 1.50 to 3.00, or 1.50 to 2.80. When the value of (C) / (D) is close to 1.0, the silica particles are solid silica particles with no void space inside their outer shells, while when the value of (C) / (D) exceeds 1.0, the silica particles are hollow silica particles with void space inside their outer shells or solid silica particles with a partially or entirely porous particle surface.

[0023] The thickness of the shell of the hollow silica particles, as determined by observation with a transmission electron microscope, can be in the range of 3.0 to 15.0 nm, 4.0 to 12.0 nm, or 5.0 to 10.0 nm. The refractive index of the hollow silica particles can be in the range of 1.20 to 1.45, 1.20 to 1.40, or 1.25 to 1.40. The silica sol can be prepared by adding SiO ２ The particle concentration is 1 to 50% by mass, or 5 to 40% by mass, and typically 10 to 30% by mass.

[0024] The pH of the sol can be adjusted from acidic to alkaline. Adjustment to acidity is achieved by adding an inorganic or organic acid. Adjustment to alkalinity is achieved by adding an inorganic or organic base, and amines can be added as organic bases to adjust the pH and surface charge. The pH can be set to 1 to less than 7 on the acidic side, or 7 or more but not more than 13 on the alkaline side. Before adding the amine, the aqueous silica sol can be set to a pH range of 2.0 to 6.0 or 2.0 to 4.5, for example. By adding the amine, the pH can be adjusted to a range of 3.0 to 10.0 or 3.0 to 9.0, for example. In the case of an organic solvent sol, the pH is measured when the organic solvent sol and an equal mass of pure water are mixed at a 1:1 ratio. The organic solvent can be measured when a water-miscible organic solvent is used. However, if the solvent is subsequently replaced with a hydrophobic organic solvent, it is preferable to measure the pH in advance at the methanol solvent sol stage.

[0025] For example, when the dispersing medium is a hydrophilic organic solvent, such as methanol sol or propylene glycol monomethyl ether sol, the measurement can be performed using a solution prepared by mixing pure water and the sol at a mass ratio of 1:1. When the dispersing medium is a hydrophobic organic solvent, such as methyl ethyl ketone sol, the measurement can be performed using a solution prepared by mixing pure water, methanol, and methyl ethyl ketone sol at a mass ratio of 1:1:1. Silica organic solvent sols undergo solvent substitution, where the aqueous medium is replaced with an alcohol solvent having 1 to 5 carbon atoms, and then with an organic solvent, but moisture can remain during this process. At the stage of hollow silica or solid silica alcohol sol, the sol can contain, for example, 0.1 to 3.0 mass% or 0.1 to 1.0 mass% residual moisture. Furthermore, at the stage of hollow silica or solid silica organic solvent sol (where the dispersing medium is an organic solvent other than alcohol), the sol can contain 0.01 to 0.5 mass% residual moisture. Furthermore, the viscosity of silica organic solvent sols can be set in the range of 1.0 to 10.0 mPa·s.

[0026] An amine can be added to the silica sol of the present invention. The amine used in the present invention can be a water-soluble amine having a water solubility of 80 g / L or more, or 100 g / L or more. The raw material silica aqueous sol and the organic solvent silica sol obtained by solvent substitution can contain an amine, or an amine and ammonia. The amine can be used to dissolve the SiO of the hollow silica particles. ２ The amine, or the amine and ammonia, can be added and contained in an amount of 0.001 to 10 mass%, or 0.01 to 10 mass%, or 0.1 to 10 mass%, based on the total mass of the amine or the amine and ammonia. The amount of these basic components in the silica particle organic solvent sol can be expressed as the total nitrogen amount, and can be contained in a range of, for example, 10 to 100,000 ppm, or 100 to 10,000 ppm, or 100 to 3,000 ppm, or 100 to 2,000 ppm, typically 200 to 2,000 ppm.

[0027] Examples of the amine include aliphatic amines and aromatic amines, with aliphatic amines being preferred. At least one amine selected from the group consisting of primary, secondary, and tertiary amines having 1 to 10 carbon atoms can be used. The amine is water-soluble and is at least one amine selected from the group consisting of primary, secondary, and tertiary amines having 1 to 10 carbon atoms. Examples of primary amines include monomethylamine, monoethylamine, monopropylamine, monoisopropylamine, monobutylamine, monoisobutylamine, monosec-butylamine, mono-tert-butylamine, monomethanolamine, monoethanolamine, monopropanolamine, monoisopropanolamine, monobutanolamine, monoisobutanolamine, monosec-butanolamine, and mono-tert-butanolamine.

[0028] Examples of secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, N-methylethylamine, N-ethylisobutylamine, dimethanolamine, diethanolamine, dipropanolamine, diisopropanolamine, N-methanolethylamine, N-methylethanolamine, N-ethanolisobutylamine, and N-ethylisobutanolamine. Examples of tertiary amines include trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, trisecbutylamine, tritertbutylamine, trimethanolamine, triethanolamine, tripropanolamine, triisopropanolamine, tributanolamine, triisobutanolamine, trisecbutanolamine, and tritertbutanolamine. The water solubility of the above amines is preferably 80 g / L or more, or 100 g / L or more. As these amines, primary amines and secondary amines are preferred, and secondary amines are preferably used due to their low volatility and high solubility, and examples thereof include diisopropylamine and diethanolamine.

[0029] In the present invention, the amine is contained, and thus the SiO of the silica particles is reduced. ２ The surface charge amount calculated per 1 g of silica particles can be set to 5 μeq / g or more, or 25 μeq / g or more. Typically, it can be set in the range of 5 to 250 μeq / g, or 25 to 250 μeq / g, or 25 to 100 μeq / g, or 25 to 80 μeq / g. In the present invention, the surface charge amount of the silica particles can be adjusted to any desired surface charge amount by adjusting the type and amount of the amine mentioned above.

[0030] In the present invention, the surface of silica particles can be coated with a silane compound. The silane compound can be a hydrolyzate of at least one silane compound selected from the group consisting of formulas (1) to (3). In formula (1), R １are each an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having a polyether group, an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a carboxyl group, a protected carboxyl group, a carboxyl group-generating group, or a cyano group, and are bonded to a silicon atom by a Si—C bond, and R ２ represents an alkoxy group, an acyloxy group, a hydroxyl group, or a halogen group, and a represents an integer of 1 to 3. In formulas (2) and (3), R ３ and R ５ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, and R ４ and R ６ each represents an alkoxy group, an acyloxy group, a hydroxyl group, or a halogen group; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer of 1 to 3; c is an integer of 0 or 1; and d is an integer of 1 to 3.

[0031] The alkyl group is an alkyl group having 1 to 18 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl- n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group , 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples include, but are not limited to, 3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and the like.

[0032] The alkylene group may be an alkylene group derived from the alkyl group described above. The aryl group is an aryl group having 6 to 30 carbon atoms, such as a phenyl group, a naphthyl group, an anthracene group, or a pyrene group.

[0033] The alkenyl group is an alkenyl group having 2 to 10 carbon atoms, and examples thereof include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3 ...2-butenyl, 1-methyl-3-butenyl, 2-methyl-2-propenyl, 2-methyl-3-butenyl, 3-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-2-propenyl, 2-methyl-3-butenyl, 3-n-propylethenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-n-propylethenyl Examples of alkyl groups include, but are not limited to, 1-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, and 2-methyl-2-pentenyl group.

[0034] The alkoxy group includes alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, and n-hexyloxy, but is not limited to these. Examples of the acyloxy group having 2 to 10 carbon atoms include, but are not limited to, a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, an n-butylcarbonyloxy group, an i-butylcarbonyloxy group, an s-butylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, a 1-methyl-n-butylcarbonyloxy group, a 2-methyl-n-butylcarbonyloxy group, a 3-methyl-n-butylcarbonyloxy group, a 1,1-dimethyl-n-propylcarbonyloxy group, a 1,2-dimethyl-n-propylcarbonyloxy group, a 2,2-dimethyl-n-propylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, an n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, and a 2-methyl-n-pentylcarbonyloxy group. The halogen group includes fluorine, chlorine, bromine, iodine, and the like.

[0035] The organic group having a polyether group includes a polyetherpropyl group having an alkoxy group. For example, (CH ３ O) ３ SiC ３ H ６ (OC ２ H ４ ) nOCH ３ n can be in the range of 1 to 100 or 1 to 10.

[0036] An example of an organic group having a carboxyl group is a silane coupling agent in which four hydrogen atoms of a disiloxane are replaced by hydroxyl groups and two hydrogen atoms are replaced by carboxyl groups or an organic group containing a carboxyl group. Examples include a compound of formula (1-1) in which two carboxyl group structures are bonded to a tetrahydroxydisiloxane skeleton, such as the product name X-12-1135 manufactured by Shin-Etsu Chemical Co., Ltd.

[0037] Examples of protected carboxyl groups and carboxyl group-generating groups include silane coupling agents having a carboxylic acid ester structure. Silane coupling agents containing an organic group containing a carboxylic acid ester group include alkyl esters, aryl esters, and arylalkyl esters in the ester moiety. For example, alkyl groups include linear or branched alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 40 carbon atoms. Arylalkyl groups include structures in which an alkylene group having 1 to 10 carbon atoms is bonded to an aryl group having 6 to 40 carbon atoms. Examples of the structure of these ester moieties include a methyl carboxylate structure, a t-butyl carboxylate structure, and a benzyl carboxylate structure. Furthermore, the carboxylic acid ester moiety and the alkoxysilyl group are connected by an alkylene group, and examples of such alkylene groups include alkylene groups having 1 to 10 carbon atoms, which may contain a heteroatom. Examples of heteroatoms include nitrogen atoms and oxygen atoms, such as NH groups and O groups. The carboxylic acid ester moiety undergoes hydrolysis to form a carboxylic acid, and if the heteroatom contains a nitrogen atom, it forms an amino acid. Organic groups containing a carboxylic acid ester group can be used as amino acid generators. For example, the product represented by formula (1-2) and manufactured by Shin-Etsu Chemical Co., Ltd., product name X-88-475, can be used. The amino acid structure may have a urea structure or a urethane structure to protect the amine moiety. The protected carboxyl group and carboxyl group-generating group can be prepared by reacting a compound having a protected carboxyl group and a carboxyl group-generating group at the respective terminals with a compound having an alkoxysilane moiety using an organic group such as an amine group, a hydroxyl group, or an isocyanate to produce the desired compound.

[0038] Examples of organic groups having an epoxy group include a 2-(3,4-epoxycyclohexyl)ethyl group and a 3-glycidoxypropyl group. The (meth)acryloyl group refers to both an acryloyl group and a methacryloyl group. Examples of organic groups having a (meth)acryloyl group include a 3-methacryloxypropyl group and a 3-acryloxypropyl group. Examples of organic groups having a mercapto group include a 3-mercaptopropyl group.

