Rotaxane dispersed hollow silica sol and method for producing the same

Abstract

To provide an organosilica sol in which hollow silica particles containing aluminum atoms are dispersed in a polymer, especially an organosilica sol formed by dispersing the hollow silica particles in a polymer having a rotaxane structure.SOLUTION: There are provided a hollow silica organosol containing components (A), (B), and (C), wherein the organosol contains component (C) in an amount of 0.001 mass% or more and 90 mass% or less based on the total amount of the organosol (100 mass%), and a method for producing the same. (A) Component: a hollow silica particle containing aluminum atoms, wherein the amount of aluminum atoms present throughout the hollow silica particle is 120 to 50,000 ppm / SiO2 per gram of the hollow silica particle, calculated as Al2O3. (B) Component: a polymer with a molecular weight of 1000 or more, containing ester, ether, or hydroxy group, and additionally possessing an acrylic structure. (C) Component: Organic solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an organosol in which hollow silica particles containing aluminum atoms are dispersed, and in particular to an organosol in which the hollow silica particles are dispersed in a polymer having a rotaxane structure, a method for producing the organosol, and a resin composition containing the organosol. [Background technology]

[0002] Silica sol is used in various fields as an abrasive, functional inorganic filler, etc. Although silica sol is stable and does not gel in the alkaline range, when alkaline silica sol is blended into a composition containing an organosilicon compound or resin as a binder, the alkaline condition tends to cause cloudiness and thickening. Furthermore, when preparing organosilica sol by solvent substitution, problems remain, such as gelation upon mixing with alcohol, etc. On the other hand, in the acidic range, the zeta potential of silica particles is small, resulting in small electrical repulsion, making silica sol unstable and prone to gelation. However, silica sol is often required in the acidic range, such as in acidic abrasives, raw materials for ceramic fibers, and chromium-based surface treatment agents.

[0003] One method for improving the stability of silica sol in acidic regions is to modify the surface of silica particles with an aluminum compound. In this method, aluminosilicate sites are formed on the silica particle surface by reaction between aluminate ions derived from the aluminum compound and silanol groups on the silica particle surface. The aluminosilicate sites impart a negative charge to the silica particles, i.e., increase the negative zeta potential of the silica particles, thereby improving the dispersion stability of the silica particles in the dispersion medium. This method also improves the compatibility of silica particles with highly polar organic solvents and charged resins. For example, a method for producing an acidic silica sol has been disclosed (see Patent Document 1), in which an aqueous alkali aluminate solution is added to a dispersion of solid silica particles so that the Al2O3 / SiO2 molar ratio is greater than 0.0006 but less than 0.004, and the resulting silica sol is heated at 80 to 250°C and then subjected to cation exchange.

[0004] Furthermore, hollow silica particles have a silica outer shell and a space inside the shell, and because of these characteristics, they have properties such as a low refractive index, low thermal conductivity (thermal insulation), and electrical insulation. Hollow silica particles consist of a core corresponding to the hollow portion and an outer shell that forms the outside of the core. An aqueous dispersion of hollow silica particles can be obtained by forming a silica layer on the outside of a template particle in an aqueous medium and then removing the template particle. For example, a method has been disclosed in which a core-shell particle having an aluminosilicate shell is produced by reacting a silane compound and an aluminum precursor with a Si / Al molar ratio of 7 to 15 on a template core made of an organic polymer in the form of a micelle or reverse micelle, and then reacting this with a basic or acidic aqueous solution to simultaneously form pores in the shell (outer shell) and remove the core, followed by a hydrothermal reaction at 160 to 200°C to produce a hollow silica sol with a high density shell (see Patent Document 2).

[0005] Recently, a molecular assembly with a so-called rotaxane structure has been proposed as a non-covalent assembly, in which a rod-shaped molecule (axis component) penetrates the ring of a ring-shaped molecule (wheel component) and the ends of the rod-shaped molecule are fixed (capped) with a large molecule that prevents the ring-shaped molecule from detaching. For example, Patent Document 3 discloses an inclusion compound in which polyethylene glycol molecules are skewered and included in α-cyclodextrin molecules, and both ends of the polyethylene glycol molecules are end-capped with 2,4-dinitrophenylamino groups. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 6-199515 [Patent Document 2] Korean Patent No. 10-1659709 [Patent Document 3] Patent No. 2810264 Summary of the Invention [Problem to be solved by the invention]

