Silica particles for coating composition, and laminated substrate

Abstract

The present invention addresses the problem of providing: a coating composition using 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 using the coating composition; and a method for producing the laminated substrate. [Solution] A silica particle to be added to a coating composition, the silica particle containing aluminum atoms in which aluminosilicate sites are formed on the silica particle, the aluminum atoms being bonded at a ratio of 120-50000 ppm / SiO2 per 1 g of SiO2 of the silica particle in terms of Al2O3, the aluminum atoms being present in the entire silica particle, and the silica particle containing aluminum atoms having aluminosilicate sites formed on the aluminosilicate sites being bonded at a ratio of 120-50000 ppm / SiO2 per 1 g of SiO2 of the silica particle in terms of Al2O3. The amount of aluminum atoms present in the entire silica particles is measured by a dissolution method by treating the silica particles with an aqueous hydrofluoric acid solution. The ratio (specific surface area (C) measured by the BET method (nitrogen adsorption method)) / (specific surface area (D) converted by a transmission electron microscope) of the silica particles is 1.00-5.00.

Description

Technical Field

[0001] This invention relates to a coating composition using silica particles containing aluminum atoms and a method for manufacturing a laminated substrate. Background Technology

[0002] Hollow silica particles, which have a silica shell and a space inside the shell, possess characteristics such as low refractive index, low thermal conductivity (thermal insulation), and electrical insulation.

[0003] Hollow silica particles consist of a core, which is equivalent to a void, and an outer shell that forms the outer side of the core. An aqueous dispersion of hollow silica particles can be obtained by forming a silica layer on the outer side of the core in an aqueous medium and then removing the core.

[0004] For example, a method for manufacturing acidic silica sol is disclosed, in which an aqueous solution of an alkali metal aluminate is added to a dispersion of solid silica particles at a ratio of 0.0006 to 0.004 (calculated as Al2O3 / SiO2 molar ratio), and the mixture is heated at 80 to 250°C to perform cation exchange on the resulting silica sol (see Patent Document 1).

[0005] A method is disclosed to obtain an aqueous solid silica sol by cation exchange of an aqueous solution of an alkali metal salt containing aluminum atoms and heating the resulting active silica at 80-300°C, or by adding an alkali metal salt of aluminate to an aqueous silica sol and heating it at 80-300°C. Silica particles containing aluminum atoms with aluminosilicate sites formed on the surface of solid silica particles obtained by these methods are dispersed in a nitrogen-containing solvent, and silica sol in which aluminum atoms, as measured by leaching, are bonded to the surface of silica particles at a ratio of 800-20000 ppm / SiO2 (as converted to Al2O3) (see Patent Document 2).

[0006] A method for manufacturing hollow silica sol is disclosed, wherein a core-shell particle with a silicate shell is formed by reacting a silane compound and an aluminum precursor in a Si / Al molar ratio of 7 to 15 in a template core formed by micelles or reverse micelles of an organic polymer, and then reacting the particle with an alkaline or acidic aqueous solution to form pores in the shell (outer shell) and remove the core, and then heating the shell at 160 to 200°C to carry out a hydrothermal reaction (see Patent Document 3).

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 6-199515

[0010] Patent Document 2: International Publication No. 2022 / 097694

[0011] Patent Document 3: Korean Patent 10-1659709B1 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] A coating composition is provided in which silicon dioxide particles are bonded to the surface of silicon dioxide particles in a specific ratio using aluminum atoms (calculated as Al2O3), a laminated substrate using the coating composition, and a method for manufacturing the laminated substrate are provided.

[0014] Methods for solving problems

[0015] In this invention, as a first aspect, there is a type of silica particle used as an additive in a coating composition. This silica particle contains aluminum atoms with aluminosilicate sites formed on it. The aluminum atoms are bonded in a ratio of 120 to 50,000 ppm / SiO2 (calculated as Al2O3) relative to 1 g of SiO2 in the total silica particles. The amount of aluminum atoms present in the total silica particles is determined by a dissolution method after treating the silica particles with an aqueous hydrofluoric acid solution.

[0016] As a second point of view, for the silica particles described in the first point of view, the ratio of [specific surface area (C) measured by the BET method (nitrogen adsorption method)] to [specific surface area (D) calculated by transmission electron microscopy] is 1.00 to 5.00.

[0017] As a third point of view, for the silica particles described in the first point of view, the ratio of [specific surface area (C) measured by the BET method (nitrogen adsorption method)] to [specific surface area (D) converted by transmission electron microscopy] is 1.40 to 5.00.

[0018] As a fourth point of view, the silica particles according to any one of the first to third points of view are defined as having a surface charge of 5 to 250 μeq / g per 1g of SiO2.

[0019] As a fifth point of view, for the silica particles according to any one of the first to fourth points of view, the silica particles are further coated with at least one silane compound selected from formula (1), formula (2) and formula (3):

[0020]

[0021] (In equation (1), R) 1Each of the following is an organic group that is alkyl, haloalkyl, alkenyl, aryl, or has an epoxy, (meth)acryloyl, mercapto, amino, urea, polyether, carboxyl, protected carboxyl, carboxyl-generating, or cyano group and is bonded to a silicon atom by a Si-C bond: R 2 Each represents an alkoxy, acyloxy, hydroxyl, or halogen group, and 'a' represents an integer from 1 to 3.

[0022] In equations (2) and (3), R 3 and R 5 Each is an alkyl group with 1 to 3 carbon atoms or an aryl group with 6 to 30 carbon atoms, bonded to silicon atoms by Si-C bonds. 4 and R 6 Each group represents an alkoxy, acyloxy, hydroxyl, or halogroup; Y represents an alkylene, NH group, or oxygen atom; b is an integer from 1 to 3; c is an integer from 0 to 1; and d is an integer from 1 to 3.

[0023] As a sixth point of view, the film thickness formed from the above-described coating composition using silica particles according to any one of the first to fifth points of view is 1 to 30 μm.

[0024] As a seventh point of view, the transmittance of the film formed from the above-described coating composition is 90% or more, provided that the silica particles according to any one of the first to sixth points of view are used.

[0025] As the eighth point of view, there is a type of silica particle derived from a sol obtained by dispersing the silica particles described in any one of the first to seventh points in a dispersion medium, wherein the average particle size, as measured by dynamic light scattering, is 20-150 nm.

[0026] As a ninth point of view, for the silica particles described in the eighth point of view, the aforementioned dispersion medium is an alcohol, ketone, ether, amide, or ester having 1 to 10 carbon atoms.

[0027] As a tenth point of view, the silica particles described according to the eighth or ninth point of view further contain amines.

[0028] As the 11th point of view, for the silica particles described in the 10th point of view, the aforementioned amine is at least one amine selected from primary amines, secondary amines, and tertiary amines having 1 to 10 carbon atoms.

[0029] As a 12th point of view, the silica particles described in the 10th or 11th point of view, wherein the amine is a water-soluble amine with a water solubility of 80 g / L or more.

[0030] As the 13th point, for the silica particles according to any one of the 10th to 12th points, the content of the aforementioned amine is 0.001 to 10% by mass relative to the SiO2 content of the silica particles.

[0031] As a 14th point of view, the silica particles according to any one of the 1st to 13th points of view are capable of being redispersed in a developing solution containing an organic solvent or an alkaline aqueous solution.

[0032] As a 15th point, for the silica particles described in the 14th point, when the organic solvent dispersion sol of the aforementioned 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, measured by dynamic light scattering, satisfies: (dynamic light scattering particle size of silica particles in the developer) / (dynamic light scattering particle size of silica particles in the organic solvent) = 0.5~4.0.

[0033] As a 16th point of view, for the silica particles described in point 14 or point 15, the alkaline component in the aforementioned developing solution is an alkali metal hydroxide or quaternary ammonium.

[0034] As the 17th point of view, the silica particles according to any one of the 14th to 16th points of view, the organic solvent component in the above-mentioned developing solution is an alcohol, ketone, ester, amide, or diol.

[0035] As the 18th point of view, the silica particles according to any one of the 1st to 17th points of view are solid silica particles with no internal space, hollow silica particles with internal space in their outer shell, or a mixture of these silica particles.

[0036] As the 19th point, there is a coating composition comprising silica particles and resin as described in any one of the 1st to 18th points.

[0037] As a 20th point of view, for the coating composition according to the 19th point of view, the resin is a polysiloxane resin, a polyacrylic resin, an epoxy resin, a thiolated epoxy resin, a phenolic varnish resin, a maleimide resin, a polyester resin, a polyamide resin, a polyimide resin, a polyhydroxyimide resin, or a polybenzoyl peroxide resin. Poly(benzimidazole) resin, poly(benzothiazole) resin, polyamic acid resin, polyhydroxyamide resin, polyhydroxyazomethyl alkali resin, polyether resin, polybenzo[azo]pyridine resin Azide resins, polystyrene resins, polyhydroxystyrene resins, polyurethane resins, polyurea resins, condensation resins, or combinations thereof,

[0038] As a 21st point of view, the coating composition according to the 19th or 20th point of view contains a free radical generator or an acid-generating agent.

[0039] As a 22nd point of view, the coating composition according to the 21st point of view is a photoresist composition.

[0040] As the 23rd viewpoint, a method for manufacturing a laminated substrate includes the following steps: (i) Step: applying the coating composition described in any one of views 19 to 22 onto a substrate and drying it to form a coating film.

[0041] (ii) Process: Curing the coating film.

[0042] As a 24th point of view, in the method for manufacturing the laminated substrate according to the 23rd point of view, the curing of the above-mentioned (ii) step is thermosetting, photosetting, or a combination thereof.

[0043] As the 25th point of view, in the method for manufacturing the laminated substrate according to the 23rd or 24th point of view, the curing of the above-mentioned (ii) step is an exposure performed on the coated film through a mask.

[0044] As the 26th point of view, for the manufacturing method of the laminated substrate according to any one of the 22nd to 25th points of view, an additional step of developing or planarizing after curing is added (iii).

[0045] As the 27th point of view, in the manufacturing method of the laminated substrate according to the 26th point of view, development or planarization is performed using an organic solvent or an alkaline aqueous solution, and

[0046] As the 28th point of view, there is a method for manufacturing a laminated substrate comprising multiple films, wherein an upper film, a lower film, or a film is formed on both sides of the coating film described in any one of the 23rd to 27th points of view.

[0047] The effects of the invention

[0048] It is known that aluminosilicate sites, formed by the reaction of aluminate ions with silanol groups on the surface of silica particles, impart a negative charge to the silica particles in the silica sol. These aluminosilicate sites enhance the stability of the dispersion medium by increasing the negative zeta potential. In particular, they improve compatibility with organic solvents and charged resins.

[0049] Furthermore, by introducing aluminum compounds into the acidic silica solution to grow particles, the aluminum compounds are encapsulated within the silica particles. Alkali metals present within the silica particles are thus trapped, resulting in a stable silica sol. However, the alkali metals encapsulated within the silica particles are released out of the system over time, contributing to instability. Moreover, because aluminosilicates are formed even inside the silica particles, which are not initially needed for stabilization, the amount of aluminum present in the silica particles increases, and more alkali metals are bound to the aluminosilicates. Consequently, these metals eventually flow out of the silica particles over time.

[0050] For solid silica particles without voids, after the silica particles are formed, aluminum compounds are impregnated from the surface to form aluminosilicate sites near the surface. Even if the aluminum compounds impregnate to the part close to the center of the silica particles, sodium is kept inside.

[0051] For hollow silica particles with cavities inside the shell, aluminum compounds infiltrate from the outside, thus permeating the shell. The aluminum compounds that infiltrate to the outside and inside of the shell each form aluminosilicate sites, which also contain alkali metals. The alkali metals present in the aluminosilicate sites on the outside of the shell can be removed during manufacturing, but the alkali metals present in the aluminosilicate sites on the inside of the shell are difficult to remove during manufacturing and may flow out through the fine pores of the shell over time.

[0052] The present invention contains aluminum atoms that can be measured by leaching on the outer side of the shell of hollow silica particles and aluminum atoms that cannot be measured by leaching but can be measured by dissolution using hydrofluoric acid aqueous solution. It aims to provide hollow silica particles with high dispersion stability in the medium and no concerns about alkali metal leaching.

[0053] When impregnating hollow silica particles with aluminum compounds from the outside, there are two scenarios: first, the hollow silica particles that have undergone pre-hydrothermal treatment to increase their shell density before impregnation are impregnated with aluminum compounds through heat treatment; second, hollow silica particles that have not undergone pre-hydrothermal treatment are impregnated with aluminum compounds through heat treatment. In both cases, it is preferable that aluminum atoms exist in a specific ratio to silica.

[0054] The silica particles of the present invention are contained in a coating composition, and are present in the coating film after being coated on a substrate and dried. The coating film is exposed through a mask and then developed with a developer to form a pattern, and the substrate is then processed by etching using a liquid or gas.

[0055] In addition, the above-mentioned coating film is a cured film after exposure without a mask, but in order to improve the planarization, the surface layer of the cured film can be peeled off with a developing solution to achieve planarization.

[0056] The present invention provides a coating composition with good coating performance when a coating composition containing aluminum silica particles is applied to a substrate to form a film. Attached Figure Description

[0057] Figure 1 This is a photograph of the membrane obtained in Example 10.

[0058] Figure 2 A photograph of the membrane obtained in Comparative Example 1. Detailed Implementation

[0059] The present invention relates to a silica particle for use in a coating composition. The silica particle contains aluminum atoms forming aluminosilicate sites on the silica particle. The aluminum atoms are bonded in a ratio of 120 to 50,000 ppm / SiO2 (calculated as Al2O3) relative to 1g of SiO2 in the silica particle. The amount of aluminum atoms present in the silica particle is determined by a dissolution method by treating the silica particle with an aqueous hydrofluoric acid solution.

[0060] In this invention, the silica particles can be solid silica particles without internal space, hollow silica particles with internal space, or a mixture of these particles. In this invention, the term "silica particle" as used in the specification refers to solid silica particles, hollow silica particles, or a mixture of these.