[0039] Examples of organic groups having an amino group include a 2-aminoethyl group, a 3-aminopropyl group, an N-2-(aminoethyl)-3-aminopropyl group, an N-(1,3-dimethyl-butylidene)aminopropyl group, an N-phenyl-3-aminopropyl group, and an N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group. An example of an organic group having a ureido group includes a 3-ureidopropyl group. An example of an organic group having a cyano group includes a 3-cyanopropyl group. The above formulas (2) and (3) are preferably compounds capable of forming trimethylsilyl groups on the surface of silica particles.

[0040] Examples of such compounds include the following. In the above formula, R １２ is an alkoxy group, for example, a methoxy group or an ethoxy group. As the silane compound, a silane compound manufactured by Shin-Etsu Chemical Co., Ltd. can be used. This is a process in which the silane compound reacts with a hydroxyl group on the surface of silica particles, for example, a silanol group in the case of silica particles, to coat the surface of the silica particles with the silane compound through a siloxane bond. The reaction temperature can be from 20°C to the boiling point of the dispersion medium, but can be in the range of 20°C to 100°C, for example. The reaction time can be about 0.1 to 10 hours.

[0041] The silane compound is applied to the surface of the silica particles in such an amount that the number of silicon atoms in the silane compound is 0.1 / nm ２ ~20.0 pieces / nm ２The silica particle surfaces can be coated by adding a silane compound equivalent to the coating amount to the silica sol. Water is required for the hydrolysis of the silane compound, and if the sol is an aqueous solvent, that aqueous solvent can be used. When the aqueous medium is replaced with an organic solvent, the water remaining in the solvent can be used. For example, water present in an amount of 0.01 to 5% by mass can be used. Furthermore, the hydrolysis can be carried out with or without a catalyst.

[0042] When the hydrolysis is performed without a catalyst, the silica particle surface is on the acidic side. When a catalyst is used, examples of the hydrolysis catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases. Examples of metal chelate compounds used as hydrolysis catalysts include triethoxy mono(acetylacetonato)titanium and triethoxy mono(acetylacetonato)zirconium. Examples of organic acids used as hydrolysis catalysts include acetic acid and oxalic acid. Examples of inorganic acids used as hydrolysis catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Examples of organic bases used as hydrolysis catalysts include pyridine, pyrrole, piperazine, and quaternary ammonium salts. Examples of inorganic bases used as hydrolysis catalysts include ammonia, sodium hydroxide, and potassium hydroxide. The organic acid is at least one organic acid selected from the group consisting of divalent aliphatic carboxylic acids, aliphatic oxycarboxylic acids, amino acids, and chelating agents. The divalent aliphatic carboxylic acids include oxalic acid, malonic acid, and succinic acid. The aliphatic oxycarboxylic acids include glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid. The amino acids include glycine, alanine, valine, leucine, serine, and threonine. The chelating agents include ethylenediaminetetraacetic acid, L-aspartic acid-N,N-diacetic acid, and diethylenetriaminepentaacetic acid. The organic acid salts include alkali metal salts, ammonium salts, and amine salts of the above organic acids. The alkali metal salts include sodium and potassium. The present invention provides a film-forming composition containing the above organic solvent sol of silica and an organic resin.

[0043] The organic resin may be a polysiloxane resin, a polyacrylic resin, an epoxy resin, a thioepoxy resin, a novolac resin, a maleimide resin, a polyester resin, a polyamide resin, a polyimide resin, a polyhydroxyimide resin, a polybenzoxazole resin, a polybenzimidazole resin, a polybenzothiazole resin, a polyamic acid resin, a polyhydroxyamide resin, a polyhydroxyazomethine resin, a polyether resin, a polybenzoxazine resin, a polystyrene resin, a polyhydroxystyrene resin, a polyurethane resin, a polyurea resin, a condensation resin, or a combination thereof. A film-forming composition can be obtained by selecting and mixing a thermosetting or photocurable organic resin. Furthermore, a curing agent such as an amine curing agent, an acid anhydride curing agent, a radical generator curing agent (thermal radical generator, photoradical generator), or an acid generator curing agent (thermal acid generator, photoacid generator) can be added to form a cured product.

[0044] This composition can form a cured product by applying or filling a film-forming composition containing an organic resin and a curing agent onto a substrate and then heating, irradiating with light, or a combination thereof. Examples of organic resins (curable resins) include resins having functional groups such as epoxy groups or (meth)acryloyl groups, and isocyanate-based resins. For example, photocurable multifunctional acrylates are preferably used. Examples of multifunctional acrylates include multifunctional acrylates having difunctional, trifunctional, tetrafunctional, or higher functional groups in the molecule, such as neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0045] These polyfunctional acrylates can also be described below.

[0046] The film-forming composition of the present invention can contain a surfactant (leveling agent). Examples of surfactants (leveling agents) that can be used include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and silicone surfactants. The surfactant (leveling agent) can be added in an amount of 0.01 to 5 phr or 0.01 to 1 phr relative to the organic resin. Examples of anionic surfactants that can be used in the present invention include sodium and potassium salts of fatty acids, alkylbenzene sulfonates, higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, α-sulfofatty acid esters, α-olefin sulfonates, monoalkyl phosphate esters, and alkanesulfonates.

[0047] For example, alkylbenzene sulfonates include sodium salts, potassium salts, and lithium salts, such as sodium C10-C16 alkylbenzene sulfonate, C10-C16 alkylbenzene sulfonic acid, sodium alkylnaphthalene sulfonate, etc. Higher alcohol sulfates include sodium dodecyl sulfate (sodium lauryl sulfate) with 12 carbon atoms, triethanolamine lauryl sulfate, triethanolammonium lauryl sulfate, etc.

[0048] Examples of polyoxyethylene alkyl ether sulfates include sodium polyoxyethylene styrenated phenyl ether sulfate, ammonium polyoxyethylene styrenated phenyl ether sulfate, sodium polyoxyethylene decyl ether sulfate, ammonium polyoxyethylene decyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, and sodium polyoxyethylene oleyl cetyl ether sulfate. Examples of α-olefin sulfonates include sodium α-olefin sulfonate. Examples of alkane sulfonates include sodium 2-ethylhexyl sulfate. Examples of cationic surfactants used in the present invention include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, and amine salts.

[0049] Alkyltrimethylammonium salts are quaternary ammonium salts that have chloride ions or bromide ions as counterions. Examples include dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, coconut alkyltrimethylammonium chloride, and alkyl(C16-18)trimethylammonium chloride. Dialkyldimethylammonium salts have two lipophilic main chains and two methyl groups. Examples include bis(hydrogenated tallow)dimethylammonium chloride. Examples include didecyldimethylammonium chloride, dicocoalkyldimethylammonium chloride, dihydrogenated tallow alkyldimethylammonium chloride, and dialkyl(C14-18)dimethylammonium chloride. Alkyldimethylbenzylammonium salts are quaternary ammonium salts that have one lipophilic main chain, two methyl groups, and a benzyl group, and examples include benzalkonium chloride. Examples include alkyl(C8-18)dimethylbenzylammonium chloride. Amine salt agents are those in which the hydrogen atoms of ammonia have been substituted with one or more hydrocarbon groups, and examples thereof include N-methylbishydroxyethylamine fatty acid ester hydrochloride.

[0050] Examples of amphoteric surfactants that can be used in the present invention include N-alkyl-β-alanine-type alkylamino fatty acid salts, alkylcarboxybetaine-type alkylbetaines, and N,N-dimethyldodecylamine oxide-type alkylamine oxides. Examples of these include lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, and lauryldimethylamine oxide. Examples of nonionic surfactants that can be used in the present invention include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, alkyl glucosides, polyoxyethylene fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and fatty acid alkanolamides. For example, examples of polyoxyethylene alkyl ethers include polyoxyethylene dodecyl ether (polyoxyethylene lauryl ether), polyoxyalkylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyalkylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene behenyl ether, polyoxyethylene-2-ethylhexyl ether, and polyoxyethylene isodecyl ether.

[0051] Examples of polyoxyethylene alkylphenol ethers include polyoxyethylene styrenated phenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene distyrenated phenyl ether, and polyoxyethylene tribenzyl phenyl ether. Examples of alkyl glucosides include decyl glucoside and lauryl glucoside. Examples of polyoxyethylene fatty acid esters include polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyethylene glycol distearate, polyethylene glycol dioleate, and polypropylene glycol dioleate.

[0052] Sorbitan fatty acid esters include sorbitan monocaprylate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monosesquioleate, and ethylene oxide adducts thereof. 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. Fatty acid alkanolamides include coconut oil fatty acid diethanolamide, beef tallow fatty acid diethanolamide, lauric acid diethanolamide, and oleic acid diethanolamide. Further examples include polyoxyalkyl ethers or polyoxyalkyl glycols such as polyoxyethylene polyoxypropylene glycol and polyoxyethylene fatty acid esters, polyoxyethylene hydrogenated castor oil ether, sorbitan fatty acid ester alkyl ether, alkyl polyglucoside, sorbitan monooleate, and sucrose fatty acid ester.

[0053] Silicone surfactants can be used. Silicone surfactants are compounds with repeating units containing siloxane bonds in the main chain. Silicone surfactants can be used with a weight-average molecular weight in the range of 500 to 50,000. These may be modified silicone surfactants, and examples include structures in which organic groups are introduced into the side chains and / or terminals of polysiloxane. Examples of organic groups include amino groups, epoxy groups, alicyclic epoxy groups, carbinol groups, mercapto groups, carboxyl groups, aliphatic ester groups, aliphatic amide groups, and polyether groups. Examples of silicone surfactants include trade names such as Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), Silwet 1-77, L-7280, L-7001, L-7002, L-7200, L-7210, L-7220, L-7230, L7500, L-7600, L-7602, L-7604, L-7605, L-7622, ​​L-765 7, L-8500, and L-8610. (all manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Silicones Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie), etc. For example, a polyether-modified silicone under the trade name L-7001 (manufactured by Dowsil Industries) can be suitably used.

[0054] The present invention provides a film-forming composition containing the organic solvent sol and an organic resin. The film-forming composition can be obtained by removing the organic solvent from the organic solvent sol to obtain a film-forming composition containing silica particles and an organic resin. In the case of a thermosetting film-forming composition, the heat curing agent can be added in a range of 0.01 to 50 phr, or 0.01 to 10 phr, relative to the resin containing a functional group such as an epoxy group or a (meth)acryloyl group. For example, the heat curing agent can be added in a ratio of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, relative to the functional group such as an epoxy group or a (meth)acryloyl group. The equivalent of the heat curing agent relative to the curable resin is expressed as the equivalent ratio of the heat curing agent to the functional group.