[0007] In order to stabilize silica sol containing hollow silica particles with cavities inside the shell, the particles are modified from the outside with an aluminum compound (i.e., impregnated with the aluminum compound). The aluminum compound penetrates the shell, and the aluminum compound that remains outside the shell (impregnated) and the aluminum compound that reaches the inside of the shell (impregnated) each form aluminosilicate sites. The alkali metal present in the silica particles and derived from the alkali metal silicate, which is the raw material for the silica sol, is captured by the respective aluminosilicate sites. However, depending on the manufacturing, use, and storage conditions of the silica particles, the alkali metal encapsulated within the silica particles may be released over time, resulting in an increase in the pH of the system and the instability described above. In the case of hollow silica particles, the alkali metal present in the aluminosilicate sites outside the shell can be removed during manufacturing by cation exchange or other methods, but it is difficult to remove the alkali metal present in the aluminosilicate sites inside the shell. Furthermore, since aluminosilicate may be generated even inside the silica particles, which is not originally involved in the dispersion stabilization of the silica particles, the amount of aluminum present in the aluminosilicate per silica particle increases, resulting in an increase in the amount of alkali metal bound to the aluminosilicate. Moreover, the alkali metal may leak into the dispersion medium through the pores of the shell over time, which may increase the pH of the system and impair the dimensional stability of the hollow silica particles and the storage stability of the silica sol.

[0008] Furthermore, the hollow silica particles described above can be combined with various polymers to form polymer dispersion sols, and it is expected that the various properties described above, such as electrical insulation, can be applied in a wide variety of fields. So far, there has been no discussion on the combination of hollow silica particles with aggregates or polymers having a rotaxane structure, nor on the dispersibility of silica particles in such aggregates or polymers. [Means for solving the problem]