[0061] Hollow silica particles have a silica shell and a space inside the shell. Hollow silica can be obtained by forming a shell with silica as the main component on the surface of a portion equivalent to the core, called a template, in a dispersion medium, and then removing the portion equivalent to the core.

[0062] In this invention, aluminum atoms can be expressed as Al2O3 by leaching, which involves leaching silica particles with an aqueous solution of at least one inorganic acid selected from sulfuric acid, nitric acid, and hydrochloric acid, to determine the aluminum present on the surface of the silica particles. Specifically, the aluminum atoms, as determined by the leaching method, are bonded to the surface of hollow silica particles at a ratio (A) of 100-20000 ppm / SiO2, or 100-15000 ppm / SiO2, or 100-10000 ppm / SiO2, or 100-3000 ppm / SiO2, or 200-5000 ppm / SiO2, or 400-5000 ppm / SiO2, or 800-3000 ppm / SiO2 relative to 1g of SiO2 in the silica particles. The presence of aluminosilicate sites on the surface of the silica particles is important for dispersion in solvents and resins. In the manufacture of acidic silica sol, it is desirable to have a high absolute value of the Zeta potential of silica particles in the acidic region. However, for an aluminum atom content of less than 100 ppm / SiO2 in proportion (A), there is a tendency for the stability of silica particles to decrease. In addition, when the content is 3000 ppm / SiO2 or more in proportion (A), in the stage of aluminum-containing hollow silica aqueous sol, there is a tendency for the dynamic light scattering particle size (DLS particle size) after aluminum atom doping due to aluminum compounds to increase over time compared with the particle size before doping.

[0063] The aluminum atoms present on the surface of silica particles in the form of aluminosilicates can be represented as follows: The silica particles are treated with an aqueous solution of at least one inorganic acid selected from sulfuric acid, nitric acid, and hydrochloric acid. The aluminum atoms are leached (dissolved) in a structure similar to aluminum salts, aluminum oxides, or aluminum hydroxides. The aluminum atoms in this solution are determined using an ICP-based spectrophotometer and converted to Al₂O₃. In particular, leaching (dissolving) can be performed using an aqueous nitric acid solution. The aqueous nitric acid solution used for leaching can have a pH range of 0.5–4.0, 0.5–3.0, 0.5–2.0, or 1.0–1.5; typically, a pH of 1.0 can be used. For example, 100 mL of the above-mentioned aqueous nitric acid solution can be added relative to 1 g of silica, and the solution can be kept at a temperature of 20–70°C or 40–60°C for 10–24 hours to dissolve the aluminum compounds from the surface of the silica particles, which can then be used as an analytical sample.

[0064] In this invention, the so-called silica particle surface can be defined as the area where aluminum compounds can dissolve through the above-mentioned leaching. It is prepared by grinding silica gel obtained by further drying silica sol at 250°C after evaporating the solvent, and then grinding it into silica powder. 0.2g of this silica powder is mixed with 20mL of a pH 1.0 nitric acid aqueous solution and shaken thoroughly. After maintaining the mixture in a constant temperature bath at 50°C for 17 hours, it is centrifuged and filtered. The aluminum content in the filtrate is determined using an ICP-based spectrophotometer. The aluminum content, converted to Al2O3, is divided by the mass of the silica powder to calculate the amount of aluminum bound to the silica particle surface (Al2O3 / SiO2) (ppm).

[0065] Furthermore, even when aluminosilicates are formed on the surface of silica particles, depending on the manufacturing method, aluminosilicates may sometimes be formed selectively not only on the surface but also inside the silica particles. Aluminum atoms present in the entire hollow silica particle, including both the surface and the interior, are bonded to the silica particles at a ratio (B) of 120~50000 ppm / SiO2, or 400~20000 ppm / SiO2, or 400~10000 ppm / SiO2, or 1000~5000 ppm / SiO2, or 1000~4000 ppm / SiO2, or 120~4000 ppm / SiO2, based on the Al2O3 content relative to 1g of SiO2 in the hollow silica particles.

[0066] In the manufacture of acidic silica sol, it is desirable to have a high absolute value of the Zeta potential of silica particles in the acidic region. However, in ratio (B), the aluminum atom content, equivalent to Al2O3, which is less than 120 ppm / SiO2, tends to reduce the stability of silica particles. Furthermore, when the content is 4000 ppm / SiO2 or more in ratio (B), there is a tendency for the dynamic light scattering particle size (DLS particle size) to increase over time relative to the undoped particle size after aluminum atom doping due to aluminum compounds in the aluminum-containing hollow silica aqueous sol stage.

[0067] The ratio of aluminum present on the surface of silicon dioxide particles and in the entirety of silicon dioxide particles, i.e., the ratio of (A) / (B) above, can be set to a range of 0.001~1.0, or 0.01~1.0, or 0.1~1.0, or 0.3~1.0, or 0.4~1.0.

[0068] Silica particles can be treated with an aqueous hydrofluoric acid solution, and the aluminum atoms present in the entire silica particle can be determined by a dissolution method and converted to Al2O3. That is, aluminum atoms present as aluminosilicates in the entire silica particle can be dissolved in an aqueous hydrofluoric acid solution, and the solution can be measured using an ICP-based spectrophotometer and converted to Al2O3 to represent the aluminum atoms present in the entire silica particle. The aqueous hydrofluoric acid solution can be used at a concentration of, for example, 48% by mass, as long as the amount is sufficient to dissolve the silica particles.

[0069] By forming aluminosilicate sites on silica particles in this way, the amount of negative charge present on the surface of silica particles, converted to 1g of SiO2 per silica particle, is measured to be in the range of 5~250μeq / g, or 5~150μeq / g, or 5~100μeq / g, or 25~150μeq / g, or 25~100μeq / g.

[0070] The aforementioned silica particles can be obtained in the form of silica sol dispersed in a dispersion medium. Hollow silica sol, consisting of silica particles dispersed in a dispersion medium, with an average particle size of 20–150 nm as measured by dynamic light scattering, can be obtained.

[0071] Hollow silica can be obtained by forming a shell with silica as the main component on the surface of a portion equivalent to the core, referred to as a template, in a dispersion medium, and then removing the portion equivalent to the core. In this state, it is a hollow silica aqueous sol.

[0072] The resulting hollow silica aqueous sol can be solvent-replaced with an alcohol solvent, which is an organic solvent. The alcohol solvent is preferably an alcohol with 1 to 5 carbon atoms having an ether bond, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. Then, after coating with a silane compound, the solvent can be further replaced with other organic solvents as desired.

[0073] In this invention, alcohols, ketones, ethers, esters, and amides having 1 to 10 carbon atoms can be cited as organic solvents.

[0074] Alcohols with 1 to 10 carbon atoms are aliphatic alcohols, including primary, secondary, and tertiary alcohols. These alcohols can also be polyols, such as diols and triols.

[0075] Examples of primary monohydric alcohols include methanol, ethanol, 1-propanol, 1-butanol, and 1-hexanol.

[0076] Examples of monohydric secondary alcohols include 2-propanol, 2-butanol, cyclohexanol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0077] Examples of monotertiary alcohols include tert-butanol.

[0078] Examples of diols include methane glycol, ethylene glycol, and propylene glycol.

[0079] Examples of trihydric alcohols include glycerol.

[0080] Aliphatic ketones are preferred as ketones having 1 to 10 carbon atoms. Examples include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl pentyl ketone, cyclohexanone, and methyl cyclopentanone.

[0081] Aliphatic ethers are preferred as ethers having 1 to 10 carbon atoms. Examples include dimethyl ether, ethyl methyl ether, diethyl ether, tetrahydrofuran, and 1,4-dioxane.

[0082] Aliphatic esters are preferred as esters with 1 to 10 carbon atoms. 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.

[0083] Examples of such amides include N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylacetamide, N,N-dimethylisobutyramide, dimethylacrylamide, acrylmorpholine, diethylacrylamide, N-methylpyrrolidone, N-ethylpyrrolidone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, etc.

[0084] In the silica aqueous sol and silica organic solvent sol used as the above raw materials, the average particle size of the hollow silica particles, as measured by dynamic light scattering (DLS method), can be in the range of 5~150nm, or 20~150nm, or 30~150nm, or 40~150nm, or 50~150nm, or 50~120nm, or 50~100nm.

[0085] In addition, the average primary particle size observed by transmission electron microscopy can be in the range of 5~150nm, or 20~150nm, or 30~150nm, or 40~150nm, or 50~150nm, or 50~120nm, or 50~100nm.

[0086] In addition, the specific surface area (C) measured by the BET method (nitrogen adsorption method) can be set to 18~550m². 2 / g, or 18~200m 2 / g, or 50~160m 2 / g, or 60~160m 2 / g, or 70~160m 2 / g, or 80~150m 2 / g.

[0087] In addition, the specific surface area (D) calculated from a transmission electron microscope can be set to 5~150 nm or 18~136 m². 2 / g, or 18~90m 2 / g, or 18~68m 2 / g, or 18~54m 2 / g, or 18~27m 2 / g, or 18~23m 2 / g.

[0088] Furthermore, the ratio of [specific surface area (C) measured by the BET method (nitrogen adsorption method)] to [specific surface area (D) converted by transmission electron microscopy] can be set to a range of 1.00~5.00, or 1.40~5.00, or 1.40~3.50, or 1.50~3.00, or 1.50~2.80. When the value of (C) / (D) is close to 1.0, it indicates a solid silica particle in which there is no space inside the shell of the silica particle. When the value of (C) / (D) exceeds 1.0, it indicates a hollow silica particle in which there is space inside the shell of the silica particle, or a solid silica particle in which part or all of the particle surface is porous.

[0089] In addition, the thickness of the shell of hollow silica particles, as observed by a transmission electron microscope, can be in the range of 3.0~15.0 nm, 4.0~12.0 nm, or 5.0~10.0 nm.

[0090] Furthermore, the refractive index of the aforementioned hollow silica particles can be obtained in the range of 1.20~1.45, or 1.20~1.40, or 1.25~1.40.

[0091] In addition, silica sol can be used with a SiO2 particle concentration of 1 to 50% by mass, or 5 to 40% by mass, typically 10 to 30% by mass.

[0092] The pH of the above sol can be adjusted to acidic to alkaline. Adjustment to acidity is achieved by adding inorganic or organic acids. Adjustment to alkalinity is achieved by adding inorganic or organic bases. As an organic base, amines can be added to adjust pH and surface charge. Regarding pH, for the acidic side, it can be set to pH 1 or higher and less than 7; for the alkaline side, it can be set to pH 7 or higher and less than 13.

[0093] Before adding amine, the aqueous silica sol can be set to a pH range of, for example, 2.0~6.0 or 2.0~4.5. By adding amine, it can be adjusted to a pH range of, for example, 3.0~10.0 or 3.0~9.0.

[0094] In the case of organic solvent sol, the above pH is the pH when the organic solvent sol and the same mass of pure water are mixed in a 1:1 ratio. It can be measured when an organic solvent that is miscible with water is used. When the solvent is subsequently replaced with a hydrophobic organic solvent, it is preferable to measure the pH in advance during the methanol solvent sol stage.

[0095] For example, for methanol sol and propylene glycol monomethyl ether sol, which are dispersed by hydrophilic organic solvents, a solution obtained by mixing pure water and sol in a mass ratio of 1:1 can be used for determination. For methyl ethyl ketone sol, which is dispersed by hydrophobic organic solvents, a solution obtained by mixing pure water, methanol and methyl ethyl ketone sol in a mass ratio of 1:1:1 can be used for determination.

[0096] Silica organic solvate can undergo solvent displacement from an aqueous medium to an alcohol solvent with 1 to 5 carbon atoms, and further to an organic solvent, but water may remain in this process. In the alcohol sol stage of hollow silica and solid silica, the residual water content may be 0.1 to 3.0% by mass, or 0.1 to 1.0% by mass. Furthermore, in the organic solvate stage of hollow silica and solid silica (where the dispersion medium is an organic solvent other than alcohol), the residual water content may be 0.01 to 0.5% by mass.

[0097] In addition, the viscosity of silica organic solvent sol can be set in the range of 1.0~10.0 mPa·s.

[0098] The silica sol of the present invention may contain amines.

[0099] The amines used in this invention can be water-soluble amines with a water solubility of 80 g / L or more, or 100 g / L or more.

[0100] In the aqueous silica sol used as a raw material, or in the silica organic solvate obtained by solvent displacement, amines, or amines and ammonia, may be contained. The amine may be added in the range of 0.001 to 10% by mass, 0.01 to 10% by mass, or 0.1 to 10% by mass relative to the SiO2 of the hollow silica particles. Furthermore, these basic components, such as amines, or amines and ammonia, in the silica particle organic solvate may be expressed as total nitrogen content, for example, in the range of 10 to 100,000 ppm, or 100 to 10,000 ppm, or 100 to 3,000 ppm, or 100 to 2,000 ppm, typically in the range of 200 to 2,000 ppm.

[0101] Examples of amines mentioned above include aliphatic amines and aromatic amines, with aliphatic amines being preferred. The amine may be at least one selected from primary, secondary, and tertiary amines having 1 to 10 carbon atoms. These amines are water-soluble and are at least one selected from primary, secondary, and tertiary amines having 1 to 10 carbon atoms.

[0102] Examples of primary amines include monomethylamine, monoethylamine, monopropylamine, monoisopropylamine, monobutylamine, monoisobutylamine, monosec-butylamine, monotert-butylamine, monomethanolamine, monoethanolamine, monopropanolamine, monoisopropanolamine, monobutanolamine, monoisobutanolamine, monosec-butanolamine, and monotert-butanolamine.

[0103] 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-ethylisobutylamine.

[0104] Examples of tertiary amines include trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, trisec-butylamine, tritert-butylamine, trimethanolamine, triethanolamine, tripropanolamine, triisopropanolamine, tributanolamine, triisobutanolamine, trisec-butanolamine, and tritert-butanolamine.