[0055] Examples of heat curing agents include phenolic resins, amine-based curing agents, polyamide resins, imidazoles, polymercaptans, acid anhydrides, thermal radical generators, and thermal acid generators. Radical generator-based curing agents, acid anhydride-based curing agents, and amine-based curing agents are particularly preferred. These solid heat curing agents can be used by dissolving them in a solvent, but evaporation of the solvent can reduce the density of the cured product and create pores, resulting in reduced strength and reduced water resistance. Therefore, it is preferable for the curing agent itself to be liquid at room temperature and normal pressure. Examples of phenolic resins include phenol novolac resins and cresol novolac resins.

[0056] Examples of amine curing agents include piperidine, N,N-dimethylpiperazine, triethylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthenediamine, isophoronediamine, diaminodicyclohexylmethane, 1,3-diaminomethylcyclohexane, xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and diethyltoluenediamine. Of these, liquids such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthenediamine, isophoronediamine, diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and diethyltoluenediamine can be preferably used.

[0057] The polyamide resin is produced by condensation of dimer acid and polyamine, and is a polyamidoamine having a primary amine and a secondary amine in the molecule. Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and epoxy imidazole adduct. The polymercaptan is, for example, one having a mercaptan group at the end of a polypropylene glycol chain or one having a mercaptan group at the end of a polyethylene glycol chain, and is preferably liquid.

[0058] As the acid anhydride curing agent, the anhydride of the compound having a plurality of carboxyl groups in one molecule is preferred.These acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, chlorendic anhydride etc.

[0059] The thermal acid generator may be a sulfonium salt or a phosphonium salt, but a sulfonium salt is preferably used. For example, the following compounds can be mentioned:

[0060] R may be an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, with an alkyl group having 1 to 12 carbon atoms being particularly preferred. Among these, the following are preferred, which are liquid at room temperature and normal pressure: methyltetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride (methylnadic anhydride, methylhimic anhydride), hydrogenated methylnadic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methylhexahydrophthalic anhydride, and a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride. These liquid acid anhydrides have a viscosity of about 10 mPa·s to 1,000 mPa·s when measured at 25°C. Examples of thermal radical generators include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylpropionate)dimethyl, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, and benzoyl peroxide. These are available from Tokyo Chemical Industry Co., Ltd.

[0061] Furthermore, when obtaining the cured product, a curing aid may be used in combination as appropriate. Examples of curing aids include organic phosphorus compounds such as triphenylphosphine and tributylphosphine; quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and methyltriphenylphosphonium diethyl phosphate; and quaternary ammonium salts such as 1,8-diazabicyclo(5,4,0)undecane-7-ene, salts of 1,8-diazabicyclo(5,4,0)undecane-7-ene and octylic acid, zinc octylate, and tetrabutylammonium bromide. These curing aids can be contained in a ratio of 0.001 to 0.1 parts by mass per part by mass of curing agent. A thermosetting varnish is obtained by mixing a resin, a curing agent, and, if desired, a curing aid. Mixing can be performed in a reaction vessel using a stirring blade or kneader. Mixing is performed by a heated mixing method at a temperature of 60°C to 100°C for 0.5 to 1 hour.

[0062] The resulting curable film-forming composition is a thermosetting coating composition and has an appropriate viscosity for use, for example, as a liquid encapsulant. Liquid thermosetting film-forming compositions can be prepared to any viscosity and can be used as transparent encapsulants for LEDs and the like by casting, potting, dispensing, printing, or other methods, allowing for partial encapsulation at any desired location. The liquid thermosetting composition is directly mounted on an LED or the like using the method described above, and then dried and cured to obtain a cured epoxy resin product. The thermosetting film-forming composition (thermosetting coating composition) is applied to a substrate and heated at a temperature of 80 to 200°C to obtain a cured product.

[0063] In the case of a photocurable resin composition in the above-mentioned film-forming composition, a photocuring agent (photoradical generator, photoacid generator) can be added in a range of 0.01 to 50 phr, or 0.01 to 10 phr, to a resin containing a functional group such as an epoxy group or a (meth)acryloyl group. For example, the photocuring agent (photoradical generator, photoacid generator) can be contained in a ratio of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, to the functional group such as an epoxy group or a (meth)acryloyl group. The equivalent of the photocuring agent to the curable resin is expressed as the equivalent ratio of the photocuring agent to the functional group. The photoradical generator is not particularly limited, as long as it generates radicals directly or indirectly upon irradiation with light.

[0064] Examples of photoradical generators include photoradical polymerization initiators such as imidazole compounds, diazo compounds, bisimidazole compounds, N-arylglycine compounds, organic azide compounds, titanocene compounds, aluminate compounds, organic peroxides, N-alkoxypyridinium salt compounds, and thioxanthone compounds. Examples of azide compounds include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, 4,4'-diazidochalcone, 4,4'-diazidodiphenyl sulfide, and 2,6-bis(4'-azidobenzal)-4-methylcyclohexanone. Examples of diazo compounds include 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzeneborofluoride, 1-diazo-4-N,N-dimethylaminobenzene chloride, and 1-diazo-4-N,N-diethylaminobenzeneborofluoride. Examples of bisimidazole compounds include 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetrakis(3,4,5-trimethoxyphenyl)1,2'-bisimidazole and 2,2'-bis(o-chlorophenyl)4,5,4',5'-tetraphenyl-1,2'-bisimidazole.Examples of titanocene compounds include dicyclopentadienyl-titanium-dichloride, dicyclopentadienyl-titanium-bisphenyl, dicyclopentadienyl-titanium-bis(2,3,4,5,6-pentafluorophenyl), dicyclopentadienyl-titanium-bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl-titanium-bis(2,4,6-trifluorophenyl), dicyclopentadienyl-titanium-bis(2,6-difluorophenyl), dicyclopentadienyl bis(methylcyclopentadienyl)-titanium-bis(2,3,4,5,6-pentafluorophenyl), bis(methylcyclopentadienyl)-titanium-bis(2,3,5,6-tetrafluorophenyl), bis(methylcyclopentadienyl)-titanium-bis(2,6-difluorophenyl), and dicyclopentadienyl-titanium-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl).

[0065] Further examples of the photoradical generator include 1,3-di(tert-butyldioxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(tert-butyldioxycarbonyl)benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone. These photoradical polymerization agents are available, for example, as Irgacure TPO (component: 2,4,6-trimethylbenzoyldiphenylphosphine oxide) (c1-1-1), manufactured by BASF, Omnirad 819 (component: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) (c1-1-2), manufactured by IGM RESINS, and Irgacure 184 (component: 1-hydroxycyclohexylphenyl ketone) (c1-1-3).

[0066]

[0067] The photoacid generator is not particularly limited as long as it generates an acid directly or indirectly upon irradiation with light. Specific examples of the photoacid generator include triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivative compounds, onium salts such as iodonium salts, sulfonium salts, phosphonium salts, and selenium salts, metallocene complexes, and iron arene complexes.

[0068] The onium salt used as the photoacid generator includes iodonium salts such as diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium mesylate, bis(p-tert-butylphenyl)iodonium tosylate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium Examples of the iodonium salt include bis(alkylphenyl)iodonium salts such as iodonium tetrafluoroborate, bis(p-tert-butylphenyl)iodonium chloride, bis(p-chlorophenyl)iodonium chloride, bis(p-chlorophenyl)iodonium tetrafluoroborate, and further bis(4-t-butylphenyl)iodonium hexafluorophosphate; alkoxycarbonylalkoxy-trialkylaryl iodonium salts (for example, 4-[(1-ethoxycarbonyl-ethoxy)phenyl]-(2,4,6-trimethylphenyl)-iodonium hexafluorophosphate); and bis(alkoxyaryl)iodonium salts (for example, bis(alkoxyphenyl)iodonium salts such as (4-methoxyphenyl)phenyliodonium hexafluoroantimonate).

[0069] Examples of sulfonium salts include triphenylsulfonium salts such as triphenylsulfonium chloride, triphenylsulfonium bromide, tri(p-methoxyphenyl)sulfonium tetrafluoroborate, tri(p-methoxyphenyl)sulfonium hexafluorophosphonate, tri(p-ethoxyphenyl)sulfonium tetrafluoroborate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, and triphenylsulfonium hexafluorophosphate; and sulfonium salts such as (4-phenylthiophenyl)diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl)diphenylsulfonium hexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluorophosphate, and (4-methoxyphenyl)diphenylsulfonium hexafluoroantimonate.

[0070] Examples of phosphonium salts include triphenylphosphonium chloride, triphenylphosphonium bromide, tri(p-methoxyphenyl)phosphonium tetrafluoroborate, tri(p-methoxyphenyl)phosphonium hexafluorophosphonate, tri(p-ethoxyphenyl)phosphonium tetrafluoroborate, 4-chlorobenzenediazonium hexafluorophosphate, benzyltriphenylphosphonium hexafluoroantimonate, etc. Examples of phosphonium salts include selenium salts such as triphenylselenium hexafluorophosphate, and metallocene complexes such as (η5 or η6-isopropylbenzene)(η5-cyclopentadienyl)iron(II) hexafluorophosphate.

[0071] The following compounds can also be used as photoacid generators.

[0072]

[0073]

[0074]

[0075] As the photoacid generator, sulfonium salt compounds and iodonium salt compounds are preferred. The anion species thereof is CF3SO3 － , C ４ F ９ SO3 － , C ８ F １７ SO3 － , camphorsulfonate anion, tosylate anion, BF4 － , PF6 － , AsF6 － and SbF6 － and the like. Anion species such as phosphorus hexafluoride and antimony hexafluoride, which exhibit strong acidity, are particularly preferred. The film-forming composition of the present invention may contain conventional additives as needed. Examples of such additives include pigments, colorants, thickeners, sensitizers, antifoaming agents, coatability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light resistance stabilizers, etc.), plasticizers, dissolution promoters, fillers, and antistatic agents. These additives may be used alone or in combination of two or more. Examples of methods for applying the film-forming composition of the present invention include flow coating, spin coating, spray coating, screen printing, casting, bar coating, curtain coating, roll coating, gravure coating, dipping, and slit coating.

[0076] In the present invention, the photo-coating composition (film-forming composition) can be applied to a substrate and cured by light irradiation. Heating can also be performed before or after light irradiation. The thickness of the coating film can be selected from a range of approximately 0.01 μm to 10 mm depending on the application of the cured product. For example, when used as a photoresist, the thickness can be approximately 0.05 to 10 μm (particularly 0.1 to 5 μm), when used as a printed wiring board, the thickness can be approximately 5 μm to 5 mm (particularly 100 μm to 1 mm), and when used as an optical thin film, the thickness can be approximately 0.1 to 100 μm (particularly 0.3 to 50 μm). When a transparent coating is obtained, the visible light transmittance of the coating can be 80% or more, or 90% or more, typically 90 to 96%.