[0009] A first aspect of the present invention is a hollow silica organosol containing the following components (A), (B), and (C): The hollow silica organosol comprises component (C) in an amount of 0.001% by mass or more and 90% by mass or less based on the total amount (100% by mass) of the organosol: Component (A): aluminum atom-containing hollow silica particles, hollow silica particles, wherein the amount of aluminum atoms present throughout the hollow silica particles is 120 to 50,000 ppm / SiO2 per 1 g of the hollow silica particles in terms of Al2O3; (B) component: a polymer having a molecular weight of 1000 or more, containing an ester, ether, or hydroxy group, and further having an acrylic structure; (C) Component: organic solvent. As a second aspect, the present invention relates to the hollow silica organosol according to the first aspect, in which component (B) is a polymer having a rotaxane structure in which a rod-shaped axis molecule passes through the ring of a ring-shaped molecule, and the axis molecule has a molecular weight of 1,000 to 50,000. As a third aspect, the present invention relates to the hollow silica organosol according to the first aspect, which satisfies the following formula (N) in a thermal stability test 1 in which the hollow silica organosol is maintained at 50° C. for one week: Formula (N): 1.3≧(X 1w ) / (X0)≧0.7 where (X0) is the average particle size measured by dynamic light scattering before thermal stability test 1, and (X 1w ) indicates the average particle size measured by dynamic light scattering after thermal stability test 1. As a fourth aspect, the present invention relates to the hollow silica organosol according to the first aspect, which satisfies the following formula (O) and the following formula (P) in a thermal stability test 2 in which the hollow silica organosol is maintained at 50° C. for 4 weeks: Formula (O): 1.2≧(X4w ) / (X0)≧0.8 where (X0) is the average particle size measured by dynamic light scattering before thermal stability test 2, and (X 4w ) indicates the average particle size measured by dynamic light scattering after thermal stability test 2, Formula (P): 1.2≧(V 4w ) / (V0)≧0.8 where (V0) indicates the viscosity measured at 25°C before the thermal stability test 2, and (V 4w ) indicates the viscosity measured at 25°C after heat stability test 2. According to a fifth aspect, the present invention relates to the hollow silica organosol according to the first aspect, wherein the (A) aluminum-containing hollow silica particles have an average particle size of 20 to 150 nm as determined by dynamic light scattering. As a sixth aspect, the present invention relates to the hollow silica organosol according to the fifth aspect, further comprising at least one of a reactive monomer as the component (D) and / or a polymer as the component (E) (excluding the polymer of the component (B)). According to a seventh aspect, the present invention relates to the hollow silica organosol according to the first aspect, in which the (A) aluminum-containing hollow silica particles satisfy the following (i) to (iv): (i) the thickness of the shell of the hollow silica particles is 3 to 8 nm; (ii) the silanol group density on the surface of the hollow silica particles is 0.2 to 6.0 groups / nm 2 That is, (iii) the surface charge amount calculated per 1 g of the hollow silica particles is 25 μeq / g to 200 μeq / g; (iv) The hollow silica particles have a carbon content of 0.1% by mass to 10.0% by mass as determined by elemental analysis. According to an eighth aspect, the present invention relates to the hollow silica organosol according to the first aspect, further comprising the following component (F): Component (F): At least one silane compound selected from the group consisting of compounds represented by the following formulas (1) and (2): [ka] (In formula (1), R 1are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si-C bond, or a combination of these groups; R 2 are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group having one or more carbon atoms, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; a represents an integer of 1 to 3; In formula (2), R 3 are groups bonded to silicon atoms, and each independently represents an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, an epoxy group, a (meth)acryloyl group, represents an organic group having a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which is bonded to a silicon atom by a Si-C bond, or represents a combination of these groups; R 4 are groups or atoms bonded to the silicon atom, which independently represent an alkoxy group, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; Y is a group or atom bonded to the silicon atom and represents an alkylene group, an NH group, or an oxygen atom; b represents an integer of 1 to 3, and c represents an integer of 0 or 1. According to a ninth aspect, the aluminum-containing hollow silica particles (A) have a surface area of ​​1 nm 2 The particles are surface-coated with the silane compound of component (F) or have the silane compound of component (F) bonded to their surfaces at a ratio of 0.1 to 10 particles per particle. The present invention relates to a hollow silica organosol according to an eighth aspect. According to a tenth aspect, the present invention relates to the hollow silica organosol according to the first aspect, which further contains a basic compound. According to an eleventh aspect, the present invention relates to the hollow silica organosol according to the first aspect, in which the organic solvent of the component (C) is selected from the group consisting of alcohols, ketones, ethers, esters, and amides. According to a twelfth aspect, the (D) reactive monomer is at least one silane compound selected from the group consisting of (meth)acrylic compounds, (meth)polyfunctional acrylates, allyl compounds, isocyanate compounds, isothiocyanate compounds, epoxy compounds, diamine-containing compounds, diol-containing compounds, dicarboxylic acid-containing compounds, disulfonyl chloride-containing compounds, dithiol-containing compounds, disulfide-containing compounds, divinyl-containing compounds, diallyl-containing compounds, styrene, tetracarboxylic acid anhydrides, bismaleimides, vinyl-containing compounds, lactone ring-containing compounds, lactide-containing compounds, fluorine-containing compounds, cyclic olefin-containing compounds, ethylene, propylene, or compounds represented by the following formulas (1) and (2): The sixth aspect relates to a hollow silica organosol. [ka] (In formula (1), R 1 are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si-C bond, or a combination of these groups; R 2 are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group having one or more carbon atoms, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; a represents an integer of 1 to 3; In formula (2), R 3 are groups bonded to silicon atoms, and each independently represents an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, an epoxy group, a (meth)acryloyl group, represents an organic group having a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which is bonded to a silicon atom by a Si-C bond, or represents a combination of these groups; R 4 are groups or atoms bonded to the silicon atom, which independently represent an alkoxy group, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; Y is a group or atom bonded to the silicon atom and represents an alkylene group, an NH group, or an oxygen atom; b represents an integer of 1 to 3, and c represents an integer of 0 or 1. According to a thirteenth aspect, the (E) polymer is a polymer containing, as a monomer component, at least one monomer selected from the group consisting of (meth)acrylic compounds, (meth)polyfunctional acrylates, allyl compounds, isocyanate compounds, isothiocyanate compounds, epoxy compounds, diamine-containing compounds, diol-containing compounds, dicarboxylic acid-containing compounds, disulfonyl chloride-containing compounds, dithiol-containing compounds, disulfide-containing compounds, divinyl-containing compounds, diallyl-containing compounds, styrene, tetracarboxylic acid