[0105] For the water solubility of the aforementioned amines, a concentration of 80 g / L or higher, or 100 g / L or higher, is preferably used. Primary and secondary amines are preferred, with secondary amines being preferred due to their low volatility and high solubility; examples include diisopropylamine and diethanolamine.

[0106] In this invention, by including the aforementioned amine, the surface charge of the silicon dioxide particles, converted to per 1g of SiO2, can be set to 5 μeq / g or more, or 25 μeq / g or more. Typically, it can be set to a range of 5~250 μeq / g, or 25~250 μeq / g, or 25~100 μeq / g, or 25~80 μeq / g.

[0107] In this invention, by adjusting the type and amount of the amine, the surface charge of the silica particles can be adjusted to any desired surface charge.

[0108] In this invention, the surface of silicon dioxide particles can be coated with a silane compound.

[0109] As the above-mentioned silane compound, it can be coated with a hydrolysate of at least one silane compound selected from formulas (1) to (3).

[0110] In equation (1), R 1 Each is an alkyl, haloalkyl, alkenyl, aryl, or an organogroup having a polyether, epoxy, (meth)acryloyl, mercapto, amino, urea, carboxyl, protected carboxyl, carboxyl-generating, or cyano group and bonded to a silicon atom by a Si-C bond, R 2 Each represents an alkoxy, acyloxy, hydroxyl, or halogen group, and 'a' represents an integer from 1 to 3.

[0111] In equations (2) and (3), R 3 and R 5 Each is an alkyl group with 1 to 3 carbon atoms or an aryl group with 6 to 30 carbon atoms, bonded to silicon atoms by Si-C bonds. 4 and R 6 Each represents an alkoxy, acyloxy, hydroxyl, or halogen group; Y represents an alkylene group, NH group, or oxygen atom; b is an integer from 1 to 3; c is an integer from 0 to 1; and d is an integer from 1 to 3.

[0112] The alkyl groups mentioned above are alkyl groups having 1 to 18 carbon atoms, and examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1 2-Dimethyl-cyclopropyl, 2,3-Dimethyl-cyclopropyl, 1-Ethyl-cyclopropyl, 2-Ethyl-cyclopropyl, n-Hexyl, 1-Methyl-n-pentyl, 2-Methyl-n-pentyl, 3-Methyl-n-pentyl, 4-Methyl-n-pentyl, 1,1-Dimethyl-n-butyl, 1,2-Dimethyl-n-butyl, 1,3-Dimethyl-n-butyl, 2,2-Dimethyl-n-butyl, 2,3-Dimethyl-n-butyl, 3,3-Dimethyl-n-butyl, 1-Ethyl-n-butyl, 2-Ethyl-n-butyl, 1,1,2-Trimethyl-n-propyl, 1 2,2-Trimethyl-n-propyl, 1-Ethyl-1-methyl-n-propyl, 1-Ethyl-2-methyl-n-propyl, Cyclohexyl, 1-Methyl-cyclopentyl, 2-Methyl-cyclopentyl, 3-Methyl-cyclopentyl, 1-Ethyl-cyclobutyl, 2-Ethyl-cyclobutyl, 3-Ethyl-cyclobutyl, 1,2-Dimethyl-cyclobutyl, 1,3-Dimethyl-cyclobutyl, 2,2-Dimethyl-cyclobutyl, 2,3-Dimethyl-cyclobutyl, 2,4-Dimethyl-cyclobutyl, 3,3-Dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl -Cyclopropyl, 1-Isopropyl-cyclopropyl, 2-Isopropyl-cyclopropyl, 1,2,2-Trimethyl-cyclopropyl, 1,2,3-Trimethyl-cyclopropyl, 2,2,3-Trimethyl-cyclopropyl, 1-Ethyl-2-methyl-cyclopropyl, 2-Ethyl-1-methyl-cyclopropyl, 2-Ethyl-2-methyl-cyclopropyl and 2-Ethyl-3-methyl-cyclopropyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecanyl, Octadecanyl, etc., but not limited to these.

[0113] In addition, alkylene derivatives derived from the aforementioned alkyl groups can be cited as examples.

[0114] The aryl groups mentioned above are aryl groups with 6 to 30 carbon atoms, such as phenyl, naphthyl, anthracene, pyrene, etc.

[0115] As an alkenyl group, it is an alkenyl group with 2 to 10 carbon atoms, and examples include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-propenyl -Butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, etc., but not limited to these.

[0116] Examples of alkoxy groups include those with 1 to 10 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, etc., but are not limited to these.

[0117] The aforementioned acyloxy group is an acyloxy group having 2 to 10 carbon atoms, and examples include methyl carbonyloxy, ethyl carbonyloxy, n-propyl carbonyloxy, isopropyl carbonyloxy, n-butyl carbonyloxy, isobutyl carbonyloxy, sec-butyl carbonyloxy, tert-butyl carbonyloxy, n-pentyl carbonyloxy, 1-methyl-n-butyl carbonyloxy, 2-methyl-n-butyl carbonyloxy, 3-methyl-n-butyl carbonyloxy, 1,1-dimethyl-n-propyl carbonyloxy, 1,2-dimethyl-n-propyl carbonyloxy, 2,2-dimethyl-n-propyl carbonyloxy, 1-ethyl-n-propyl carbonyloxy, n-hexyl carbonyloxy, 1-methyl-n-pentyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, etc., but are not limited to these.

[0118] Examples of halogen groups include fluorine, chlorine, bromine, and iodine.

[0119] As an organic group having a polyether group, an example is a polyetherpropyl group having an alkoxy group. For example, (CH3O)3SiC3H6(OC2H4)nOCH3. It can be used in the range of n from 1 to 100 or from 1 to 10.

[0120] Examples of silane coupling agents containing carboxyl groups include those in which four hydrogen atoms of a disiloxane are replaced by hydroxyl groups, two hydrogen atoms are replaced by carboxyl groups, or other organic groups containing carboxyl groups. Examples include compounds of formula (1-1) with two carboxyl groups bonded to the tetrahydroxydisiloxane skeleton, such as Shin-Etsu Chemical Co., Ltd., under the trade name X-12-1135.

[0121]

[0122] Examples of protected carboxyl groups and carboxyl-generating groups include silane coupling agents having a carboxylic acid ester structure. Examples of silane coupling agents containing an organic group containing a carboxylic acid ester group include alkyl esters, aryl esters, and arylalkyl esters. Examples of alkyl groups include straight-chain or branched alkyl groups with 1 to 10 carbon atoms, aryl groups with 6 to 40 carbon atoms, and arylalkyl groups with 1 to 10 carbon atoms bonded to the aryl group with 6 to 40 carbon atoms. Examples of the structures of these ester groups include methyl carboxylate, tert-butyl carboxylate, and benzyl carboxylate. Furthermore, the carboxylic acid ester group and the alkoxysilyl group can be linked by an alkylene group, and examples of alkylene groups with 1 to 10 carbon atoms that can contain heteroatoms can be included. Examples of heteroatoms include nitrogen atoms, oxygen atoms, NH groups, and O groups. The carboxylic acid ester moiety hydrolyzes to form a carboxylic acid, which, when a nitrogen atom is included as a heteroatom, becomes an amino acid. Organic groups containing the carboxylic acid ester group can be used as amino acid generating agents. These can be, for example, manufactured by Shin-Etsu Chemical Industry Co., Ltd., under the trade name X-88-475, as shown in formula (1-2). It should be noted that the amino acid structure can also use a urea structure or a carbamate structure to protect the amine site. Furthermore, regarding the protected carboxyl group and carboxyl generating group, the target compound can be prepared by reacting a compound having a protected carboxyl group and carboxyl generating group at its respective end with an organic group selected from amine, hydroxyl, and isocyanate groups with a compound having an alkoxysilane site.

[0123]

[0124] Examples of organic groups with epoxy groups include 2-(3,4-epoxycyclohexyl)ethyl and 3-epoxypropoxypropyl.

[0125] The term (meth)acryloyl group refers to both acryloyl group and methacryloyl group. Examples of organic groups having a (meth)acryloyl group include, for example, 3-methacryloyloxypropyl and 3-acryloyloxypropyl.

[0126] Examples of organic groups containing a thiol group include 3-mercaptopropyl.

[0127] Examples of organic groups containing amino groups include 2-aminoethyl, 3-aminopropyl, N-2-(aminoethyl)-3-aminopropyl, N-(1,3-dimethyl-butylene)aminopropyl, N-phenyl-3-aminopropyl, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl, etc.

[0128] Examples of organic groups containing a urea group include 3-ureopropyl.

[0129] Examples of organic groups containing a cyano group include 3-cyanopropyl.

[0130] Formulas (2) and (3) above are preferably compounds that can form trimethylsilyl groups on the surface of silica particles.

[0131] Examples of these compounds are as follows.

[0132]

[0133] In the above formula, R 12 The alkoxy group can be , for example, methoxy or ethoxy. The silane compounds described above can be silane compounds manufactured by Shin-Etsu Chemical Co., Ltd.

[0134] The process involves reacting the hydroxyl groups (or silanol groups, if applicable) on the surface of silica particles with the aforementioned silane compound, thereby coating the silica particles with the silane compound through siloxane bonds. The reaction temperature can be carried out in the range from 20°C to the boiling point of the dispersion medium, for example, in the range of 20°C to 100°C. The reaction time can be approximately 0.1 to 10 hours.

[0135] The aforementioned silane compound, as a coating on the surface of silica particles, can be added to the silica sol at a rate equivalent to 0.1 silicon atoms / nm. 2 ~20.0 units / nm 2 The surface of silica particles is coated with silane compounds.

[0136] The hydrolysis of the aforementioned silane compounds requires water, and these aqueous solvents can be used in the sol form. When replacing the aqueous medium with an organic solvent, residual water in the solvent can be used. For example, water present in quantities of 0.01 to 5% by mass can be used. Furthermore, hydrolysis can be carried out using a catalyst or without one.

[0137] In the absence of a catalyst, the silica particles exhibit acidic sites on their surface. When a catalyst is used, examples of hydrolysis catalysts include metal chelates, organic acids, inorganic acids, organic bases, and inorganic bases. Examples of metal chelates as hydrolysis catalysts include triethoxy-mono(acetylacetone)titanium and triethoxy-mono(acetylacetone)zirconium. Examples of organic acids as hydrolysis catalysts include acetic acid and oxalic acid. Examples of inorganic acids as hydrolysis catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Examples of organic bases as hydrolysis catalysts include pyridine, pyrrole, piperazine, and quaternary ammonium salts. Examples of inorganic bases as hydrolysis catalysts include ammonia, sodium hydroxide, and potassium hydroxide.

[0138] The organic acid is at least one organic acid selected from dialiphatic carboxylic acids, aliphatic hydroxycarboxylic acids, amino acids, and chelating agents. Examples of dialiphatic carboxylic acids include oxalic acid, malonic acid, and succinic acid; examples of aliphatic hydroxycarboxylic acids include glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid; examples of amino acids include glycine, alanine, valine, leucine, serine, and threonine; and examples of chelating agents include ethylenediaminetetraacetic acid, L-aspartic-N,N-diacetic acid, and diethylenetriaminepentaacetic acid. Examples of organic acid salts include alkali metal salts, ammonium salts, and amine salts of the above-mentioned organic acids. Examples of alkali metals include sodium and potassium.

[0139] In this invention, a film-forming composition comprising the above-mentioned silica organic solvent sol and organic resin can be obtained.

[0140] Organic resins that can be used include polysiloxane resins, polyacrylic resins, epoxy resins, thiolated epoxy resins, phenolic varnish resins, maleimide resins, polyester resins, polyamide resins, polyimide resins, polyhydroxyimide resins, and polybenzo[a]ethylene glycol [B]. Poly(benzimidazole) resin, poly(benzothiazole) resin, polyamic acid resin, polyhydroxyamide resin, polyhydroxyazomethyl alkali resin, polyether resin, polybenzo[azo]pyridine resin Azine resins, polystyrene resins, polyhydroxystyrene resins, polyurethane resins, polyurea resins, condensation resins, or combinations thereof.

[0141] A composition for film formation can be obtained by mixing organic resins that are either thermosetting or photocurable. Furthermore, cured products can be prepared by using curing agents containing amine-based curing agents, anhydride-based curing agents, free radical generating agents (thermal free radical generators, photofree radical generators), or acid-generating agents (thermal acid generators, or photoacid generators).

[0142] Regarding this composition, a film-forming composition comprising an organic resin and a curing agent can be applied or filled onto a substrate and cured by heating, light irradiation, or a combination thereof. Examples of organic resins (curable resins) include resins having functional groups such as epoxy or (meth)acryloyl groups, and isocyanate-based resins. For example, light-curable polyfunctional acrylates are preferably used.

[0143] As a polyfunctional acrylate, examples include polyfunctional acrylates with 2, 3, 4 or more 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.

[0144] These multifunctional acrylates can also be described below.

[0145]

[0146]

[0147]

[0148]

[0149] The film-forming composition of the present invention may contain a surfactant (leveling agent).

[0150] As surfactants (leveling agents), anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and silicone surfactants can be used. The surfactant (leveling agent) can be added relative to the organic resin in the range of 0.01~5 phr or 0.01~1 phr.

[0151] Examples of anionic surfactants used in this invention include sodium and potassium salts of fatty acids, alkylbenzene sulfonates, higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, α-sulfonyl fatty acid esters, α-olefin sulfonates, monoalkyl phosphates, and alkane sulfonates.

[0152] Examples of alkylbenzene sulfonates include sodium, potassium, and lithium salts, such as C10-C16 sodium alkylbenzene sulfonate, C10-C16 alkylbenzene sulfonic acid, and sodium alkylnaphthalene sulfonate.

[0153] As higher alcohol sulfate salts, there are sodium dodecyl sulfate (sodium lauryl sulfate), triethanolamine lauryl sulfate, and triethanolamine lauryl sulfate, which have 12 carbon atoms.