[0077] When a photoacid generator is used, the light to be irradiated or exposed may be, for example, gamma rays, X-rays, ultraviolet light, or visible light, and is usually visible light or ultraviolet light, particularly ultraviolet light. The wavelength of the light is, for example, about 150 to 800 nm, preferably about 150 to 600 nm, and more preferably about 150 to 400 nm. The amount of irradiation light varies depending on the thickness of the coating film, but is, for example, about 2 to 20,000 mJ / cm. 2 , preferably 5 to 5000 mJ / cm 2 The light source can be selected depending on the type of light to be exposed. For example, in the case of ultraviolet light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a deuterium lamp, a halogen lamp, or laser light (e.g., a helium-cadmium laser or an excimer laser) can be used. Such light irradiation causes the curing reaction of the composition to proceed. When a thermal acid generator is used, or when a photoacid generator is used, heating of the coating film, which is optionally performed after light irradiation, is carried out at, for example, 60 to 350°C, preferably about 100 to 300°C. The heating time can be selected from the range of 3 seconds or more (e.g., about 3 seconds to 5 hours), for example, 5 seconds to 2 hours, preferably about 20 seconds to 30 minutes, and typically about 1 minute to 3 hours (e.g., about 5 minutes to 2.5 hours).

[0078] Furthermore, when forming a pattern or image (for example, when producing a printed wiring board, etc.), the coating film formed on the substrate may be subjected to pattern exposure. This pattern exposure may be performed by scanning with laser light or by irradiating with light through a photomask. The non-irradiated areas (unexposed areas) generated by such pattern exposure are developed (or dissolved) with a developer to form a pattern or image. Examples of the developer include aqueous alkaline solutions and organic solvents. Examples of aqueous alkaline 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, ethyltrimethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine.

[0079] The alkaline developer is generally an aqueous solution of 10% by weight or less, preferably a 0.1 to 3.0% by weight aqueous solution. Furthermore, alcohols or surfactants can be added to the developer, each of which is preferably added in an amount of 0.05 to 10 parts by weight per 100 parts by weight of the developer. Among these, a 0.1 to 2.38% by weight aqueous solution of tetramethylammonium hydroxide or ethyltrimethylammonium hydroxide can be used. Furthermore, the organic solvent used in the developer can be a common organic solvent, such as acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, ethyl lactate, or cyclohexanone. These can be used alone or in combination. In particular, propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, etc. can be preferably used.

[0080] In the present invention, an adhesion promoter can be added for the purpose of improving adhesion to the substrate after development. These adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; vinyltrichlorosilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, and 3-chloropropyltrimethoxysilane; Examples of adhesion promoters include silanes such as 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-(N-piperidinyl)propyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. These adhesion promoters can be used alone or in combination of two or more. The amount of these adhesion promoters added is typically 18% by mass or less, preferably 0.0008 to 9% by mass, and more preferably 0.04 to 9% by mass, based on the solid content.

[0081] The present invention may contain a sensitizer. Usable sensitizers include anthracene, phenothiazene, perylene, thioxanthone, and benzophenone thioxanthone. Further examples of sensitizing dyes include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, and pyrylium salt dyes. Anthracene sensitizers are particularly preferred. When used in combination with a cationic curing catalyst (radiation-sensitive cationic polymerization initiator), they dramatically improve sensitivity and also possess radical polymerization initiation capabilities. In hybrid systems that combine the cationic curing system and radical curing system of the present invention, the catalyst species can be simplified. Specific anthracene compounds that are effective include dibutoxyanthracene and dipropoxyanthraquinone. The amount of the sensitizer added is 0.01 to 20% by mass, preferably 0.01 to 10% by mass, based on the solid content. The composition of the present invention can be photocured or thermally cured using a photoradical generator, a thermal radical generator, a photoacid generator, or a thermal acid generator. When a photoacid generator or a thermal acid generator is used, for example, commonly used epoxy curing agents (e.g., amines or acid anhydrides) are not used, or even if they are used, the content of these agents is extremely small, thereby improving the storage stability of the composition.

[0082] The above composition has been found to be applicable to photocationic polymerization. It has a higher curing rate than conventional liquid epoxy compounds (e.g., alicyclic epoxy compounds with an epoxycyclohexyl ring). Because of its fast curing rate, it is possible to reduce the amount of acid generator added or use a weak acid generator. Reducing the amount of acid generator is important for preventing metal corrosion, as active acid species may remain even after UV irradiation. Because of its fast curing rate, thick films can be cured. UV curing is applicable to heat-sensitive materials (equipment). Thermosetting and photocuring materials using the film-forming composition of the present invention are characterized by fast curing, transparency, and minimal cure shrinkage, making them suitable for coating and bonding electronic components, optical components (anti-reflective coatings), and precision mechanical components. For example, it can be used to bond mobile phone and camera lenses, optical elements such as light-emitting diodes (LEDs) and semiconductor lasers (LDs), liquid crystal panels, biochips, camera lenses and prisms, magnetic parts in hard disks of computers and the like, pickups in CD and DVD players (the part that captures the optical information reflected from the disc), speaker cones and coils, motor magnets, circuit boards, electronic parts, and parts inside automobile engines.

[0083] As a hard coating material for surface protection of automobile bodies, lamps, electrical appliances, building materials, plastics, etc., it can be applied to, for example, automobile and motorcycle bodies, headlight lenses and mirrors, plastic eyeglass lenses, mobile phones, game consoles, optical films, ID cards, etc. As an ink material for printing on metals such as aluminum and plastics, it can be applied to cards such as credit cards and membership cards, switches for electrical appliances and office equipment, printing ink for keyboards, and inkjet printer ink for CDs, DVDs, etc. It can also be applied to a technology for curing resins in combination with 3D CAD to create complex three-dimensional objects, photolithography for manufacturing industrial product models, optical fiber coating, adhesives, optical waveguides, thick-film resists, etc.

[0084] Furthermore, the film-forming composition of the present invention is suitable for use as an insulating resin for electronic materials, such as anti-reflection films, semiconductor encapsulation materials, adhesives for electronic materials, printed wiring board materials, interlayer insulating film materials, and encapsulants for power modules, as well as for insulating resins used in high-voltage equipment, such as generator coils, transformer coils, and gas-insulated switchgear. The present invention also allows the coating composition to contain silica particles that are redispersible in developers containing organic solvents or aqueous alkaline solutions. Hollow silica particles can be soluble in developers based on the surface potential present on their surfaces, but by attaching organic functional groups to the surface, they can be selectively developable only with organic solvents or aqueous alkaline solutions. These organic functional groups can be achieved by coating the silica particles with a silane coupling agent, adding an amine to the silica sol, or adding a surfactant.

[0085] For example, when the developer is an organic solvent, hydrophobic functional groups such as alkyl groups and aryl groups exhibit redispersibility of the silica particles. These functional groups are preferably used in silane coupling agents having one hydrolyzable group (i.e., silane coupling agents having three organic groups), two hydrolyzable groups (i.e., silane coupling agents having two organic groups), or a combination thereof. It is also possible to combine a silane coupling agent having one hydrolyzable group with a silane coupling agent having two hydrolyzable groups, and the ratio of the silyl groups can be in the range of 1:3 to 1:1. Examples of alkyl groups include methyl, ethyl, and propyl groups, and examples of aryl groups include phenyl groups. Preferred examples of the silyl groups include methylphenylsilyl and trimethylsilyl groups. The silica particles can have 2 to 6 or 2 to 4 silyl groups per square nanometer. The organic solvent is an alcohol, a ketone, an ester, or a glycol, and examples thereof include methanol, acetone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, n-butyl acetate, and ethyl lactate.

[0086] For example, when the developer is an alkaline aqueous solution, C1-C3 alkyl groups, carboxyl groups, protected carboxyl groups, and amino acid ester groups (e.g., N-methylpropylamino propionate) exhibit redispersibility of the silica particles. These functional groups are provided by a silane coupling agent having one hydrolyzable group (i.e., a silane coupling agent having three organic groups), or a secondary amine (diisopropanolamine), or a tertiary amine (e.g., tripentylamine). The silica particles have 2 to 6, 2 to 4, or 1 to 2 silyl groups per square nanometer, but a single silyl group is acceptable to enhance solubility in alkaline aqueous solutions. The alkaline aqueous solution may be an alkali metal hydroxide or a quaternary ammonium, such as an aqueous solution of quaternary ammonium hydroxide (e.g., tetramethylammonium hydroxide, ethyltrimethylammonium hydroxide, etc.), or an aqueous solution of potassium hydroxide.

[0087] The solubility of the silica particles can be tested by drying an organic solvent dispersion sol of the silica particles under drying conditions of 60°C and 50 Torr, and then redispersing it in a developer containing an organic solvent or an alkaline aqueous solution, and the average particle size measured by dynamic light scattering in the developer can be (dynamic light scattering particle size of silica particles in developer) / (dynamic light scattering particle size of silica particles in organic solvent) = 0.5 to 4.0, or 0.5 to 2.0. If the silica particles do not redisperse in the developer, they will become a suspension in the developer, and the dynamic light scattering particle size (DLS particle size) may increase.

[0088] The method for producing a laminated substrate of the present invention can include step (i) of applying a coating composition to a substrate and drying it to form a coating film, and step (ii) of curing the coating film. The curing in step (ii) can be performed by thermal curing, photocuring, or a combination thereof. The curing in step (ii) can be performed by exposure to light through a mask on the coating film.

[0089] The above-mentioned method for producing a laminated substrate can further include a step (iii) of developing or planarizing the coating after curing. The development or planarization can be performed using an organic solvent or an alkaline aqueous solution. If the coating film is a resist film, the substrate can be processed by gas etching (dry etching) or developer etching (wet etching) after development. The above-mentioned coating film can be used to produce a laminated substrate including a multilayer film in which a film is formed on an upper layer, a lower layer, or both layers. The upper and lower layers can be formed into an anti-reflection film in which a low refractive index film and a high refractive index film are alternately stacked.

[0090] The coating composition contains silica particles and a resin, and the resin can be a polysiloxane resin, a polyacrylic resin, an epoxy resin, a thioepoxy resin, a novolac resin, a maleimide resin, a polyester resin, a polyamide resin, a polyimide resin, a polyhydroxyimide resin, a polybenzoxazole resin, a polybenzimidazole resin, a polybenzothiazole resin, a polyamic acid resin, a polyhydroxyamide resin, a polyhydroxyazomethine resin, a polyether resin, a polybenzoxazine resin, a polystyrene resin, a polyhydroxystyrene resin, a polyurethane resin, a polyurea resin, a condensation resin, or a combination thereof. These can be heat-cured, photo-cured, or a combination thereof, and can contain a radical generator or an acid generator (thermal acid generator, photo-acid generator). Among the above resins, polysiloxane resins, for example, can be obtained by hydrolysis of a silane compound followed by dehydration condensation. This hydrolysis and condensation can be achieved by adjusting the hydrolysis conditions of the silane coupling agent described above.