anhydrides, bismaleimides, vinyl-containing compounds, lactone ring-containing compounds, lactide-containing compounds, fluorine-containing compounds, cyclic olefin-containing compounds, ethylene, propylene, and at least one silane compound selected from the group consisting of compounds represented by the following formulas (1) and (2): The sixth aspect relates to a hollow silica organosol. [ka] (In formula (1), R1 are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si-C bond, or a combination of these groups; R 2 are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group having one or more carbon atoms, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; a represents an integer of 1 to 3; In formula (2), R 3 are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si-C bond, or a combination of these groups; R 4 are groups or atoms bonded to the silicon atom, which independently represent an alkoxy group, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; Y is a group or atom bonded to the silicon atom, and is an alkylene group, an NH group, or an oxygen atom. represents b represents an integer of 1 to 3, and c represents an integer of 0 or 1. According to a fourteenth aspect, the present invention relates to a resin composition including the hollow silica organosol according to the first aspect and an organic resin material or a polysiloxane resin. According to a fifteenth aspect, the present invention relates to the resin composition according to the fourteenth aspect, in which the organic resin material is at least one selected from the group consisting of a styrene-based resin, an epoxy-based resin, a thioepoxy resin, a novolac-based resin, a cyanate-based resin, a phenol-based resin, an acrylic-based resin, a maleimide-based resin, a polyester-based resin, a urethane-based resin, a polyurea resin, a polyimide-based resin, a polyamide-based resin, a polyamic acid resin, a polyhydroxyimide resin, a polybenzoxazole resin, a polybenzimidazole resin, a polybenzothiazole resin, a polyhydroxyamide resin, a polyhydroxyazomethine resin, a polyether-based resin, a polybenzoxazine resin, a polytetrafluoroethylene-based resin, a cycloolefin polymer-based resin, an unsaturated polyester-based resin, a vinyl triazine-based resin, a polyphenylene sulfide-based resin, a crosslinkable polyphenylene oxide-based resin, a curable polyphenylene ether-based resin, and a condensation-based resin. According to a sixteenth aspect, the present invention relates to the resin composition according to the fourteenth or fifteenth aspect, wherein the resin composition is used for a semiconductor device material, a semiconductor element material, a semiconductor resist material, an insulating film material, a copper-clad laminate material, a printed circuit board material, a printing plate material, a printing ink material, a pigment, a paint, a sealant material, a hard coat material, a 3D print material, an anti-reflective film material, an in-vehicle part material, an electronic part material, a machine element part, an adhesive material, a battery material, a power generation material, a chargeability-imparting material, a conductivity-imparting material, a powder fluidity-imparting material, a cosmetic material, a flexible wiring material, a liquid crystal display material, an organic electroluminescence display material, a micro LED display material, a QD-EL display material, a flexible display material, an antenna material, an optical wiring material, or a sensing material. As a seventeenth aspect, the present invention relates to the hollow silica organosol according to the first aspect or the resin composition according to the fourteenth aspect, which further contains a polymerization inhibitor. As an eighteenth aspect, the present invention relates to a method for producing the hollow silica organosol according to the first aspect, comprising a step of substituting an organic solvent for a water-dispersed silica sol containing aluminum atom-containing hollow silica particles by ultrafiltration, heating under reduced pressure, or heating under normal pressure. According to a nineteenth aspect, the present invention relates to a method for producing a hollow silica organosol according to the eighteenth aspect, which further comprises, before or after the step of replacing with an organic solvent, a step of adding at least one silane compound selected from the group consisting of compounds represented by formula (1) and formula (2) to a sol containing aluminum atom-containing silica particles, and heating and stirring the mixture at 10°C to 95°C for 0.1 to 20 hours. [ka] (In formula (1), R 1 are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si-C bond, or a combination of these groups; R 2 are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group having one or more carbon atoms, an acyloxy group, a hydroxy group, or a halogen atom; represents a combination of these groups or atoms, a represents an integer of 1 to 3; In formula (2), R 3 are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si-C bond, or a combination of these groups; R 4 are groups or atoms bonded to the silicon atom, which independently represent an alkoxy group, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; Y is a group or atom bonded to the silicon atom and represents an alkylene group, an NH group, or an oxygen atom; b represents an integer of 1 to 3, and c represents an integer of 0 or 1. According to a twentieth aspect, the present invention relates to a method for producing a hollow silica organosol according to the nineteenth aspect, in which the step of adding a silane compound and heating and stirring is carried out a plurality of times. According to a twenty-first aspect, the present invention relates to a method for producing a hollow silica organosol according to the nineteenth or twentieth aspect, further comprising a step of adding a basic compound and increasing the pH by 0.1 to 6 before or after the step of adding the silane compound and heating and stirring. As a twenty-second aspect, the present invention relates to the method for producing a hollow silica organosol according to the nineteenth aspect or the twentieth aspect, further comprising, after the step of adding the silane compound and heating and stirring, a step of substituting with the organic solvent. As a 23rd aspect, the present invention relates to the method for producing a hollow silica organosol according to the 21st aspect, further comprising, after the pH increasing step, a step of replacing with the organic solvent. According to a twenty-fourth aspect, the present invention relates to a method for producing a hollow silica organosol according to the twenty-first aspect, further comprising, after the pH increasing step, a step of adding the silane compound and heating and stirring, and a step of replacing with the organic solvent. According to a twenty-fifth aspect, the present invention relates to a method for producing a hollow silica organosol according to the eighteenth aspect, comprising, after the step of replacing with an organic solvent, a step of adding a polymer having a molecular weight of 1,000 or more, containing an ester, ether, or hydroxy group, and further having an acrylic structure, so that the content of the organic solvent is 0.001% by mass or more and 90% by mass or less, based on the total amount (100% by mass) of the organosol. As a 26th aspect, the present invention relates to a method for producing a hollow silica organosol according to the 25th aspect, further comprising a step of adding a polymerization inhibitor. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a polymer-containing organosilica sol of aluminum atom-containing hollow silica particles, in particular an organosilica sol containing a polymer having a rotaxane structure. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention relates to a hollow silica organosol comprising (A) aluminum atom-containing hollow silica particles, (B) a polymer having a specific structure, and (C) an organic solvent, and is particularly characterized in that the polymer (B) is a polymer having a rotaxane structure.