[0154] As polyoxyethylene alkyl ether sulfates, there are sodium polyoxyethylene styrene phenyl ether sulfate, sodium polyoxyethylene styrene phenyl ether sulfate, sodium polyoxyethylene decyl ether sulfate, sodium polyoxyethylene decyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, sodium polyoxyethylene oleyl hexadecyl ether sulfate, etc.

[0155] As α-olefin sulfonates, there are sodium α-olefin sulfonate, etc.

[0156] Examples of alkane sulfonates include sodium 2-ethylhexyl sulfate.

[0157] Examples of cationic surfactants used in this invention include alkyl trimethylammonium salts, dialkyl dimethylammonium salts, alkyl dimethyl benzylammonium salts, and amine salts.

[0158] Alkyltrimethylammonium salts are quaternary ammonium salts with chloride and bromide ions as counterions. Examples include dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, cocoyltrimethylammonium chloride, and alkyl(C16-18)trimethylammonium chloride.

[0159] Dialkyl dimethyl ammonium salts have two lipophilic main chains and two methyl groups. Examples include bis(hydrogenated tallow) dimethyl ammonium chloride. Other examples include dialcyl dimethyl ammonium chloride, dicosyl dimethyl ammonium chloride, dihydrogenated tallow alkyl dimethyl ammonium chloride, and dialkyl (C14-18) dimethyl ammonium chloride.

[0160] Alkyl dimethyl benzyl ammonium salts are quaternary ammonium salts having one lipophilic main chain, two methyl groups, and a benzyl group; examples include benzalkonium chloride. Alkyl (C8-18) dimethyl benzyl ammonium chloride is another example.

[0161] As an amine salt agent, it is a substance in which the hydrogen atom of ammonia is replaced by one or more hydrocarbon groups, such as N-methylbis(hydroxyethyl)amine fatty acid ester hydrochloride.

[0162] Examples of amphoteric surfactants used in this invention include N-alkyl-β-alanine type alkylamino fatty acid salts, alkyl carboxybetaine type alkyl betaines, and N,N-dimethyldodecylamine oxide type alkylamine oxides. Examples of these include lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazoline betaine, and lauryl dimethylamine oxide.

[0163] The nonionic surfactants used in this invention are selected from 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. Examples of polyoxyethylene alkyl ethers include polyoxyethylene dodecyl ether (polyoxyethylene lauryl ether), polyoxyethylene alkylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene alkylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene oil-based ether, polyoxyethylene stearyl ether, polyoxyethylene sorbitanyl ether, polyoxyethylene-2-ethylhexyl ether, and polyoxyethylene isodecyl ether.

[0164] As polyoxyethylene alkylphenol ethers, there are polyoxyethylene styrene phenyl ethers, polyoxyethylene nonylphenyl ethers, polyoxyethylene styrene phenyl ethers, and polyoxyethylene tribenzylphenyl ethers.

[0165] As alkyl glucosides, there are decyl glucoside, lauryl glucoside, etc.

[0166] As polyoxyethylene fatty acid esters, there are polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyethylene glycol distearate, polyethylene glycol dioleate, and polypropylene glycol dioleate, etc.

[0167] As sorbitan fatty acid esters, there are sorbitan monocaprylate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monosesquioleate, and their ethylene oxide adducts, etc.

[0168] As polyoxyethylene sorbitan fatty acid esters, there are polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan triisostearate, etc.

[0169] In addition, as fatty acid alkanolamides, there are coconut oil fatty acid diethanolamide, tallow fatty acid diethanolamide, lauric acid diethanolamide, oleic acid diethanolamide, etc.

[0170] Furthermore, examples include polyoxyethylene polyoxypropylene glycol, polyoxyethylene fatty acid esters and other polyoxyalkyl ethers or polyoxyalkyl glycols, polyoxyethylene hydrogenated castor oil ether, sorbitan fatty acid ester alkyl ether, alkyl polyglucoside, sorbitan monooleate, sucrose fatty acid ester, etc.

[0171] Organosilicon surfactants can be used. Organosilicon surfactants are compounds with repeating units containing siloxane bonds in their main chain. Organosilicon surfactants can be used with a weight-average molecular weight in the range of 500 to 50,000. They can be modified organosilicon surfactants, for example, structures with organic groups introduced into the side chains and / or ends of polysiloxanes. Examples of organic groups include amino, epoxy, alicyclic epoxy, methanol, mercapto, carboxyl, aliphatic ester, aliphatic amide, and polyether groups. Examples of organosilicon surfactants include those with trade names... DC3PA SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (and above) (Manufactured by [Company Name]), Silwet L-77, L-7280, L-7001, L-7002, L-7200, L-7210, L-7220, L-7230, L7500, L-7600, L-7602, L-7604, L-7605, L-7622, ​​L-7657, L-8500, L-8610 (the above are...) Company-made), KP-341, KF-6001, KF-6002 (and above), Co., Ltd.), BYK307, BYK323, BYK330 (above, (e.g., company-made). For example, as a polyether-modified silicone, it is suitable to use the trade name L-7001 (made by DOWSIL).

[0172] In this invention, a film-forming composition containing the above-mentioned organic solvent sol and organic resin can be obtained. The film-forming composition can be formed by removing the organic solvent from the organic solvent sol, thereby forming a film-forming composition containing silica particles and organic resin.

[0173] When the above-mentioned film-forming composition is a thermosetting film-forming composition, a thermosetting agent can be added in the range of 0.01 to 50 phr or 0.01 to 10 phr relative to the resin containing functional groups such as epoxy groups or (meth)acryloyl groups. For example, the thermosetting agent can be contained in a ratio of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, relative to functional groups such as epoxy groups or (meth)acryloyl groups. The equivalent of the thermosetting agent relative to the curable resin is expressed as the equivalent ratio of the thermosetting agent to the functional group.

[0174] Examples of thermosetting agents include phenolic resins, amine-based curing agents, polyamide resins, imidazoles, polythiols, acid anhydrides, thermal free radical generators, and thermal acid-generating agents. Free radical generator-based curing agents, acid anhydride-based curing agents, and amine-based curing agents are particularly preferred.

[0175] These thermosetting agents, even if solid, can be used by dissolving them in a solvent. However, due to the evaporation of the solvent, the density of the cured product decreases and pores are formed, which leads to a decrease in strength and water resistance. Therefore, it is preferable that the curing agent itself is liquid at room temperature and pressure.

[0176] Examples of phenolic resins include phenolic varnish resin and cresol varnish resin.

[0177] Examples of amine-based curing agents include piperidine, N,N-dimethylpiperazine, triethylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthene diamine, isophorone diamine, diaminodicyclohexylmethane, 1,3-diaminomethylcyclohexane, phenylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and diethyltoluenediamine. Among them, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthene diamine, isophorone diamine, diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, diethyltoluene diamine, etc., can be preferably used as liquids.

[0178] As a polyamide resin, it is generated by the condensation of dimer acid and polyamine, and is a polyamide amine with primary and secondary amines in its molecule.

[0179] Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-undecylimidazole. Triterpenoids, epoxide imidazole adducts, etc.

[0180] Polythiols are substances containing thiol groups at the ends of polypropylene glycol chains or polyethylene glycol chains, and are preferably in liquid form.

[0181] As an anhydride-based curing agent, anhydrides containing multiple carboxyl groups in one molecule are preferred. Examples of such anhydride-based curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol dipreptyltrimethacrylate, glycerol trimellitic trimethacrylate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylenetetrahydrophthalic anhydride, methylmethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, and chlorhexidine anhydride.

[0182] Examples of heat-generating acid agents include matte salts, Salts, but sulfite salts are preferred. Examples of such compounds include the following.

[0183]

[0184] Examples of R include alkyl groups having 1 to 12 carbon atoms and aryl groups having 6 to 20 carbon atoms, with alkyl groups having 1 to 12 carbon atoms being particularly preferred.

[0185] The preferred formulations are mixtures of methyltetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride (methylnadic anhydride), hydrogenated methylnadic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methylhexahydrophthalic anhydride, and hexahydrophthalic anhydride, which are liquid at room temperature and pressure. The viscosity of these liquid anhydrides is measured at 25°C to be approximately 10 mPa·s to 1000 mPa·s.

[0186] Examples of thermal free radical generators include, for instance, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanitrile), 4,4'-azobis(4-cyanopentanoic acid), dimethyl 2,2'-azobis(2-methylpropionic acid) ester, 2,2'-azobis(2-methylpropanediol) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, tert-butyl hydroperoxide, cumyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, etc. These are available from Tokyo Chemical Industry Co., Ltd.

[0187] In addition, when obtaining the above-mentioned cured product, a curing aid may be appropriately used in conjunction. Examples of curing aids include organophosphorus compounds such as triphenylphosphine and tributylphosphine, and ethyltriphenyl bromide. methyltriphenyl diethyl phosphate and other quaternary compounds Salts, quaternary ammonium salts such as 1,8-diazabicyclo(5,4,0)undecane-7-ene, 1,8-diazabicyclo(5,4,0)undecane-7-ene and octanoic acid salts, zinc octanoate, and tetrabutylammonium bromide. These curing aids may be contained in a proportion of 0.001 to 0.1 parts by weight relative to 1 part by weight of the curing agent.

[0188] The composition can be obtained by mixing resin, curing agent, and optional curing aids to obtain a thermosetting varnish. Mixing can be carried out in a reaction vessel using stirring blades or a kneader.

[0189] Mixing is carried out by heating at a temperature of 60℃ to 100℃ for 0.5 to 1 hour.

[0190] The resulting curable film-forming composition is a thermosetting coating composition, for example, having a suitable viscosity for use as a liquid sealing material. The liquid thermosetting film-forming composition can be formulated to any viscosity, allowing for partial sealing at any location for use as a transparent sealing material for LEDs, etc., via casting, potting, dispenser methods, printing, etc. After directly mounting the liquid thermosetting composition onto LEDs, etc., using the above method, followed by drying and curing, an epoxy resin cured body is obtained.

[0191] A thermosetting film-forming composition (thermosetting coating composition) is applied to a substrate and heated at a temperature of 80~200°C to obtain a cured product.

[0192] When the above-mentioned film-forming composition is a photocurable resin composition, a photocuring agent (photoradical generator, photoacid generator) can be added in the range of 0.01 to 50 phr or 0.01 to 10 phr relative to the resin containing functional groups such as epoxy groups or (meth)acryloyl groups. 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, relative to functional groups such as epoxy groups or (meth)acryloyl groups. The equivalent of the photocuring agent relative to the curable resin is expressed as the equivalent ratio of the photocuring agent to the functional group.

[0193] Photoradical generators are any substances that can generate free radicals directly or indirectly through light irradiation; there are no particular limitations.

[0194] Examples of photoradical generators and photoradical polymerization initiators include imidazole compounds, diazo compounds, diimidazole compounds, N-arylglycine compounds, organic azide compounds, titanocene compounds, aluminate compounds, organic peroxides, and N-alkoxypyridines. Salt compounds and thioxanone compounds, etc. Examples of azide compounds include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzylacetylphenylene, 4,4'-diazidochalcone, 4,4'-diazidodiphenyl sulfide, and 2,6-bis(4'-azidobenzylene)-4-methylcyclohexanone. Examples of diazo compounds include 1-diazo-2,5-diethoxy-4-p-tolyl mercaptophenyl fluoroboride, 1-diazo-4-N,N-dimethylaminochlorobenzene, and 1-diazo-4-N,N-diethylaminophenyl fluoroboride. Examples of bisimidazole compounds include 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetra(3,4,5-trimethoxyphenyl)1,2'-bisimidazole and 2,2'-bis(o-chlorophenyl)4,5,4',5'-tetraphenyl-1,2'-bisimidazole. Examples of diacetalpine 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), and dicyclopentadienyl-titanium-bis(2,6-difluorophenyl). Alkenyl-titanium-bis(2,4-difluorophenyl), 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-pyrrole-1-yl)-phenyl), etc.

[0195] Other examples of photoradical generators include 1,3-bis(tert-butyldioxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-butyldioxycarbonyl)benzophenone, and 3-phenyl-5-isobenzophenone. Zyrazole, 2-mercaptobenzimidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, etc.

[0196] These photoradical polymerizing agents can be obtained, for example, as BASF's Irgacure TPO (containing 2,4,6-trimethylbenzoyl diphenylphosphine oxide) (c1-1-1), IGM RESINS' Omnirad 819 (containing bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) (c1-1-2), and IGM RESINS' Irgacure 184 (containing 1-hydroxycyclohexylphenyl ketone) (c1-1-3).

[0197]

[0198] Photoacid generators are any substances that can produce acid directly or indirectly through light irradiation; there are no special limitations.

[0199] Specific examples of photoacid-generating agents include triazine compounds, acetophenone derivatives, disulfone compounds, diazomethane compounds, sulfonic acid derivatives, and iodine. Salt, matte salt, Salt, selenium salt, etc. Salts, metallocene complexes, iron aromatic hydrocarbon complexes, etc.

[0200] Used as the aforementioned photoacid generator Salt, as iodine Examples of salts include diphenyl iodine chloride. diphenyliodine Trifluoromethanesulfonate, diphenyliodine Methanesulfonate, diphenyliodine Toluenesulfonate, diphenyliodine bromide diphenyliodine Tetrafluoroborate, diphenyliodide Hexafluoroantimonate, diphenyliodine Hexafluoroarsenate, bis(p-tert-butylphenyl)iodine Hexafluorophosphate, bis(p-tert-butylphenyl)iodine Methanesulfonate, bis(p-tert-butylphenyl)iodine Toluenesulfonate, bis(p-tert-butylphenyl)iodide Trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodine Tetrafluoroborate, bis(p-tert-butylphenyl)iodine chloride bis(p-chlorophenyl)iodine chloride bis(p-chlorophenyl)iodine Tetrafluoroborate and bis(4-tert-butylphenyl)iodide Bis(alkylphenyl)iodine, such as hexafluorophosphate Salt, alkoxycarbonylalkoxy-trialkylaryliodine Salts (e.g., 4-[(1-ethoxycarbonyl-ethoxy)phenyl]-(2,4,6-trimethylphenyl)iodine) Hexafluorophosphate, etc., bis(alkoxyaryl)iodine Salts (e.g., (4-methoxyphenyl)phenyl iodide) Hexafluoroantimonate and other bis(alkoxyphenyl)iodine Salt).