[0091] Silane compounds can be produced by combining tetrafunctional silanes (silane compounds having four hydrolyzable groups), trifunctional silanes (silane compounds having three hydrolyzable groups and one organic group), bifunctional silanes (silane compounds having two hydrolyzable groups and two organic groups), and monofunctional silanes (silane compounds having one hydrolyzable group and three organic groups). For example, polysiloxane resins can be produced by combining tetrafunctional silanes with trifunctional silanes. Examples of tetrafunctional silanes include tetraethoxysilane and tetramethoxysilane. Tetraethoxysilane is particularly preferred. Examples of trifunctional silanes include alkyl silanes such as methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, and decyltrimethoxysilane;

[0092] Aryl silanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyltrimethoxysilane, and phenylmethyltriethoxysilane; Vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; Epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; Styryl silanes such as p-styryltrimethoxysilane; Methacrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; Acrylic silanes such as 3-acryloxypropyltrimethoxysilane; Amine-based silanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxyirane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N,N-dimethylaminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; isocyanurate-based silanes such as tris-(trimethoxysilylpropyl)isocyanurate and diallyl(trimethoxysilylpropyl)isocyanurate; ureido-based silanes such as 3-ureidopropyltrialkoxysilane; mercapto-based silanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; Examples include isocyanate-based silanes such as 3-isocyanatepropyltriethoxysilane.

[0093] Examples of polysiloxane resins include polysiloxane resins obtained by copolymerizing tetraethoxysilane, methyltrimethoxysilane, and phenyltrimethoxysilane, and polysiloxane resins obtained by copolymerizing diallyl(trimethoxysilylpropyl)isocyanurate, tetraethoxysilane, methyltrimethoxysilane, and N,N-dimethylaminopropyltrimethoxysilane. The weight-average molecular weight of these linear or spherical polysiloxane resins can be set in the range of 1,000 to 100,000, or 1,000 to 5,000.

[0094] For example, the polysiloxane resin can be dissolved in a glycol solvent such as propylene glycol ethyl ether and mixed with silica particles at a blending ratio of 100 phr. The solvent can then be replaced with propylene glycol monomethyl ether at 50 Torr and 80°C to produce a varnish as a coating composition. The silica concentration in these coating compositions can be set to 1 to 30% by mass, 5 to 30% by mass, or 10 to 3% by mass. The particle diameter measured by dynamic light scattering in the coating composition can be set to 10 to 200 nm, 10 to 100 nm, or 30 to 90 nm. For example, when a transparent film substrate is used, the coating composition can be applied and dried by heating at 80 to 100°C for 1 to 60 minutes to obtain a laminated substrate having a film thickness of 0.1 to 100 μm, 0.1 to 30 μm, 1 to 10 μm, or 1 to 3 μm. The dielectric constant and dielectric loss tangent of these transparent film substrates can be measured.

[0095] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited in any way by the following examples. The abbreviations for compounds used in the following examples are as follows. (Solvent, developer) PGME: Propylene glycol monomethyl ether PGEE: Propylene glycol monoethyl ether PGMEA: Propylene glycol monomethyl ether acetate EL: Ethyl lactate DMAC: N-dimethylacetamide ACBu: Butyl acetate MeOH: Methanol AC: Acetone CHO: Cyclohexanone ETMAH: Ethyl methyl ammonium hydroxide NMP: N-methyl-2-pyrrolidone KOH: Potassium hydroxide MEK: Methyl ethyl ketone (Amines) TnPA: Tripentylamine DiPA: Diisopropylamine DiPEA: Diisopropylethylamine

[0096] (Silanes) MPDMS: methylphenyldimethoxysilane TMSO: hexamethyldisiloxane MTMS: methyltrimethoxysilane PTMS: phenyltrimethylsilane TEOS: tetraethoxysilane APS: 3-aminopropyltriethoxysilane M33TMOSPAP: methyl 3-((3-(trimethoxysilyl)propyl)amino)propanoate, manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-88-475 (Isocyanate compounds) AOI-VM: 2-acryloyloxyethyl isocyanate, manufactured by Resonac Corporation, trade name AOI-VM EICYA: ethyl isocyanatoacetate

[0097] The silica sols, particles, product names, and abbreviations used are as follows: (Water-dispersed silica sol, organic solvent-dispersed silica sol) Trade name Snowtex O-40: Water-dispersed silica sol with an average primary particle size of 22 nm (manufactured by Nissan Chemical Industries, Ltd., water-dispersed sol of solid silica particles) Trade name Snowtex MSH: Water-dispersed silica sol with an average primary particle size of 17 nm (manufactured by Nissan Chemical Industries, Ltd., water-dispersed sol of solid silica particles) Trade name HKT-A20-40: Water-dispersed silica sol with an average primary particle size of 40 nm (manufactured by Ningbo Dilat Co., Ltd., water-dispersed sol of hollow silica particles) Trade name PL-3: Water-dispersed silica sol with an average primary particle size of 35 nm (manufactured by Fuso Chemical Industries, Ltd., water-dispersed sol of solid silica particles) Trade name MT-ST: Methanol-dispersed silica sol with an average primary particle size of 12 nm (manufactured by Nissan Chemical Industries, Ltd., methanol-dispersed sol of solid silica particles) Product name MA-ST-L: Methanol-dispersed silica sol with an average primary particle size of 45 nm (manufactured by Nissan Chemical Industries, Ltd., methanol-dispersed sol of solid silica particles)

[0098] (Silica (SiO ２ ) Measurement of concentration) The silica concentration of the water-dispersed silica sol, organic solvent-dispersed silica sol, and dispersion of surface-modified silica particles was calculated by placing the silica sol or dispersion in a crucible, heating to remove the solvent, calcining at 1000°C, and weighing the calcination residue. (Measurement of composition concentration) The concentration of the composition was calculated by weighing out about 1.00 g into an aluminum cup, calcining at 200°C for 2 hours, and weighing the calcination residue.

[0099] (Method for measuring pH of water-dispersed silica sol) The pH of the water-dispersed silica sol was measured using a pH meter (manufactured by DKK Toa Corporation, product name: MM-43X). (Method for measuring pH of organic solvent-dispersed silica sol) The pH of the organic solvent-dispersed silica sol was measured using a pH meter (manufactured by DKK Toa Corporation, product name: MM-43X) for a liquid obtained by mixing a target sample containing organic solvent-dispersed silica sol with methanol and pure water in a mass ratio of 1:1:1.

[0100] (Water content) The water content contained in the dispersion of surface-modified silica particles and the silica sol during the production process thereof was measured by Karl Fischer titration using a Karl Fischer moisture meter (manufactured by Kyoto Electronics Manufacturing Co., Ltd., product name: MKA-610). (Organic solvent content) The organic solvent content in the dispersion of surface-modified silica particles was determined by gas chromatography (manufactured by Shimadzu Corporation, product name: GC-2014s). Gas chromatography conditions: Column: 3 mm x 1 m glass column Packing: Polarpack Q Column temperature: 130 to 230°C (heat increase 8°C / min) Carrier: N ２ 40 mL / min Detector: FID Injection volume: 1 μL Internal standard: acetonitrile was used.

[0101] (Measurement of Viscosity) The viscosity of the dispersion liquid during the surface-treated silica particle production process was measured at 25°C using an Ostwald viscometer (manufactured by Shibata Scientific Co., Ltd.). Ｎ２ Measurement of the specific surface area (S) of silica particles in a water-dispersed silica sol by nitrogen adsorption method Ｎ２ The specific surface area of ​​the water-dispersed silica sol was measured by removing water-soluble cations in the water-dispersed silica sol with a cation exchange resin (manufactured by The Dow Chemical Company, trade name: Amberlite IR-120B), drying the silica sol at 290°C to prepare a measurement sample, which was then measured using a nitrogen adsorption specific surface area measurement device (trade name: Monosorb, manufactured by Quantachrome Instruments Japan, LLC). (IR Measurement) A sample (surface treatment agent: a mixture of M33TMOSPAP, MEK, and AOI-VM, as described later in Synthesis Example 13, etc.) was applied to a silicon substrate, heated to 100°C for 10 minutes to remove the solvent, and then infrared absorption spectroscopy (instrument name: iS50FT-IR, manufactured by Thermo Fisher Scientific Co., Ltd.) was used to perform IR measurement (measurement range: 4000-400 cm) in transmission with 32 accumulations. －１ ) was performed. From the graph obtained by IR measurement, the IR peak position (cm －１ ) was obtained.

[0102] (Average primary particle diameter by nitrogen adsorption method) The average primary particle diameter by nitrogen adsorption method is calculated by dividing the specific surface area S Ｎ２ (m ２The average primary particle diameter (nm) measured by the nitrogen adsorption method was calculated in terms of spherical particles using the following formula: Ｎ２ (m ２ / g) (Dynamic Light Scattering Particle Diameter (Average Particle Diameter (nm) by DLS Method)) The average particle diameter (Z-average particle diameter) by DLS method was measured using a dynamic light scattering particle size measurement device (manufactured by Malvern Panalytical, product name: Zetasizer Nano). The dilution solvent used when measuring the average particle diameter by DLS method was the same solvent as the main component contained in the dispersion medium of the silica particle dispersion.

[0103] (Measurement of average primary particle diameter by TEM (transmission electron microscope)) Particles in the silica sol were photographed using a transmission electron microscope (manufactured by JEOL Ltd., trade name JEM-F200), and approximately 300 arbitrarily selected particles were binarized using an automatic image processing analyzer (manufactured by Nireco Corporation, trade name LUZEX' AP), and the diameter obtained by converting the projected area into a circle was measured as the average primary particle diameter (HEYWOOD diameter). (Measurement of the amount of aluminum (B) present in all silica particles / dissolution method) Accurately weighed silica sol was dried, treated with a hydrofluoric acid solution to remove the silica component, and the residue was dissolved in an aqueous nitric acid solution. The amount of aluminum in the resulting aqueous solution was measured using an ICP emission spectrometer, and the amount of aluminum present in all silica particles was determined as Al ２ O ３ Converted to SiO ２ per 1 g of (Al ２ O ３ (ppm) / SiO ２ ) was sought.