[0201] Examples of sulfonium salts include triphenylsulfonium chloride, triphenylsulfonium bromide, tri(p-methoxyphenyl)sulfonium tetrafluoroborate, tri(p-methoxyphenyl)sulfonium hexafluorophosphonate, tri(p-ethoxyphenyl)sulfonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, etc.; (4-phenylthienyl)diphenylsulfonium hexafluoroantimonate, (4-phenylthienyl)diphenylsulfonium hexafluorophosphate, bis[4-(diphenylsulfonium)phenyl]sulfide-bis-hexafluoroantimonate, bis[4-(diphenylsulfonium)phenyl]sulfide-bis-hexafluorophosphate, (4-methoxyphenyl)diphenylsulfonium hexafluoroantimonate, etc.

[0202] As Salts, for example, triphenylchloride Triphenylbromide Tris(p-methoxyphenyl) Tetrafluoroborate, tris(p-methoxyphenyl) Hexafluorophosphonate, tris(p-ethoxyphenyl) Tetrafluoroborate, 4-chlorobenzyldiazo Hexafluorophosphate, benzyltriphenyl Hexafluoroantimonates, etc. Salt.

[0203] Examples of selenium salts include triphenylselenohexafluorophosphate, and metallocene complexes include (η5 or η6-isopropylbenzene)(η5-cyclopentadienyl)iron(II)hexafluorophosphate.

[0204] In addition, the following compounds can also be used as photoacid generators.

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214] As photoacid-generating agents, sulfonium salt compounds and iodine are preferred. Salt compounds. Examples of their anions include CF3SO3-, C4F9SO3-, and C8F4SO3-. 17 SO3-, camphorsulfonic acid anion, toluenesulfonic acid anion, BF4-, PF6-, AsF6 - and SbF6 - Etc. Especially preferred are anionic compounds such as phosphorus hexafluoride and antimony hexafluoride, which exhibit strong acidity.

[0215] Depending on the requirements, the film-forming composition of the present invention may contain conventional additives. Examples of such additives include pigments, colorants, thickeners, sensitizers, defoamers, coatability modifiers, lubricants, stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), plasticizers, solubilizers, fillers, antistatic agents, etc. These additives may be used alone or in combination of two or more.

[0216] Examples of coating methods for the film-forming composition of the present invention include flow coating, spin coating, spray coating, screen printing, casting, bar coating, curtain coating, roller coating, gravure coating, immersion coating, and slot coating.

[0217] In this invention, a photocoating composition (a composition for film formation) can be applied to a substrate and cured by light irradiation. Alternatively, heating can be performed before or after light irradiation.

[0218] The thickness of the coating can be selected from about 0.01μm to 10mm depending on the application of the cured material. For example, it can be about 0.05 to 10μm (especially 0.1 to 5μm) for photoresist, about 5μm to 5mm (especially 100μm to 1mm) for printed circuit boards, and about 0.1 to 100μm (especially 0.3 to 50μm) for optical films.

[0219] When a transparent coating is obtained, the visible light transmittance of the coating can be above 80% or 90%, typically 90-96%.

[0220] The light used for irradiation or exposure when using photoacid-generating agents can be, for example, gamma rays, X-rays, ultraviolet light, or visible light, typically visible light or ultraviolet light, especially ultraviolet light. The wavelength of the light is, for example, 150-800 nm, preferably 150-600 nm, and more preferably around 150-400 nm. The amount of irradiated light varies depending on the thickness of the coating, for example, it can be 2-20000 mJ / cm². 2 Preferably, it is 5~5000mJ / cm 2The light source can be selected based on the type of light being exposed. For example, under ultraviolet light, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, deuterium lamps, halogen lamps, lasers (helium-cadmium lasers, excimer lasers, etc.) can be used. The composition undergoes a curing reaction under such light irradiation.

[0221] When using a heat-generating acid agent, or a photo-generating acid agent, the coating film is heated as needed after light irradiation, for example, at 60~350℃, preferably around 100~300℃. The heating time can be selected from a range of more than 3 seconds (e.g., 3 seconds to about 5 hours), for example, 5 seconds to 2 hours, preferably around 20 seconds to 30 minutes, and usually around 1 minute to 3 hours (e.g., 5 minutes to 2.5 hours).

[0222] Furthermore, in cases where patterns or images are formed (e.g., in the manufacture of printed circuit boards), the coating film formed on the substrate can be pattern-exposed. This pattern exposure can be performed by laser scanning or by irradiation through a photomask. By developing (or dissolving) the unexposed areas (unexposed portions) generated by such pattern exposure with a developer, patterns or images can be formed.

[0223] As a developer, alkaline aqueous solutions and organic solvents can be used.

[0224] Examples of alkaline aqueous solutions include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, ethyltrimethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine.

[0225] The aforementioned alkaline developer is generally an aqueous solution of 10% by mass or less, preferably an aqueous solution of 0.1% to 3.0% by mass. Furthermore, alcohols and surfactants can also be added to the aforementioned developer, preferably in amounts of 0.05 to 10 parts by mass relative to 100 parts by mass of the developer.

[0226] One of the methods is to use an aqueous solution of tetramethylammonium hydroxide or ethyltrimethylammonium hydroxide at a mass percentage of 0.1 to 2.38%.

[0227] In addition, common organic solvents can be used as the developing solution, such as acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, ethyl lactate, cyclohexanone, etc., and one or a mixture of two or more of them can be used. Propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, etc. are particularly preferred.

[0228] In this invention, to improve the adhesion between the substrate and the substrate after development, an adhesion promoter can be added. Examples of such adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; and alkoxysilanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, and dimethyltrimethylsilyl... Silazanes such as silylamine and trimethylsilylimidazolium; silanes such as vinyltrichlorosilane, 3-chloropropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, and 3-(N-piperidinyl)propyltrimethoxysilane; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzo[] Heterocyclic compounds such as azoles, urazoles, thiouracil, mercaptoimidazoles, and mercaptopyrimidines, and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. One or more of the above-mentioned adhesion promoters may be used. The amount of these adhesion promoters added is generally less than 18% by mass in the solid content, preferably 0.0008 to 9% by mass, more preferably 0.04 to 9% by mass.

[0229] In this invention, a sensitizer may also be included. Examples of usable sensitizers include anthracene, phenothiazine, perylene, thioxanthone, and benzophenone-thioxanthone. Furthermore, thiopyran can be used as a sensitizing pigment. Thiopyrylium salt pigments, anthocyanin pigments, quinoline pigments, styrylylquinoline pigments, ketocoumarin pigments, thiopyrrolidone pigments Tonylene pigments, Oxonol pigments, Anthocyanin pigments, Rhodamine pigments, Pyranylene pigments Salt-based pigments, etc. Anthracene-based sensitizers are particularly preferred, as their sensitivity is dramatically increased when used in conjunction with a cationic curing catalyst (radiosensitive cationic polymerization initiator), while also possessing free radical polymerization initiation capabilities. In hybrid systems combining the cationic curing system and the free radical curing system of this invention, the type of catalyst can be simplified. Specific anthracene compounds such as dibutoxyanthracene and dipropoxyanthraquinone are effective. The sensitizer is used in a proportion of 0.01 to 20% by mass, preferably 0.01 to 10% by mass, of the solid component.

[0230] The compositions of the present invention can be photocured or thermally cured using photoradicals, thermalradicals, photoacid generators, or thermal acid generators. When using photoacid generators or thermal acid generators, conventional epoxy curing agents (e.g., amines, anhydrides) are not used, or even if they are used, their content is very low, thus improving the storage stability of the compositions.

[0231] The above composition was found to be suitable for photocationic polymerization. It exhibits a higher curing speed than existing liquid epoxy compounds (e.g., alicyclic epoxy compounds with an epoxy cyclohexyl ring). Due to the rapid curing speed, the amount of acid-generating agent added can be reduced, or a weak acid-based acid-generating agent can be used. Reducing the amount of acid-generating agent is important for preventing metal corrosion caused by residual acidic active species after UV irradiation. Due to the rapid curing speed, thick film curing is possible.

[0232] Curing by UV irradiation can be applied to heat-sensitive materials (mechanical materials).

[0233] The thermosetting and photocuring materials using the film-forming compositions of the present invention have characteristics such as rapid hardening, transparency, and low curing shrinkage, and can be used for coating and bonding electronic components, optical components (anti-reflective films), and precision mechanical components. For example, they can be used for bonding optical components such as lenses for mobile phones or cameras, light-emitting diodes (LEDs), and semiconductor lasers (LDs), liquid crystal panels, biochips, camera lenses or prisms, magnetic components of hard drives for personal computers, pickups (the part that picks up light information reflected from the disc) in CD and DVD players, conical diaphragms and coils in loudspeakers, magnets in electric motors, circuit boards, electronic components, and internal components of automobile engines.

[0234] As a hard coating material for surface protection of automobile bodies, lamps or electrical products, building materials, plastics, etc., it can be applied to automobile and motorcycle bodies, headlight lenses or reflectors, plastic lenses for eyeglasses, mobile phones, game consoles, optical films, ID cards, etc.

[0235] As ink materials are intended for printing on metals such as aluminum and plastics, examples include inks used for cards such as credit cards and membership cards, switches for electrical products or OA equipment, inks for keyboard printing, and inks for inkjet printers such as CDs and DVDs.

[0236] Examples include technologies that combine resin with 3D CAD to form complex three-dimensional objects through curing; light modeling suitable for industrial product model making; and coatings, bonding, waveguides, and thick-film resists suitable for optical fibers.

[0237] In addition, the film-forming composition of the present invention can be used as an insulating resin for electronic materials such as anti-reflective films, semiconductor sealing materials, adhesives for electronic materials, printed circuit board materials, interlayer insulating film materials, and sealing materials for power supply components, or as an insulating resin used in high-voltage equipment such as generator coils, transformer coils, and gas-insulated switching devices.

[0238] In this invention, silica particles capable of redispersibility in a developer containing organic solvents or alkaline aqueous solutions can be incorporated into the coating composition. Solubility in the developer is achieved based on the surface potential present on the surface of the hollow silica particles, and selective developability to organic solvents or alkaline aqueous solutions can be achieved by attaching organic functional groups to the surface. 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.

[0239] As an example, when the developer is an organic solvent, hydrophobic functional groups such as alkyl and aryl groups contribute to the redispersibility of the silica particles. These functional groups are preferably silane coupling agents having one hydrolyzable group (i.e., silane coupling agents having three organic groups), silane coupling agents having two hydrolyzable groups (i.e., silane coupling agents having two organic groups), or combinations thereof. A silane coupling agent having one hydrolyzable group can be combined with a silane coupling agent having two hydrolyzable groups, and can be used in a ratio of 1:3 to 1:1 based on the aforementioned silane groups. Alkyl groups include methyl, ethyl, and propyl, and aryl groups include phenyl. Methylphenylsilane and trimethylsilane are preferably examples of silane groups. Each square nm of silica particles may have 2 to 6 or 2 to 4 of the aforementioned silane groups. The organic solvent is an alcohol, ketone, ester, or glycol, such as methanol, acetone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, n-butyl acetate, ethyl lactate, etc.

[0240] As an example, when the developing solution is an alkaline aqueous solution, C1-C3 alkyl groups, carboxyl groups, protected carboxyl groups, and amino acid ester groups (e.g., N-methylpropylamino propionate) contribute to the redispersibility of the silica particles. These functional groups can be provided by silane coupling agents having one hydrolyzable group (i.e., silane coupling agents having three organic groups), or secondary amines (diisopropanolamine) and tertiary amines (e.g., tripentylamine). The silica particles have 2-6, 2-4, or 1-2 of the aforementioned silyl groups per square nm, but one can be used to improve solubility in alkaline aqueous solutions. Examples of alkaline aqueous solutions being alkali metal hydroxides or quaternary ammonium hydroxides include aqueous solutions of tetramethylammonium hydroxide, ethyltrimethylammonium hydroxide, and potassium hydroxide.

[0241] As a test method for the solubility of the aforementioned silica particles, after the organic solvent dispersion of the silica particles is dried under drying conditions of 60°C and 50 Torr, the average particle size in the developing solution when redispersed in a developing solution containing an organic solvent or an alkaline aqueous solution, measured by dynamic light scattering (DLS), can be (DLS particle size of silica particles in the developing solution) / (DLS particle size of silica particles in the organic solvent) = 0.5~4.0 or 0.5~2.0. When the silica particles are not redispersed in the developing solution, they form a suspension, and sometimes the DLS particle size increases.

[0242] The method for manufacturing the laminated substrate of the present invention may include the following steps: (i) applying a coating composition onto a substrate and drying it to form a coating film, and (ii) curing the coating film.

[0243] The curing of step (ii) above can be achieved by heat curing, light curing, or a combination thereof.

[0244] (ii) The curing of the process can be achieved by exposure on the coated film through a mask.

[0245] The above-described method for manufacturing laminated substrates may include an additional step (iii) of developing or planarizing after curing. Developing or planarizing may be performed using organic solvents or alkaline aqueous solutions.

[0246] When the coating film is a resist film, the substrate can be processed by gas etching (dry etching) or developer etching (wet etching) after development.

[0247] The aforementioned coating film can be formed into an upper film, a lower film, or films formed on both sides to create a multilayer substrate containing multiple films. The upper and lower films can be formed into an anti-reflective film with alternating layers of low-refractive-index and high-refractive-index films.

[0248] The coating composition comprises silica particles and a resin, which may include polysiloxane resins, polyacrylic resins, epoxy resins, thiolated epoxy resins, phenolic varnish resins, maleimide resins, polyester resins, polyamide resins, polyimide resins, polyhydroxyimide resins, and polybenzo[a]ethylene glycol resins. Poly(benzimidazole) resin, poly(benzothiazole) resin, polyamic acid resin, polyhydroxyamide resin, polyhydroxyazomethyl alkali resin, polyether resin, polybenzo[azo]pyridine resin Azide resins, polystyrene resins, polyhydroxystyrene resins, polyurethane resins, polyurea resins, condensation resins, or combinations thereof. They may contain free radical generating agents or acid-generating agents (thermal acid-generating agents, photo-acid-generating agents) for thermocuring, photocuring, or combinations thereof.

[0249] The aforementioned resins, such as polysiloxane resins, can be obtained by hydrolysis of the silane compound and subsequent dehydration condensation. This hydrolysis and condensation can be achieved according to the hydrolysis conditions of the aforementioned silane coupling agent.

[0250] Silane compounds can be manufactured by combining tetrafunctional silanes (silane compounds having four hydrolyzable groups) with trifunctional silanes (silane compounds having three hydrolyzable groups and one organic group), difunctional 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 based on combinations of tetrafunctional and trifunctional silanes can be cited.

[0251] Examples of tetrafunctional silanes include tetraethoxysilane and tetramethoxysilane. Tetraethoxysilane is particularly preferred.

[0252] Examples of trifunctional silanes include: methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, and other alkyl silanes.

[0253] aryl silanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyltrimethoxysilane, and phenylmethyltriethoxysilane.

[0254] Vinyltrimethoxysilane, vinyltriethoxysilane, and other vinyl silanes

[0255] Epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, and 3-epoxypropoxypropyltriethoxysilane are epoxy silanes.

[0256] For styrene-based silanes such as styrenetrimethoxysilane,

[0257] 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropylmethyldiethoxysilane, 3-Methacryloxypropyltriethoxysilane, and other methacryloyl silanes

[0258] 3-Acryloyloxypropyltrimethoxysilane and other acryloyl silanes,

[0259] N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N,N-dimethylaminopropyltrimethoxysilane, and the hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, etc., are amine silanes.

[0260] Tri-(trimethoxysilylpropyl)isocyanurate, diallyl(trimethoxysilylpropyl)isocyanurate, and other isocyanurate-based silanes

[0261] 3-Urea-propyltrialkoxysilane and other urea-based silanes

[0262] 3-Mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and other mercaptosilanes

[0263] Isocyanate-based silanes such as 3-isocyanate-propyltriethoxysilane.

[0264] Examples of polysiloxane resins include those obtained by copolymerizing tetraethoxysilane, methyltrimethoxysilane, and phenyltrimethoxysilane, and those 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.

[0265] For example, the aforementioned polysiloxane resin can be dissolved in a glycol solvent such as propylene glycol ethyl ether, and silica particles can be mixed at a mixing ratio of 100 phr. Then, the solvent can be replaced with propylene glycol monomethyl ether at 50 Torr 80°C, and the resulting varnish can be used as a coating composition. The concentration of silica in these coating compositions can be set to 1-30% by mass, or 5-30% by mass, or 10-3% by mass. Furthermore, the dynamic light scattering particle size in the coating composition can be set to a range of 10-200 nm, or 10-100 nm, or 30-90 nm. For example, when a transparent film is used as a substrate, a laminated substrate with a film thickness of 0.1-100 μm, or 0.1-30 μm, or 1-10 μm, or 1-3 μm can be obtained by coating the above-mentioned coating composition and heating and drying at 80-100°C for 1-60 minutes.

[0266] The dielectric constant and dielectric loss tangent of these transparent film substrates can be measured.

[0267] Example

[0268] The following describes specific embodiments of the present invention. It should be noted that the present invention is not limited in any way by the following embodiments.

[0269] The abbreviations of the compounds used in the following examples are shown below.

[0270] (Solvent, developer)

[0271] PGME: Propylene Glycol Monomethyl Ether

[0272] PGEE: Propylene Glycol Monoethyl Ether

[0273] PGMEA: Propylene glycol monomethyl ether acetate

[0274] EL: Ethyl lactate

[0275] DMAC: N-Dimethylacetamide

[0276] ACBu: Butyl acetate

[0277] MeOH: Methanol

[0278] AC: Acetone

[0279] CHO: Cyclohexanone

[0280] ETMAH: Ethyltrimethylammonium hydroxide

[0281] NMP: N-methyl-2-pyrrolidone

[0282] KOH: Potassium hydroxide

[0283] MEK: Methyl Ethyl Ketone

[0284] (amines)

[0285] TnPA: Triamylamine

[0286] DiPA: Diisopropylamine

[0287] DiPEA: Diisopropylethylamine

[0288] (Silanes)

[0289] MPDMS: Methylphenyldimethoxysilane

[0290] TMSO: Hexamethyldisiloxane

[0291] MTMS: Methyltrimethoxysilane

[0292] PTMS: Phenylacetyltrimethylsilane

[0293] TEOS: Tetraethoxysilane

[0294] APS: 3-Aminopropyltriethoxysilane

[0295] M33TMOSPAP: Methyl 3-((3-(trimethoxysilyl)propyl)amino)propionate, manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name X-88-475

[0296] (Isocyanate compounds)

[0297] AOI-VM: 2-Acryloyloxyethyl Isocyanate Co., Ltd. Manufacturer, Trade Name AOI-VM

[0298] EICYA: Ethyl isocyanate

[0299] The silica sol, particles, product name, and abbreviation used are shown below.

[0300] (Water-dispersed silica sol, organic solvent-dispersed silica sol)

[0301] Product Name O-40: Aqueous silica sol with an average primary particle size of 22 nm (manufactured by Nissan Chemical Co., Ltd., aqueous dispersible sol of solid silica particles).

[0302] Product Name MSH: Aqueous silica sol with an average primary particle size of 17 nm (manufactured by Nissan Chemical Co., Ltd., aqueous sol of solid silica particles)

[0303] • Product Name HKT-A20-40: Aqueous Dispersed Silica Sol with an Average Primary Particle Size of 40nm (Made by Ningbo Dilato, Aqueous Dispersed Silica Particles)

[0304] • Product Name PL-3: Aqueous Dispersible Silica Sol with an Average Primary Particle Size of 35nm (Manufactured by Fuso Chemical Co., Ltd., Aqueous Dispersible Sol of Solid Silica Particles)

[0305] • Trade name MT-ST: Methanol-dispersed silica sol with an average primary particle size of 12nm (manufactured by Nissan Chemical Co., Ltd., methanol-dispersed sol of solid silica particles)

[0306] • Trade name MA-ST-L: Methanol-dispersed silica sol with an average primary particle size of 45nm (manufactured by Nissan Chemical Co., Ltd., methanol-dispersed sol of solid silica particles)

[0307] (Determination of silicon dioxide (SiO2) concentration)

[0308] The silica concentration of water-dispersed silica sol, organic solvent-dispersed silica sol, and dispersions of surface-modified silica particles is calculated by taking these silica sols or dispersions into a crucible, removing the solvent by heating, calcining at 1000°C, and measuring the residual components after calcination.

[0309] (Determination of composition concentration)

[0310] The concentration of the composition was calculated by measuring approximately 1.00 g in an aluminum cup and firing it at 200°C for 2 hours to measure the residual components after firing.

[0311] (pH determination method for water-dispersed silica sol)

[0312] The pH of water-dispersed silica sol is determined using a pH meter. (Manufactured by (Company Name: MM-43X)) was tested.

[0313] (pH determination method for silica sol dispersed in organic solvents)

[0314] Regarding the pH of organic solvent-dispersed silica sol, the liquid obtained by mixing the sample containing organic solvent-dispersed silica sol with methanol and pure water at a mass ratio of 1:1:1 was measured using a pH meter. The product (manufactured by (Company Name), trade name MM-43X) was tested.

[0315] (Moisture content)

[0316] The water content of the dispersion of surface-modified silica particles and the silica sol in its manufacturing process was determined by Karl Fischer titration using a Karl Fischer moisture meter (manufactured by Kyoto Electronics Co., Ltd., trade name: MKA-610).

[0317] (Organic solvent content)

[0318] The organic solvent content in the dispersion of surface-modified silica particles was determined by gas chromatography (Shimadzu Corporation, product name: GC-2014s).

[0319] Gas chromatography conditions:

[0320] Column: 3mm x 1m glass column

[0321] Filler: Porapak Q

[0322] Column temperature: 130~230℃ (heating rate 8℃ / min)

[0323] Carrier gas: N2 40 mL / min

[0324] Detector: FID

[0325] Injection volume: 1μL

[0326] Internal standard: Acetonitrile was used.

[0327] (Viscosity measurement)

[0328] The viscosity of the dispersion in the surface-treated silica particle manufacturing process was measured at 25°C using an Ostwald viscometer (manufactured by Shibata Scientific Co., Ltd.).

[0329] Specific surface area (S) of nitrogen adsorption method N2 (determination)

[0330] The specific surface area (S) of silica particles in water-dispersed silica sol by nitrogen adsorption method N2 The water-soluble cations in the water-dispersed silica sol are treated with a cation exchange resin ( Company structure, product name: After removing the silica sol (IR-120B), the silica sol was dried at 290°C to serve as the test sample. The sample was then analyzed using a nitrogen adsorption method with a surface area measuring device (trade name Monosorb). The measurement was conducted using a contract company system.

[0331] (IR measurement)

[0332] A sample (surface treatment agent: a mixture of M33TMOSPAP, MEK, and AOI-VM, as described in Synthesis Example 13 below) was coated on a silicon substrate. After removing the solvent by heating at 100°C for 10 minutes, the sample was analyzed using an infrared absorption spectroscopy apparatus (apparatus name: iS50FT-IR). (Manufactured by [Company Name]) A total of 32 transmission-based IR measurements were performed (measurement range: 4000–4000 cm⁻¹). -1 The positions of the IR peaks (cm) are obtained from the spectrum measured by IR. -1 ).

[0333] (Average primary particle size measured by nitrogen adsorption method)

[0334] The average primary particle size measured by nitrogen adsorption method is derived from the specific surface area S obtained by the nitrogen adsorption method described above. N2 (m 2 / g) is calculated using the following formula to convert to spherical particles.

[0335] The average primary particle size (nm) measured by nitrogen adsorption method was 2720 / S. N2 (m 2 / g)

[0336] (Dynamic light scattering particle size (average particle size (nm) measured by DLS method))

[0337] The average particle size (Z-average particle size) obtained by DLS was measured using a dynamic light scattering particle size analyzer (manufactured by Malvern Panalytical, product name: Zetasizer Nano). It should be noted that the diluent used to measure the average particle size by DLS was the same solvent as the main component contained in the dispersion medium of the silica particle dispersion.

[0338] (Mean primary particle size determination by TEM (transmission electron microscopy))

[0339] The particles in the silica sol were photographed using a transmission electron microscope (JEM-F200, manufactured by Nippon Electron Ltd.), and the images were analyzed using an automatic image processing and analysis device. The product (trade name LUZEX'AP) is used to binarize approximately 300 randomly selected particles, and the diameter of the projected area converted into a circle is used as the average first particle size (HEYWOOD diameter) for measurement.

[0340] (Determination of the amount of aluminum (B) present in all silica particles / dissolution method)

[0341] The precisely weighed silica sol was dried, and the silica components were removed by treatment with hydrofluoric acid solution, dissolving the residue in a nitric acid aqueous solution. The aluminum content in the resulting aqueous solution was determined using an ICP-based luminescence analyzer. The aluminum content present in the entire silica particles was converted to Al2O3, and the content of 1g SiO2 relative to silica was calculated (Al2O3(ppm) / SiO2).

[0342] (Determination of aluminum content (A) on the surface of silica particles / Leaching method)

[0343] The cationic components in the silica sol were removed using an H-type cation exchange resin. The dried product, after solvent removal by heat treatment, was pulverized in a mortar and further treated at 250°C for 2 hours. A polypropylene container (PP) was then prepared by adding 20 mL of 0.1 mol / L (N / 10) nitric acid aqueous solution. Add 0.2g of the obtained powder to a 50mL bottle and mix vigorously by hand. Then, use an ultrasonic cleaner ( The powder (trade name ASU CLEANER ASU-10M) was ultrasonically treated for 10 minutes to ensure thorough wetting of the powder with nitric acid aqueous solution. It was then placed in a 50°C constant temperature bath and maintained for 17 hours. The solution was then cooled to 25°C and added to a centrifugal ultrafiltration filter (trade name Amicon Ultra-15, molecular weight cutoff 10,000). The aluminum content in the filtrate obtained from the centrifugation process was determined using an ICP-C luminescence analyzer. The aluminum content bound to the surface of the silica particles was converted to Al2O3, and the content of 1g SiO2 relative to silica (Al2O3(ppm) / SiO2) was calculated.

[0344] (Determination of the surface charge of silicon dioxide particles)

[0345] The sample for analysis was prepared by diluting 10 mL of methanol with silica sol to a silica concentration of 0.5% by mass. The sample was then analyzed using a particle charge meter. (Manufactured by [Company Name], trade name PCD-06), using a 0.001 mol / L (N / 1000) DADMAC solution as the cation standard titrant. (Manufactured by [Company Name]), the titration value was determined until the flow potential of the sample became 0. The resulting titration value was converted to a value relative to 1 g of hollow silica particles by dividing the mass of silica contained in the sample, and this value was taken as the surface charge (μeq / g-SiO2). It should be noted that DADMAC stands for poly(diallyldimethylammonium chloride).