[0104] (Measurement of the amount of aluminum (A) bound to the silica particle surface / Leaching method) Cationic components in the silica sol were removed using an H-type cation exchange resin, and the dried product, from which the solvent was removed by heat treatment, was pulverized in a mortar and further treated at 250°C for 2 hours. 0.2 g of the obtained powder was placed in a polypropylene container (PP sampler bottle, 50 mL) containing 20 mL of 0.1 mol / L (N / 10) aqueous nitric acid solution, and vigorously shaken and mixed by hand. Next, ultrasonic treatment was performed for 10 minutes in an ultrasonic cleaner (manufactured by AS ONE, product name ASU CLEANER ASU-10M) to thoroughly blend the powder with the aqueous nitric acid solution. The powder was then placed in a 50°C thermostatic bath and maintained for 17 hours. Thereafter, the solution was cooled to 25°C and charged into a centrifugal ultrafiltration filter (trade name Amicon Ultra-15, molecular weight cutoff 10,000). The amount of aluminum in the filtrate obtained by centrifugation was measured using an ICP emission spectrometer. The amount of aluminum bound to the silica particle surface was determined as Al ２ O ３ Converted to SiO ２ per 1 g of (Al ２ O ３ (ppm) / SiO ２ ) was sought.

[0105] (Measurement of Surface Charge Amount of Silica Particles) Silica sol was added to 10 mL of methanol and diluted to a silica concentration of 0.5 mass %, to prepare a measurement sample. Using a particle charge meter (manufactured by Voith Turbo K.K., product name PCD-06), a 0.001 mol / L (N / 1000) DADMAC solution (manufactured by Voith Turbo K.K.) was used as a standard cation titrant to measure the titration value until the streaming potential of the measurement sample reached zero. The obtained titration value was divided by the mass of silica contained in the measurement sample, and the value converted to a value per 1 g of hollow silica particles was determined as the surface charge amount (μeq / g-SiO ２ ) where DADMAC represents poly(diallyldimethylammonium chloride).

[0106] (Synthesis Example 1) Synthesis of MeOH Dispersion Sol (a1) of Aluminum-Containing Hollow Silica Particles (1) Preparation of Aqueous Dispersion Sol (a) of Aluminum-Containing Hollow Silica Particles 2015 g of commercially available hollow silica aqueous sol HKT-A20-40 (trade name) was placed in a 3 L plastic container, and Al２ O ３ 169 g of diluted sodium aluminate diluted to a concentration of 1.0 mass % in terms of sodium sulfate was added dropwise over 1 minute, and then an aqueous sodium sulfate solution (Na ２ SO ４ 6 g of an aqueous solution (10% by mass concentration in terms of SiO ) was added dropwise, and the mixture was stirred for 30 minutes at a rotation speed of 600 rpm using a mechanical stirrer equipped with a glass stirring blade. Next, 800 g of this mixture was placed in a separable glass flask, heated at 80°C for 5 hours, and cooled to 25°C. Next, the mixture was passed through a column-packed cation exchange resin (product name: H-type Amberlite IR-120B) at a space velocity (SV) of 5 / hour, to obtain an aqueous dispersion sol (a) of aluminum-containing hollow silica particles. The physical properties of the obtained sol were measured, and the results showed that SiO ２ Concentration 16.9% by mass, pH 2.6, average particle size by DLS method 54 nm, specific surface area by BET method (C) 149 m ２ / g, the amount of aluminum bound to the particle surface (A) was 1500 ppm, and the amount of aluminum present in the entire silica particle was Al ２ O ３ Converted to SiO ２ The aluminum content (B) per 1 g of the powder was 1900 ppm, the (A / B ratio) was 0.79, the average primary particle diameter by TEM observation was 43 nm, and the TEM-converted specific surface area (D) was 63 m ２ / g, specific surface area ratio (C / D ratio) 2.4, particle refractive index 1.26, shell thickness 6.7 nm. (2) Preparation of MeOH dispersion sol (a1) of aluminum-containing hollow silica particles 118.3 g of the water dispersion sol (a) of aluminum-containing hollow silica particles was placed in a 300 mL recovery flask, and 15.0 g of methanol was further added. The pressure was reduced to 580 Torr in a rotary evaporator, and methanol substitution was carried out while heating at 120°C, to obtain MeOH dispersion sol (a1) of aluminum-containing hollow silica particles. The physical properties of the obtained sol were pH 3.7, average particle diameter by DLS method 64 nm, SiO ２ Concentration 24.2% by mass, water content 0.3% by mass, viscosity 1.9 mPa s, SiO of hollow silica particles ２ The surface charge amount calculated per gram of the powder was 59 μeq / g.

[0107] (Synthesis Example 2) Synthesis of MeOH-dispersed solid silica sol (a2) 14,000 g of Snowtex O-40 (trade name) was subjected to water substitution by ultrafiltration using MeOH, and the substitution was stopped when the water content reached 0.5% by mass, thereby obtaining a MeOH-dispersed solid silica sol. The physical properties of the obtained sol were SiO ２ Concentration: 40.6% by mass, water content: 0.5% by mass, viscosity: 5.4 mPa·s, average particle size by DLS method: 18 nm, amount of Na present in the entire silica particle: ２ SiO of silica converted to O ２ 2210 ppm / SiO per 1 g ２ The amount of sulfate ions present in the silica sol is expressed as SO ４ Converted to SiO ２ For 1g of SO ４ 0.7ppm / SiO ２ The amount of aluminum present in the entire silica particle was ２ O ３ Converted to SiO ２ 2500 ppm / SiO per 1 g ２ It was.

[0108] Synthesis Example 3 Synthesis of MeOH-dispersed solid silica sol (a3) ​​250 g of Snowtex MSH (trade name) was charged into a 300 mL SUS autoclave reactor and subjected to hydrothermal treatment at 230±10° C. for 2.5 hours. 100 g of the obtained sol was added with a 5% diluted sodium sulfate aqueous solution and dissolved in SO . ３ The resulting solution was added to a concentration of 20 to 50 ppm, mixed with 30 g of hydrogen-type strongly acidic cation exchange resin (trade name: Amberlite IR-120B), stirred for 30 minutes, and filtered to obtain 130 g of acidic silica sol (pH 3, SiO ２ Concentration 23% by mass, average primary particle diameter 28nm, Na ２ O: 344ppm, SO ３130 g of the acidic silica sol obtained above was placed in a 1 L evaporator equipped with a recovery flask, and then MeOH was gradually added while the flask was heated to 120°C at 550 Torr to distill off the water, thereby replacing the water dispersing medium with MeOH. When the water content of this dispersion liquid reached 2.0 mass % or less, the replacement was terminated, and after adding MeOH, SiO ２ After adjusting the amount to 30 parts by mass, 92 g of MeOH-dispersed silica sol (a3) ​​was obtained. ２ Concentration: 30.0 mass%, water content: 1.5 mass%, viscosity: 5.4 mPa·s, average particle size by DLS method: 48.3 nm, amount of Na present in the entire silica particle: ２ SiO of silica converted to O ２ 1700 ppm / SiO per 1 g ２ The amount of sulfate ions present in the silica sol is expressed as SO ４ Converted to SiO ２ 36 ppm / SiO per 1 g ２ The amount of aluminum present in the entire silica particle was ２ O ３ Converted to SiO ２ 470 ppm / SiO per 1 g ２ It was.

[0109] Synthesis Example 4 Synthesis of MeOH-Dispersed Silica Sol (a4) 100 g of PL-3 (trade name) was placed in a 500 mL eggplant-shaped flask-equipped evaporator, and then MeOH was gradually added while the flask was heated to 120°C at 580 Torr to distill off the water, thereby replacing the water dispersing medium with MeOH. When the water content of this dispersion liquid reached 2.0 mass% or less, the replacement was terminated, and MeOH was added and adjusted to 30 mass parts, to obtain 100 g of MeOH-dispersed silica sol (a3). The obtained sol contained SiO ２ The concentration was 30.0 mass%, the average particle size by DLS method was 69.1 nm, and the amount of Na present in the entire silica particles was ２ SiO of silica converted to O ２ 2210 ppm / SiO per 1 g ２ The amount of sulfate ions present in the silica sol is expressed as SO ４Converted to SiO ２ 0.7 ppm / SiO per 1 g ２ The amount of aluminum present in the entire silica particle was ２ O ３ Converted to SiO ２ 0.026 ppm / SiO per 1 g ２ It was.

[0110] Synthesis Example 5 Synthesis of Surface-Treated MeOH-Dispersed Solid Silica Sol (a5) 4.44 g of MTMS was added to a 500 mL recovery flask equipped with a condenser containing 200 g of MeOH-dispersed solid silica sol (a3). The mixture was then heated at 65°C for 3 hours while stirring with a magnetic stirrer to obtain the target sol. The SiO of the obtained sol ２ The concentration was 20.5% by mass, the average particle size measured by DLS was 48.5 nm, the pH was 3.43, the viscosity was 1.2 mPa·s, and the water content was 0.9% by mass. No sediment was observed, indicating good dispersibility.

[0111] Synthesis Example 6 Synthesis of Surface-Treated MeOH-Dispersed Hollow Silica Sol (a6) 1.35 g of TnPA diluted to 10% by mass with MeOH was added to a 500 mL recovery flask equipped with a condenser containing 200 g of MeOH-dispersed sol (a1). The mixture was then stirred with a magnetic stirrer at 25°C for 630 minutes to obtain the target sol. The obtained sol contained SiO ２ The concentration was 19.9% ​​by mass, the average particle size measured by DLS was 75.7 nm, the pH was 4.8, the viscosity was 0.9 mPa·s, and the water content was 1.1% by mass. No sediment was observed, and good dispersibility was demonstrated.

[0112] (Synthesis Example 7) Synthesis of surface-treated MeOH-dispersed solid silica sol (a7) 0.63 g of pure water, 50 g of MeOH, 0.05 g of DiPA, and 1.56 g of M33TMOSPAP were added to a 200 mL recovery flask equipped with a condenser containing 50 g of MT-ST. The mixture was then heated at 60°C for 3 hours while stirring with a magnetic stirrer to obtain the target sol. The SiO ２The concentration was 15.2% by mass, the average particle size measured by DLS was 17.3 nm, the pH was 10.4, the viscosity was 1.0 mPa·s, and the water content was 1.5% by mass. No sediment was observed, and good dispersibility was demonstrated.

[0113] (Synthesis Example 8) Synthesis of Surface-Treated MEK-Dispersed Hollow Silica Sol (a8) 1.27 g of PTMS was added to a 500 mL recovery flask equipped with a condenser containing 150 g of MeOH-dispersed sol (a1), and the mixture was heated at 65°C for 3 hours while stirring with a magnetic stirrer. MEK was then added to the mixture, and distillation was carried out while supplying MEK in an evaporator at a bath temperature of 80°C and a reduced pressure of 550 to 350 Torr, thereby replacing the solvent with MEK. MEK was then added to the mixture to obtain a sol of 20% by mass in terms of solid residue at 200°C, thereby obtaining the target sol. The SiO of the obtained sol ２ The concentration was 20.0% by mass, the average particle size measured by DLS was 67.8 nm, the pH was 3.4, the water content was 0.1% by mass, and the MeOH content was less than 0.1% by mass. No sediment was observed, and the dispersion was well-dispersed.

[0114] Synthesis Example 9 Synthesis of Surface-Treated MEK-Dispersed Hollow Silica Sol (a9) 50 g of MeOH-dispersed sol (a1) was placed in a 100 mL eggplant-shaped flask, and while stirring with a magnetic stirrer, 0.4 g of pure water, 7.5 g of MEK, and 0.60 g of MPDMS were added, and the mixture was heated to 60 ° C. and maintained for 3 hours. 0.87 g of TMSO was then added, and the mixture was heated to 60 ° C. and maintained for 3 hours. DiPA was then added so that the pH was 8.0 to 10.0, and the mixture was heated to 60 ° C. and maintained for 1 hour. The eggplant-shaped flask containing the resulting sol was then placed in a rotary evaporator, and distillation was carried out while supplying MEK at a bath temperature of 80 ° C. and a reduced pressure of 550 to 350 Torr. The dispersion medium was replaced with MEK, and the target sol was obtained. The resulting sol had an average particle size of 65.9 nm by DLS, a pH of 7.1, and SiO ２ The concentration was 19.1% by mass, the water content was 0.15% by mass, and the MeOH content was less than 0.1% by mass. No sediment was observed, and good dispersibility was demonstrated.

[0115] Synthesis Example 10 Synthesis of Surface-Treated MEK-Dispersed Solid Silica Sol (a10) 50 g of MA-ST-L was placed in a 100 mL eggplant-shaped flask, and while stirring with a magnetic stirrer, 7.5 g of MEK and 1.11 g of MPDMS were added, and the mixture was heated to 60°C and maintained for 3 hours. Next, 1.65 g of TMSO was added, and the mixture was heated to 60°C and maintained for 3 hours. Thereafter, DiPA was added so that the pH was 8.0 to 10.0, and the mixture was heated to 60°C and maintained for 1 hour. The eggplant-shaped flask containing the obtained sol was placed in a rotary evaporator, and distillation was performed while supplying MEK at a bath temperature of 80°C under a reduced pressure of 550 to 350 Torr, replacing the dispersion medium with MEK to obtain the desired sol. The obtained sol had an average particle size of 78.6 nm by DLS, a pH of 7.3, and SiO ２ The concentration was 42.7% by mass, the water content was less than 0.1% by mass, and the MeOH content was less than 0.1% by mass. No sediment was observed, and good dispersibility was demonstrated.

[0116] (Synthesis Example 11) Synthesis of Surface-Treated MEK-Dispersed Solid Silica Sol (a11) 50 g of MeOH-dispersed silica sol (a2) was placed in a 100 mL eggplant-shaped flask, and while stirring with a magnetic stirrer, 1.5 g of pure water and 2.45 g of PTMS were added, and the mixture was heated to 60 ° C. and maintained for 3 hours. Thereafter, DiPEA was added so that the pH was 7.0 to 9.0, and the mixture was heated to 62 ° C. and maintained for 1 hour. Thereafter, the eggplant-shaped flask containing the obtained sol was placed in a rotary evaporator, and distillation was carried out while supplying MEK at a bath temperature of 80 ° C. and a reduced pressure of 550 to 350 Torr, and the dispersion medium was replaced with MEK to obtain the desired sol. The obtained sol had an average particle size of 32.7 nm by DLS, a pH of 7.4, and SiO ２ The concentration was 40.7% by mass, the water content was 0.2% by mass, and the MeOH content was 0.4% by mass. No sediment was observed, and good dispersibility was demonstrated.

[0117] Synthesis Example 12 Synthesis of Polysiloxane (P1) 14.58 g of TEOS (70 mol% in total silane compounds), 3.57 g of MTMS (20 mol% in total silane compounds), 1.98 g of PTMS (10 mol% in total silane compounds), and 31 g of acetone were placed in a 200 mL flask, and while the mixed solution was stirred with a magnetic stirrer, 6.67 g of 0.01 mol / L hydrochloric acid was added dropwise thereto. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C., and the reaction was allowed to proceed for 240 minutes under heated reflux. Thereafter, the reaction solution was cooled to 25 ° C., and 40 g of PGMEA was added to the reaction solution. The reaction by-products, methanol, ethanol, water, and hydrochloric acid, were removed by distillation under reduced pressure, and the mixture was concentrated to obtain a hydrolysis condensate (polymer) PGMEA solution. PGEE was added thereto, and solvent replacement was performed by solvent removal, obtaining a PGEE polymer solution. The resulting solution was adjusted with PGEE so that the concentration was 15% by mass in terms of solid residue at 200° C. The weight average molecular weight of the resulting polymer was Mw 1,500 in terms of polystyrene.

[0118] (Synthesis Example 13) Synthesis of MeOH-dispersed solid silica sol (a12) 2.49 g of M33TMOSPAP was added to 16 g of MEK in a 100 mL recovery flask and dissolved, and 1.51 g of AOI-VM was added thereto, followed by stirring at 25°C for 3 hours. －１ ) were 3370, 2947, 1729, 1635, 1537, 1268, 1193, and 1085. Then, 13 g of this surface treatment agent solution was added to a 500 mL recovery flask equipped with a condenser containing 150 g of MeOH dispersion sol (a1), 18.5 g of methanol, and 2 g of pure water, and heated to 65°C for 3 hours while stirring with a magnetic stirrer to obtain the target sol. The obtained sol had an average particle size of 44.1 nm by DLS method, a pH of 3.4, and SiO ２ The concentration was 20% by mass and the water content was 1.2% by mass. No sediment was observed, and good dispersibility was observed.

[0119] Synthesis Example 14 Synthesis of Surface-Treated MeOH-Dispersed Hollow Silica Sol (a13) 2.52 g of APS was added to 16 g of MEK in a 100 mL recovery flask and dissolved, and 1.47 g of EICYA was added and stirred at 25°C for 3 hours. The IR (cm-1) of the prepared surface treatment agent was 3361, 2976, 1748, 1644, 1574, 1281, 1199, and 1081. 13 g of this surface treatment agent solution was then added to a 500 mL recovery flask equipped with a condenser containing 150 g of MeOH-Dispersed Sol (a1), 18.5 g of methanol, and 2 g of pure water, and heated to 65°C for 3 hours while stirring with a magnetic stirrer to obtain the target sol. The obtained sol had an average particle size of 62.3 nm by DLS, a pH of 6.8, and SiO ２ The concentration was 20% by mass and the water content was 1.2% by mass. No sediment was observed, and good dispersibility was observed.

[0120] (Test for Confirmation of Redispersibility in Developer) Example 1: A 100 mL eggplant-shaped flask containing 50 g of the sol obtained in Synthesis Example 6 was placed in a rotary evaporator, and the dispersion solvent was removed under a bath temperature of 60°C and a reduced pressure of 50 Torr to obtain a dried sol. The resulting dried product was crushed with a mortar and pestle to obtain a dry sol powder. Then, 0.05 g of the resulting dry sol powder was placed in a 20 mL glass vial, and 2.0 mL of either an aqueous alkaline solution or an organic solvent listed in Tables 1 and 2 was added. Next, using a test tube mixer (manufactured by AS ONE Corporation, product name: MVM-10), the dry sol powder was mixed with either an aqueous alkaline solution or an organic solvent listed in Tables 1 and 2, and the appearance was confirmed. If the appearance was transparent, the sol was deemed redispersible; if the appearance was opaque or powder remained, the sol was deemed unredispersible. Furthermore, the average particle size after redispersion of the redispersible sol was obtained using the DLS method. In Table 1, the results are shown as "◯" when redispersible, "×" when redispersible, and "-" when not redispersible. Table 1 also shows the ratio X of (particle size of silica particles in developer measured by DLS) / (particle size of silica particles in organic solvent measured by DLS) based on the average particle size measurement results after redispersion by DLS. When the silica particles aggregated and the particle size could not be measured by DLS, the ratio X was recorded as "0." Examples 2 to 7: Dried powders of the sols obtained in Synthesis Examples 6, 7, 9, 10, 13, and 14 were prepared in the same manner as in Example 1, and mixed with either an aqueous alkali solution or an organic solvent listed in Tables 1 and 2, and the redispersibility was confirmed. The redispersibility results obtained and the DLS measurement results after redispersion are shown in Tables 1 and 2.

[0121] Note that MeOH (methanol), AC (acetone), PGME (propylene glycol monomethyl ether), PGMEA (propylene glycol monomethyl ether acetate), NMP (N-methyl-2-pyrrolidone), DMAC (N-dimethylacetamide), ACBu (butyl acetate), and EL (ethyl lactate) were used as undiluted solutions, ETMAH (ethylmethylammonium hydroxide) was used as a 2.38 mass % aqueous solution, and KOH was used as a 1 mass % aqueous solution.

[0122]

[0123]

[0124] As shown in Tables 1 and 2, the silica particles contain aluminum atoms that form aluminosilicate sites, and the aluminum atoms present in the entire silica particles are Al ２ O ３ Converted to SiO of silica particles ２ 120 to 50,000 ppm / SiO per 1 g ２ The silica particles are silica particles bonded at a ratio (B) of methylphenyldimethoxysilane having a methyl group and a phenyl group, and the dried powder of the sol according to the present invention (Synthesis Example 9, Example 4) exhibits good redispersibility in both alkaline aqueous solutions and organic solvents by modifying the silica particle surface by bonding or coating with methylphenyldimethoxysilane having a methyl group and hexamethyldisiloxane having a trimethylsilyl group, confirming that the silica particles according to the present invention are redispersible in both developers including organic solvents and alkaline aqueous solutions. Furthermore, as described in Example 1 (Synthesis Example 5), Example 2 (Synthesis Example 6), Example 3 (Synthesis Example 7), Example 6 (Synthesis Example 13), and Example 7 (Synthesis Example 14), it was confirmed that the silica particle surface can be modified by bonding or coating with an alkyl group-containing silane such as methyltrimethoxysilane having a methyl group, secondary or tertiary amines such as tertiary amines such as tripentylamine, protected carboxyl groups such as amino acid esters, carboxyl group-generating groups, or organic functional groups having a carboxyl group, thereby exhibiting selective developability only in alkaline aqueous solutions or selective developability only in organic solvents.