[0346] (Synthesis example 1)

[0347] Synthesis of MeOH dispersion sol containing aluminum hollow silica particles (a1)

[0348] (1) Preparation of aqueous dispersion sol containing aluminum hollow silica particles (a)

[0349] 2015g of commercially available hollow silica aqueous sol HKT-A20-40 (trade name) was placed in a 3L plastic container. 169g of sodium aluminate diluted to a 1.0% (w / w) concentration (based on Al2O3 conversion) was added dropwise over 1 minute. 6g of sodium sulfate aqueous solution (based on a 10% (w / w) concentration (based on Na2SO4 conversion) was then added dropwise. The mixture was stirred for 30 minutes at 600 rpm using a mechanical stirrer with glass blades. Next, 800g of the mixture was added to a glass separable flask and heated at 80°C for 5 hours, then cooled to 25°C. Subsequently, the mixture was passed through a column-packed cation exchange resin (trade name H-type) at a space velocity (SV) of 5 / hour. An aqueous dispersion sol containing aluminum hollow silica particles was obtained using IR-120B (a). The physical properties of the obtained sol were determined, showing a SiO2 concentration of 16.9% by mass, pH 2.6, an average particle size of 54 nm (measured by DLS), and a specific surface area (C) of 149 m² (measured by BET). 2 / g, Aluminum content bound to the particle surface (A) 1500ppm, Aluminum content in the entire silica particles converted to Al2O3 relative to 1g SiO2 of silica (B) 1900ppm, (A / B ratio) 0.79, Average primary particle size observed by TEM 43nm, TEM-converted specific surface area (D) 63m² 2 / g, specific surface area ratio (C / D ratio) 2.4, particle refractive index 1.26, shell thickness 6.7nm.

[0350] (2) Preparation of MeOH dispersion sol containing aluminum hollow silica particles (a1)

[0351] 118.3 g of an aqueous dispersion sol (a) containing aluminum hollow silica particles was added to a 300 mL round-bottom flask, followed by the addition of 15.0 g of methanol. The methanol was replaced in a rotary evaporator under reduced pressure of 580 Torr and heating at 120 °C to obtain a MeOH dispersion sol (a1) containing aluminum hollow silica particles. The properties of the resulting sol were: pH 3.7, average particle size of 64 nm (measured by DLS), SiO2 concentration of 24.2% by mass, water content of 0.3% by mass, viscosity of 1.9 mPa·s, and surface charge of the hollow silica particles converted to 59 μeq / g per g of SiO2.

[0352] (Synthesis example 2)

[0353] Synthesis of MeOH Dispersed Solid Silica Sol (a2)

[0354] 14000g O-40 (trade name) was produced by ultrafiltration of MeOH to remove water. The replacement was stopped when the water content reached 0.5% by mass, resulting in a MeOH-dispersed solid silica sol. The physical properties of the obtained sol were as follows: SiO2 concentration 40.6% by mass, water content 0.5% by mass, viscosity 5.4 mPa·s, average particle size measured by DLS 18 nm, Na content in the silica particles (converted to Na2O per 1g SiO2) 2210 ppm / SiO2, sulfate ion content in the silica sol (converted to SO4 per 1g SiO2) 0.7 ppm / SiO2, and aluminum content in the silica particles (converted to Al2O3 per 1g SiO2) 2500 ppm / SiO2.

[0355] (Synthesis example 3)

[0356] Synthesis of MeOH Dispersed Solid Silica Sol (a3)

[0357] Add to a 300 mL SUS autoclave reactor MSH (trade name) 250g was subjected to hydrothermal treatment at 230±10℃ for 2.5 hours. A 5% sodium sulfate aqueous solution was added to 100g of the resulting sol at a concentration equivalent to 20-50 ppm SO3, along with a hydrogen-form strong acid cation exchange resin (trade name). Mix 30g of IR-120B, stir for 30 minutes, and then filter to obtain 130g of acidic silica sol (pH 3, SiO2 concentration 23% by mass, average primary particle size 28nm, Na2O: 344ppm, SO3 concentration 30ppm).

[0358] 130g of the acidic silica sol obtained above was added to an evaporator equipped with a 1L eggplant flask. Then, while slowly adding MeOH, water was distilled off at 550 Torr and 120°C to replace the water, which served as the dispersion medium, with MeOH. The replacement was stopped when the water content of the dispersion reached below 2.0% by mass. After adding MeOH and adjusting the SiO2 content to 30 parts by mass, 92g of MeOH-dispersed silica sol (a3) ​​was obtained. Regarding the obtained sol, the SiO2 concentration was 30.0% by mass, the water content was 1.5% by mass, the viscosity was 5.4 mPa·s, the average particle size measured by DLS was 48.3 nm, the amount of Na present in the silica particles was converted to 1700 ppm / SiO2 (Na2O relative to 1g SiO2), and the amount of sulfate ions present in the silica sol was converted to 36 ppm / SiO2 (SO4 relative to 1g SiO2). In addition, the amount of aluminum present in the entire silicon dioxide particles is converted to Al2O3 relative to 1g SiO2 of silicon dioxide, which is 470ppm / SiO2.

[0359] (Synthesis Example 4)

[0360] Synthesis of MeOH-dispersed silica sol (a4)

[0361] 100g of PL-3 (trade name) was added to an evaporator with a 500mL eggplant flask. Water was then slowly added while heating at 580 Torr and 120°C to remove it by distillation, thus replacing the water, which served as the dispersion medium, with MeOH. The replacement was stopped when the water content of the dispersion fell below 2.0% by mass. After adding MeOH and adjusting to 30 parts by mass, 100g of MeOH-dispersed silica sol (a3) ​​was obtained. Regarding the obtained sol, the SiO2 concentration was 30.0% by mass, the average particle size was 69.1nm as measured by DLS, the amount of Na present in the silica particles was converted to 2210 ppm / SiO2 (Na2O relative to 1g SiO2), and the amount of sulfate ions present in the silica sol was converted to 0.7 ppm / SiO2 (SO4 relative to 1g SiO2). In addition, the amount of aluminum present in all silicon dioxide particles is converted to Al2O3 relative to 1g SiO2 of silicon dioxide, which is 0.026ppm / SiO2.

[0362] (Synthesis Example 5)

[0363] Synthesis of surface-treated MeOH-dispersed solid silica sol (a5)

[0364] 4.44 g of MTMS was added to a 500 mL 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 resulting sol had a SiO2 concentration of 20.5% by mass, an average particle size of 48.5 nm (measured by DLS), a pH of 3.43, a viscosity of 1.2 mPa·s, and a water content of 0.9% by mass. Furthermore, no sediment was observed, indicating good dispersibility.

[0365] (Synthesis Example 6)

[0366] Synthesis of surface-treated MeOH-dispersed hollow silica sol (a6)

[0367] 1.35 g of TnPA diluted to 10% by mass with MeOH was added to a 500 mL round-bottom flask equipped with a condenser containing 200 g of MeOH dispersion sol (a1). The mixture was then stirred with a magnetic stirrer at 25 °C for 630 minutes to obtain the target sol. The resulting sol had a SiO2 concentration of 19.9% ​​by mass, an average particle size of 75.7 nm (measured by DLS), a pH of 4.8, a viscosity of 0.9 mPa·s, and a water content of 1.1% by mass. Furthermore, no sediment was observed, indicating good dispersibility.

[0368] (Synthesis Example 7)

[0369] Synthesis of surface-treated MeOH-dispersed solid silica sol (a7)

[0370] In a 200 mL round-bottom flask equipped with a condenser and containing 50 g of MT-ST, 0.63 g of pure water, 50 g of MeOH, 0.05 g of DiPA, and 1.56 g of M33TMOSPAP were added. The mixture was then heated at 60 °C for 3 hours while stirring with a magnetic stirrer to obtain the target sol. The resulting sol had a SiO2 concentration of 15.2% by mass, an average particle size of 17.3 nm (measured by DLS), a pH of 10.4, a viscosity of 1.0 mPa·s, and a water content of 1.5% by mass. Furthermore, no sediment was observed, indicating good dispersibility.

[0371] (Synthesis Example 8)

[0372] Synthesis of surface-treated MEK dispersed hollow silica sol (a8)

[0373] After adding 1.27 g of PTMS to a 500 mL flask equipped with a condenser containing 150 g of MeOH dispersion sol (a1), the mixture was heated at 65 °C for 3 hours while stirring with a magnetic stirrer. Next, MEK was added, and the solvent was replaced with MEK by distillation under reduced pressure (550–350 Torr) at a bath temperature of 80 °C. The sol was then adjusted with MEK to a concentration of 20% by mass based on the solid residue at 200 °C, yielding the target sol. The resulting sol had a SiO2 concentration of 20.0% by mass, an average particle size of 67.8 nm (measured by DLS), a pH of 3.4, a water content of 0.1% by mass, and a MeOH content of less than 0.1% by mass. Notably, no sediment was observed, indicating good dispersibility.

[0374] (Synthesis Example 9)

[0375] Synthesis of surface-treated MEK dispersed hollow silica sol (a9)

[0376] Add 50 g of MeOH dispersion sol (a1) to a 100 mL pear-shaped flask. While stirring with a magnetic stirrer, add 0.4 g of pure water, 7.5 g of MEK, and 0.60 g of MPDMS. Heat to 60 °C and maintain for 3 hours. Then, add 0.87 g of TMSO and heat to 60 °C and maintain for 3 hours. Finally, add DiPA to adjust the pH to 8.0–10.0 and heat to 60 °C and maintain for 1 hour.

[0377] Then, the eggplant-shaped flask containing the obtained sol was placed in a rotary evaporator, and distillation was carried out while MEK was supplied under reduced pressure at a bath temperature of 80°C and 550~350 Torr, so that the dispersion medium was replaced with MEK, thereby obtaining the target sol.

[0378] The resulting sol, measured by DLS, had an average particle size of 65.9 nm, a pH of 7.1, a SiO2 concentration of 19.1% by mass, a water content of 0.15% by mass, and a MeOH content of less than 0.1% by mass. It should be noted that there was no sediment, indicating good dispersibility.

[0379] (Synthesis Example 10)

[0380] Synthesis of surface-treated MEK dispersed solid silica sol (a10)

[0381] Add 50 g of MA-ST-L to a 100 mL pear-shaped flask, and while stirring with a magnetic stirrer, add 7.5 g of MEK and 1.11 g of MPDMS, heating to 60 °C and maintaining for 3 hours. Next, add 1.65 g of TMSO, heating to 60 °C and maintaining for 3 hours. Then, add DiPA at a pH of 8.0–10.0, heating to 60 °C and maintaining for 1 hour. Place the pear-shaped flask containing the obtained sol in a rotary evaporator, and distill while supplying MEK under reduced pressure at a bath temperature of 80 °C and a pressure of 550–350 Torr, replacing the dispersion medium with MEK to obtain the target sol. The obtained sol, measured by DLS, has an average particle size of 78.6 nm, pH 7.3, SiO2 concentration of 42.7% by mass, water content less than 0.1% by mass, and MeOH content less than 0.1% by mass. It should be noted that there is no sediment, indicating good dispersibility.

[0382] (Synthesis Example 11)

[0383] Synthesis of surface-treated MEK dispersed solid silica sol (a11)

[0384] 50 g of MeOH-dispersed silica sol (a2) was added to a 100 mL pear-shaped flask. 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. Then, DiPEA was added at a pH of 7.0–9.0, and the mixture was heated to 62 °C and maintained for 1 hour. The pear-shaped flask containing the obtained sol was then placed in a rotary evaporator. Distillation was performed under reduced pressure (550–350 Torr) at a bath temperature of 80 °C, with MEK supplied to replace the dispersion medium, thus obtaining the target sol. The obtained sol exhibited the following characteristics as measured by DLS: average particle size 32.7 nm, pH 7.4, SiO2 concentration 40.7% by mass, water content 0.2% by mass, and MeOH content 0.4% by mass. It should be noted that no sediment was observed, indicating good dispersibility.

[0385] (Synthesis Example 12)

[0386] Synthesis of polysiloxane (P1)

[0387] 14.58 g of TEOS (70 mol% of all silane compounds), 3.57 g of MTMS (20 mol% of all silane compounds), 1.98 g of PTMS (10 mol% of all silane compounds), and 31 g of acetone were added to a 200 mL flask. While stirring the mixture with a magnetic stirrer, 6.67 g of 0.01 mol / L hydrochloric acid was added dropwise. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was allowed to proceed under reflux for 240 minutes. The reaction solution was then cooled to 25 °C, and 40 g of PGMEA was added. Methanol, ethanol, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was concentrated to obtain a hydrolyzed condensate (polymer) PGMEA solution. PGEE was then added, and solvent displacement was performed by solvent distillation to obtain a PGEE polymer solution. The resulting solution was adjusted with PGEE to achieve a solid residue of 15% by mass at 200°C. Additionally, the weight-average molecular weight of the resulting polymer was converted to Mw 1,500 for polystyrene.

[0388] (Synthetic Example 13) Synthesis of MeOH Dispersed Solid Silica Sol (a12)

[0389] 16g of MEK was dissolved in a 100mL round-bottom flask with 2.49g of M33TMOSPAP, followed by 1.51g of AOI-VM. The mixture was stirred at 25°C for 3 hours. It should be noted that the IR (cm²) of the prepared surface treatment agent... -1 The values ​​are 3370, 2947, 1729, 1635, 1537, 1268, 1193, and 1085.

[0390] Then, 13g of the surface treatment agent solution was added to a 500mL round-bottom flask equipped with a condenser, containing 150g of MeOH dispersion sol (a1), 18.5g of methanol, and 2g of pure water. The mixture was stirred with a magnetic stirrer and heated at 65°C for 3 hours to obtain the target sol. The obtained sol, measured by DLS, had an average particle size of 44.1nm, a pH of 3.4, a SiO2 concentration of 20% by mass, and a water content of 1.2% by mass. It should be noted that there was no sediment, indicating good dispersibility.

[0391] (Synthesis Example 14) Synthesis of Surface-Treated MeOH Dispersed Hollow Silica Sol (a13)

[0392] Dissolve 2.52 g of APS in 16 g of MEK in a 100 mL round-bottom flask, then add 1.47 g of EICYA and stir at 25 °C for 3 hours. It should be noted that the IR (cm⁻¹) of the prepared surface treatment agent is 3361, 2976, 1748, 1644, 1574, 1281, 1199, and 1081.

[0393] Then, 13g of the surface treatment agent solution was added to a 500mL round-bottom flask equipped with a condenser, containing 150g of MeOH dispersion sol (a1), 18.5g of methanol, and 2g of pure water. The mixture was stirred with a magnetic stirrer and heated at 65°C for 3 hours to obtain the target sol. The obtained sol exhibited the following properties, measured by DLS: average particle size of 62.3nm, pH of 6.8, SiO2 concentration of 20% by mass, and water content of 1.2% by mass. It should be noted that no sediment was observed, indicating good dispersibility.

[0394] (Confirmation test of redispersibility in developer)

[0395] Example 1: A 100 mL pear-shaped flask containing 50 g of the sol obtained in Synthesis Example 6 was placed in a rotary evaporator. The dispersing solvent was removed under reduced pressure at a bath temperature of 60°C and 50 Torr to obtain a dried sol. Further, the dried sol was ground using a mortar and pestle to obtain a dried sol powder. Then, 0.05 g of the dried sol powder was added to a 20 mL glass vial, along with 2.0 mL of any one of the alkaline aqueous solutions and organic solvents listed in Tables 1-2. Next, a test tube mixer was used... The dried powder of the sol (manufactured by [Company Name], trade name: MVM-10) was mixed with any of the alkaline aqueous solutions and organic solvents listed in Tables 1-2, and the appearance was checked. If the appearance was transparent, it could be redispersed; if the appearance was opaque or powder residue remained, it could not be redispersed. Furthermore, the average particle size of the redispersed sol, measured by DLS, was obtained. The results are recorded in Table 1 as follows: "○" indicates redispersibility, "×" indicates non-redispersibility, and "-" indicates no redispersibility. Table 1 records the ratio X of (particle size of silica particles in the developer measured by DLS) / (particle size of silica particles in the organic solvent measured by DLS) based on the average particle size measured by DLS after redispersibility. In cases where silica particles agglomerate and the particle size cannot be measured by DLS, the ratio X is recorded as "0".

[0396] Examples 2-7: Dry powders of the sols obtained in Synthetic Examples 6, 7, 9, 10, 13, and 14 were prepared using the same method as in Example 1. These powders were then mixed with any of the alkaline aqueous solutions and organic solvents listed in Tables 1-2, and redispersibility was confirmed. The results of the redispersibility and the DLS measurements after redispersibility are recorded in Tables 1-2.

[0397] It should be noted 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 in their original solutions, ETMAH (ethyltrimethylammonium hydroxide) was used in a 2.38% by mass aqueous solution, and KOH was used in a 1% by mass aqueous solution.

[0398] [Table 1]

[0399]

[0400] [Table 2]

[0401]

[0402] As shown in Tables 1-2, the sol-derived dry powder of the present invention (Synthesis Example 9, Example 4) contains aluminum atoms forming aluminosilicate sites on the silica particles, and the aluminum atoms are bonded in a ratio of 120-50000 ppm / SiO2 per 1g of silica particles (calculated as Al2O3) to the total number of aluminum atoms in the silica particles (B). By modifying the surface of the silica particles with binding or coating using methylphenyldimethoxysilane having methyl and phenyl groups, and with binding or coating using hexamethyldisiloxane having trimethylsilyl groups, the silica particles exhibit good redispersibility in both alkaline aqueous solutions and organic solvents. It has been confirmed that the silica particles of the present invention can be redispersed in both organic solvents and alkaline aqueous solutions. It was further confirmed that, as described in Examples 1 (Synthesis Example 5), 2 (Synthesis Example 6), 3 (Synthesis Example 7), 6 (Synthesis Example 13), and 7 (Synthesis Example 14), modifying the surface of silica particles by bonding or coating it with alkyl-containing silanes such as methyltrimethoxysilane containing methyl groups, secondary to tertiary amines represented by tertiary amines such as tripentylamine, protected carboxyl groups such as amino acid esters, carboxyl-generating groups, or carboxyl groups, can result in selective developability only in alkaline aqueous solutions or only in organic solvents.

[0403] (Composition Evaluation)

[0404] Example 8: A round-bottom flask containing a solution of the polymer from Synthesis Example 12 and silica sol (trade name MA-ST-L) mixed in a 50:50 solid ratio was placed in an evaporator. MeOH was removed by distillation at a bath temperature of 80°C and 250 Torr to prepare the target composition listed in Table 3. After determining the concentration of the composition, it was then processed in a spin coater (…). 5×5cm alkali-free glass substrate manufactured by [Company Name], product name: MS-A100 Company name and product name: The composition was dropped onto an XG plate and coated at 1500 rpm for 30 seconds. Then, the coated film was fired at 100°C for 2 minutes on a hot plate, followed by a further firing at 180°C for 30 minutes. The resulting coated film was transparent, and the total transmittance (TT) measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name: NHD-5000) was 92.8%. Furthermore, the film thickness was measured to be 1.102 μm using a product name F20-EXR (manufactured by FILMETRICS Co., Ltd.). The conditions and results are shown in Tables 3-4.

[0405] Examples 9 and 10: The silica sol and film-forming conditions were changed, but otherwise performed in the same manner as in Example 8. The resulting films were transparent. The conditions and results are shown in Tables 3 and 4.

[0406] Comparative Example 1: The sol used was changed to MeOH dispersed silica sol (a4), and otherwise the same procedure was followed as in Example 8. The resulting film cracked after firing, and the target coated film was not obtained. The conditions and results are shown in Tables 3-4.

[0407] [Table 3]

[0408]

[0409] [Table 4]

[0410]

[0411] Film-forming properties are evaluated as follows.

[0412] A: Capable of forming films larger than 1.5 μm.

[0413] B: Capable of forming films with a thickness of 1.0 μm to 1.5 μm.

[0414] C: Formation of films smaller than 1.0 μm, or inability to form films.

[0415] The results above show that silica particles containing aluminum atoms exhibit high compatibility with the resin, resulting in a coated film. Conversely, silica particles without aluminum atoms failed to produce the desired coated film.

[0416] (Evaluation of photosensitizing compositions)

[0417] 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 added to a 100 ml flask. The mixture was then subjected to reduced pressure at 60 °C / 100 Torr to prepare a PGEE sol with a SiO2 concentration of 20% by mass. 2.3 g of this solution was then transferred to a 30 ml amber sample bottle under a yellow light chamber. Next, 3 g of the polysiloxane (p1) PGEE solution obtained in Synthesis Example 12, 0.14 g of P-200 (trade name of Toyo Synthetic, structure: a photosensitizer synthesized by the condensation reaction of 1 mole of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol and 2 moles of 1,2-naphthoquinone-2-diazo-5-sulfonyl chloride), and 0.37 g of PGEE were added. The mixture was then stirred at 23 °C for 4 hours using a stirring rotor to obtain the target photosensitive resin composition. The composition was dropped onto a 4-inch silicon wafer and coated using a spin coater at 800 rpm for 5 seconds. It was then fired at 100°C for 2 minutes on a hot plate, followed by a further firing at 180°C for 30 minutes, resulting in a 1.4 μm temporary fired coating. The film thickness was evaluated using a contact thickness gauge (ULVAC Co., Ltd., trade name Dektak 3ST). A chromium mask was then placed on top, and a portion of the coating was cured using a UV curing conveyor system (Iwasaki Electric Co., Ltd., trade name...). 4KW) applied to the coating at 1J / cm 2 Exposure was performed. The exposed coating 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.

[0418] The results above show that the silica particles containing aluminum atoms exhibit high compatibility with the resin, resulting in a photosensitive coating film. Furthermore, the unexposed areas did not require development to obtain a film, while no residue was observed in the exposed areas after alkaline development.

[0419] It has been confirmed that the coating film formed by the coating composition of the present invention exhibits solubility in organic solvents or alkaline aqueous solutions, enabling pattern formation on a substrate and planarization of the surface layer on the coating film by peeling off the surface layer. Furthermore, due to its properties of being soluble in both organic solvents and alkaline aqueous solutions, soluble only in organic solvents, and soluble only in alkaline aqueous solutions, it possesses positive, negative, or dual developability, thus exhibiting excellent performance for photolithography. In addition, the coating layer can be planarized by surface layer peeling, making it suitable as a lower layer in processes where upper layers are further laminated on the coating layer, and enabling its use in multilayer processes.

[0420] Furthermore, in this invention, since silica particles form aluminosilicates through aluminum atoms, the coating film formed from the coating composition containing these silica particles exhibits high coating performance. Even in thick films, no cracking or other breakage occurs, and a highly transparent film can be formed on the substrate. Moreover, due to its low viscosity, spin coating is possible, and the curing temperature is also low, allowing coating on various substrates such as glass substrates, semiconductor substrates, and organic films.

[0421] Industrial availability

[0422] A coating composition comprising silica particles having aluminum atoms bonded to the surface of silica particles in a specific ratio (calculated as Al2O3) can be provided, as well as a laminated substrate using the coating composition and a method for manufacturing the laminated substrate.

Claims

1. A silica particle for addition to a coating composition, the silica particle containing aluminum atoms forming aluminosilicate sites on the silica particle, the aluminum atoms being bonded in a ratio of 120 to 50,000 ppm / SiO2 (calculated as Al2O3) relative to 1 g SiO2 of the silica particle, the amount of aluminum atoms present in the silica particle being determined by a dissolution method by treating the silica particle with an aqueous hydrofluoric acid solution.

2. The ratio of the specific surface area (C) measured by the BET method, i.e., nitrogen adsorption method, to the specific surface area (D) calculated by transmission electron microscopy of the silica particles according to claim 1 is 1.00 to 5.

00.

3. The ratio of the specific surface area (C) measured by the BET method, i.e., nitrogen adsorption method, to the specific surface area (D) calculated by transmission electron microscopy of the silica particles according to claim 1 is 1.40 to 5.

00.

4. The silica particles according to any one of claims 1 to 3, wherein the silica particles are converted to a surface charge of 5 to 250 μeq / g per 1g SiO2.

5. The silica particles according to any one of claims 1 to 4, wherein the silica particles are further coated with at least one silane compound selected from formula (1), formula (2), and formula (3). In equation (1), R 1 Each of the following is an organic group that is alkyl, haloalkyl, alkenyl, aryl, or has an epoxy, (meth)acryloyl, mercapto, amino, urea, polyether, carboxyl, protected carboxyl, carboxyl-generating, or cyano group and is bonded to a silicon atom by a Si-C bond: R 2 Each represents an alkoxy, acyloxy, hydroxyl, or halogen group, and 'a' represents an integer from 1 to 3. In equations (2) and (3), R 3 and R 5 Each is an alkyl group with 1 to 3 carbon atoms or an aryl group with 6 to 30 carbon atoms, bonded to silicon atoms by Si-C bonds. 4 and R 6 Each represents an alkoxy, acyloxy, hydroxyl, or halogen group; Y represents an alkylene group, NH group, or oxygen atom; b is an integer from 1 to 3; c is an integer from 0 to 1; and d is an integer from 1 to 3.

6. The silica particles according to any one of claims 1 to 5, wherein the film thickness formed by the coating composition is 1 to 30 μm.

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

8. A type of silica particles derived from a sol obtained by dispersing silica particles according to any one of claims 1 to 7 in a dispersion medium, wherein the average particle size measured by dynamic light scattering method is 20 to 150 nm.

9. The 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 primary amines, secondary amines and tertiary amines having 1 to 10 carbon atoms.

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

13. The silica particles according to any one of claims 10 to 12, wherein the content of the amine is 0.001 to 10 by mass relative to the SiO2 of the silica particles.

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

15. The 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 dispersed 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, satisfies: (dynamic light scattering particle size of silica particles in the developer) / (dynamic light scattering particle size of silica particles in the organic solvent) = 0.5~4.

0.

16. The silica particles according to claim 14 or 15, wherein the alkaline component in the developing solution is an alkali metal hydroxide or a quaternary ammonium.

17. The silica particles according to any one of claims 14 to 16, wherein the organic solvent component in the developing solution is an alcohol, ketone, ester, amide, or diol.

18. The silica particles according to any one of claims 1 to 17, wherein the silica particles are solid silica particles with no internal space, hollow silica particles with space inside the shell, or a mixture of these silica particles.

19. A coating composition comprising silica particles and resin as described in any one of claims 1 to 18.

20. The coating composition according to claim 19, wherein the resin is a polysiloxane resin, a polyacrylic resin, an epoxy resin, a thiolated epoxy resin, a phenolic varnish resin, a maleimide resin, a polyester resin, a polyamide resin, a polyimide resin, a polyhydroxyimide resin, or a polybenzo[a]ethylene glycol resin. Poly(benzimidazole) resin, poly(benzothiazole) resin, polyamic acid resin, polyhydroxyamide resin, polyhydroxyazomethyl alkali resin, polyether resin, polybenzo[azo]pyridine resin Azine resins, polystyrene resins, polyhydroxystyrene resins, polyurethane resins, polyurea resins, condensation resins, or combinations thereof.

21. The coating composition according to claim 19 or 20, comprising a free radical generator or an acid-producing agent.

22. The coating composition according to claim 21, wherein the coating composition is a resist composition.

23. A method for manufacturing a laminated substrate, comprising the following steps: (i) Step: Applying the coating composition according to any one of claims 19 to 22 onto a substrate and drying it to form a coating film; (ii) Process: Curing the coating film.

24. The method for manufacturing a laminated substrate according to claim 23, wherein the curing of step (ii) is thermosetting, photosetting, or a combination thereof.

25. The method for manufacturing a multilayer substrate according to claim 23 or 24, wherein the curing of step (ii) is performed by exposure on the coated film through a mask.

26. The method for manufacturing a laminated substrate according to any one of claims 22 to 25 further includes a step of developing or planarizing after curing (iii).

27. The method for manufacturing a laminated substrate according to claim 26, wherein development or planarization is performed using an organic solvent or an alkaline aqueous solution.

28. A method for manufacturing a laminated substrate comprising multiple films, wherein, The coating film of any one of claims 23 to 27 is formed into an upper film, a lower film, or a film on both sides thereof.

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