[0125] (Composition Evaluation) Example 8: A recovery flask containing a solution obtained by mixing the polymer of Synthesis Example 12 and silica sol (product name MA-ST-L) in a 50:50 solids ratio was placed in an evaporator, and MeOH was distilled off at a bath temperature of 80°C and 250 Torr to prepare the target composition shown in Table 3. After measuring the composition concentration, the composition was dropped onto a 5 x 5 cm alkali-free glass substrate (manufactured by Corning Incorporated, product name: Eagle XG) set on a spin coater (manufactured by Mikasa Co., Ltd., product name: MS-A100) and coated under film-forming conditions of 1500 rpm x 30 seconds. The substrate was then baked on a hot plate at 100°C for 2 minutes and then further baked at 180°C for 30 minutes to obtain a coating film. The resulting coating film was transparent, and the total light transmittance (T.T.) was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: NHD-5000), resulting in a value of 92.8%. The film thickness was measured using a product name F20-EXR (manufactured by FILMETRICS Co., Ltd.) and was found to be 1.102 μm. The conditions and results obtained are shown in Tables 3 and 4. Examples 9 and 10: The same procedure as in Example 8 was carried out except that the silica sol used and the film-forming conditions were changed. The film obtained was transparent. The conditions and results obtained are shown in Tables 3 and 4. Comparative Example 1: The same procedure as in Example 8 was carried out except that the sol used was changed to MeOH-dispersed silica sol (a4). The film obtained after firing had cracks, and the desired coating film was not obtained. The conditions and results obtained are shown in Tables 3 and 4.

[0126]

[0127] The film-forming properties were evaluated as follows: A: A film of more than 1.5 μm could be formed; B: A film of 1.0 μm to 1.5 μm could be formed; C: A film of less than 1.0 μm or no film could be formed. From the above results, silica particles containing aluminum atoms showed high compatibility with resin, and a coating film was obtained. On the other hand, silica particles not containing aluminum atoms could not obtain the desired coating film. (Photosensitive composition evaluation) Example 11: 10 g of the surface-treated MeOH-dispersed hollow silica sol (a13) obtained in Synthesis Example 14 and 8 g of PGEE were placed in a 100 ml recovery flask, and the pressure was reduced to 60° C. / 100 Torr to form a SiO ２A 20% by mass PGEE sol was prepared. Subsequently, 2.3 g of this solution was placed in a 30 ml brown sample bottle under a yellow room, followed by the addition of 3 g of the polysiloxane (p1) PGEE solution obtained in Synthesis Example 12, 0.14 g of P-200 (trade name of Toyo Gosei, structure: photosensitizer synthesized by condensation reaction of 1 mol of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride), and 0.37 g of PGEE. The mixture was then stirred for 4 hours at 23°C using a mix rotor to obtain the desired photosensitive resin composition. This composition was dropped onto a 4-inch silicon wafer and applied using a spin coater at 800 rpm for 5 seconds. The wafer was then baked on a hot plate at 100°C for 2 minutes and then at 180°C for 30 minutes to form a pre-baked coating film of 1.4 μm. The film thickness was evaluated using a contact film thickness meter (manufactured by ULVAC, product name: Dektak 3ST). A chrome mask was then placed over the coating film, and a portion of the coating film was exposed to 1 J / cm using an ultraviolet curing conveyor system (manufactured by Iwasaki Electric, product name: iGrandage 4KW). ２ The exposed coating film was immersed in a 0.1% KOH aqueous solution for 30 seconds, and the exposed area was developed. The film thickness of the unexposed area was 1.2 μm, and no residue was observed in the exposed area. From the above results, it was found that silica particles containing aluminum atoms exhibit high compatibility with resin, and a photosensitive coating film could be obtained. Furthermore, a film was obtained without development in the unexposed area, while no residue was observed in the exposed area after alkaline development.

[0128] The coating film produced by the coating composition of the present invention has been confirmed to exhibit solubility in organic solvents or alkaline aqueous solutions, enabling pattern formation on substrates and planarization by surface peeling of the surface layer on the coating film. Furthermore, since the coating composition has the property of being soluble in both organic solvents and alkaline aqueous solutions, or only in organic solvents, or only in alkaline aqueous solutions, it has positive-tone developability, negative-tone developability, or both, thereby providing excellent performance for lithography. Furthermore, the coating layer can be made into a planarized film by surface peeling, making it suitable as an underlayer film in the process of laminating an upper layer on the coating layer, and can be used in multilayer processes. Furthermore, since the silica particles in the present invention form aluminosilicates with aluminum atoms, coating films produced by coating compositions containing these silica particles have high film performance, are free of cracks and other fissures even in thick films, and can form highly transparent coatings on substrates. Furthermore, the low viscosity allows for spin coating, and the low curing temperature allows for coating on various substrates such as glass substrates, semiconductor substrates, and organic films.

[0129] Aluminum atoms are attached to the surface of the silica particles. ２ O ３ It is possible to provide a coating composition using silica particles bonded at a specific ratio in terms of converted value, a laminated substrate using the coating composition, and a method for producing the laminated substrate.

Claims

1. Silica particles for addition to a coating composition, the silica particles containing aluminum atoms forming aluminosilicate sites in the silica particles, the aluminum atoms being determined by dissolving the silica particles in an aqueous hydrofluoric acid solution, and the aluminum atoms present throughout the silica particles being Al ２ O ３ Converted to SiO of silica particles ２ 120 to 50,000 ppm / SiO per 1 g ２ Silica particles bonded at a ratio of 2. Silica particles according to claim 1, in which the ratio of the specific surface area (C) measured by the BET method (nitrogen gas adsorption method) to the specific surface area (D) measured by a transmission electron microscope is 1.00 to 5.

00.

3. Silica particles according to claim 1, in which the ratio of the specific surface area (C) measured by the BET method (nitrogen gas adsorption method) to the specific surface area (D) measured by a transmission electron microscope is 1.40 to 5.

00.

4. SiO of the above silica particles ２ 4. The silica particles according to claim 1, wherein the surface charge amount calculated per gram of silica particles is 5 to 250 μeq / g.

5. The silica particles further comprise a compound represented by the formula (1), (2), or (3): (In formula (1), R １ each represents an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxyl group, a protected carboxyl group, a carboxyl group-generating group, or a cyano group, and is bonded to a silicon atom via a Si—C bond; R ２ each represents an alkoxy group, an acyloxy group, a hydroxyl group, or a halogen group, a represents an integer of 1 to 3, and in formula (2) and formula (3), R ３ and R ５ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, R ４ and R ６ each represents an alkoxy group, an acyloxy group, a hydroxyl group, or a halogen group, Y represents an alkylene group, an NH group, or an oxygen atom, b is an integer of 1 to 3, c is an integer of 0 or 1, and d is an integer of 1 to 3. The silica particles according to any one of claims 1 to 4, which are coated with at least one silane compound selected from the group consisting of:

6. Silica particles according to any one of claims 1 to 5, wherein the coating film formed by the coating composition has a thickness of 1 to 30 μm.

7. Silica particles according to any one of claims 1 to 6, wherein the transmittance of the coating film formed by the coating composition is 90% or more.

8. Silica particles derived from a sol in which the silica particles according to any one of claims 1 to 7 are dispersed in a dispersion medium, the silica particles having an average particle size of 20 to 150 nm as measured by a dynamic light scattering method.

9. Silica particles according to claim 8, wherein the dispersion medium is an alcohol, ketone, ether, amide, or ester having 1 to 10 carbon atoms.

10. The silica particles according to claim 8 or 9, further comprising an amine.

11. The silica particles according to claim 10, wherein the amine is at least one amine selected from the group consisting of primary amines, secondary amines, and tertiary amines having 1 to 10 carbon atoms.

12. Silica particles according to claim 10 or 11, wherein the amine is a water-soluble amine having a water solubility of 80 g / L or more.

13. The content of the above amine is SiO of the silica particles ２ The silica particles according to any one of claims 10 to 12, wherein the content is 0.001 to 10 mass% based on the total mass of the silica particles.

14. Silica particles according to any one of claims 1 to 13, which are redispersible in a developer containing an organic solvent or an aqueous alkaline solution.

15. Silica particles according to claim 14, wherein when the organic solvent dispersion sol of the silica particles is dried under drying conditions of 60°C and 50 Torr and then redispersed in a developer containing an organic solvent or an alkaline aqueous solution, the average particle size of the silica particles in the developer as measured by dynamic light scattering method is (particle size of the silica particles in the developer as measured by dynamic light scattering method) / (particle size of the silica particles in the organic solvent as measured by dynamic light scattering method)=0.5 to 4.

0.

16. Silica particles according to claim 14 or 15, wherein the alkaline component in the developer is an alkali metal hydroxide or a quaternary ammonium.

17. Silica particles according to any one of claims 14 to 16, wherein the organic solvent component in the developer is an alcohol, a ketone, an ester, an amide, or a glycol.

18. Silica particles described in any one of claims 1 to 17, which are solid silica particles with no space inside the particle, hollow silica particles with space inside the outer shell, or a mixture of these particles.

19. A coating composition comprising the silica particles according to any one of claims 1 to 18 and a resin.

20. The coating composition according to claim 19, wherein the resin is a polysiloxane-based resin, a polyacrylic-based resin, an epoxy-based resin, a thioepoxy resin, a novolac-based resin, a maleimide resin, a polyester-based resin, a polyamide-based resin, a polyimide-based resin, a polyhydroxyimide resin, a polybenzoxazole resin, a polybenzimidazole resin, a polybenzothiazole resin, a polyamic acid resin, a polyhydroxyamide resin, a polyhydroxyazomethine resin, a polyether-based resin, a polybenzoxazine resin, a polystyrene resin, a polyhydroxystyrene resin, a polyurethane resin, a polyurea resin, a condensation resin, or a combination thereof.

21. The coating composition according to claim 19 or claim 20, further comprising a radical generator or an acid generator.

22. The coating composition of claim 21, wherein said coating composition is a resist composition.

23. A method for producing a laminated substrate, comprising the steps of (i) applying the coating composition according to any one of claims 19 to 22 onto a substrate and drying the composition to form a coating film, and (ii) curing the coating film.

24. The method for producing a laminated substrate according to claim 23, wherein the curing in step (ii) is thermal curing, photocuring, or a combination thereof.

25. The method for producing a laminated substrate according to claim 23 or 24, wherein the curing in step (ii) is performed by exposing the coating film to light through a mask.

26. A method for producing a laminated substrate according to any one of claims 22 to 25, further comprising the additional step of (iii) developing or planarizing the substrate after curing.

27. The method for producing a layered substrate according to claim 26, wherein the development or planarization is carried out with an organic solvent or an alkaline aqueous solution.

28. A method for producing a laminated substrate comprising a multilayer film, comprising forming an upper layer film, a lower layer film, or both a layer and a coating film according to any one of claims 23 to 27.

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