[0012] As mentioned above, the rotaxane structure, in which rod-shaped molecules penetrate the rings of ring-shaped molecules and the ends of the rod-shaped molecules are capped, can be incorporated into the cross-linking points of a polymer, for example. This allows the cross-linking points, which are fixed and unevenly distributed in conventional cross-linked polymers, to move freely within the molecular chain. In conventional cross-linked polymers, external stress is concentrated on the short molecular chains formed by fixed cross-linking points, causing the polymer to break. However, the cross-linking points of the rotaxane structure can move freely when external stress is applied, so stress does not concentrate on specific molecular chains. Therefore, it is expected that not only will polymer materials be able to demonstrate their inherent strength, but they will also be able to demonstrate a variety of high functionalities such as high elongation, recovery, swelling, and toughness.

[0013] The hollow silica organosol of the present invention is a dispersion system containing (A) aluminum atom-containing hollow silica particles (hereinafter simply referred to as "hollow silica particles," "hollow silica," or "silica particles"), (B) a specific polymer, and (C) an organic solvent, in which the hollow silica particles (A) are dispersed as a dispersoid in the dispersion media (B) and (C). The hollow silica particles have a silica (SiO2)-containing outer shell with a void space inside the shell.

[0014] The dispersion stability of the hollow silica organosol of the present invention can be evaluated, for example, by the following Thermal Stability Test 1 and Thermal Stability Test 2. <Thermal stability test 1> In the thermal stability test 1, the hollow silica organosol was kept at 50°C for one week. The average particle size measured by dynamic light scattering before the thermal stability test 1 was (X0), and the average particle size measured by dynamic light scattering after the thermal stability test 1 was (X 1w ), the ratio of particle diameter before and after the test: (X 1w The stability of the sol is evaluated by the ratio (X0) / (X). In the hollow silica organosol of the present invention, (X 1w The value of (X0) / (X0) is preferably 0.7 to 1.3, and the ratio is preferably, for example, 1.0 to 1.2.

[0015] <Thermal stability test 2> In the thermal stability test 2, the hollow silica organosol was kept at 50°C for 4 weeks. The average particle size measured by dynamic light scattering before the thermal stability test 2 was (X0), the viscosity measured at 25°C was (V0), and the average particle size measured by dynamic light scattering after the thermal stability test 2 was (X 4w ), and the viscosity measured at 25°C (V 4w ), the ratio of particle diameter before and after the test: (X 4w ) / (X0) and viscosity ratio: (V 4w ) / (V0) evaluates the stability of the sol. In the hollow silica organosol of the present invention, the particle diameter ratio: (X 4w It is at least required that the ratio (X0) / (X0) is 2.0 or less, and in a preferred embodiment, the ratio can be set to 0.8 to 1.2. Also, the viscosity ratio: (V 4w The ratio (V) / (V0) is at least required to be 1.5 or less, and in a preferred embodiment, the ratio can be set to 0.8 to 1.2, and in a more preferred embodiment, 0.9 to 1.1. A sol that exhibits good dispersion stability after such a so-called severe test at 50°C for 4 weeks can be evaluated as a sol that exhibits good dispersion stability for a long period at room temperature.

[0016] [(A) Aluminum atom-containing hollow silica particles] The aluminum atom-containing hollow silica particles of component (A) according to the present invention are particles having a silica (SiO2)-containing outer shell with a space inside the shell.

[0017] In the aluminum atom-containing hollow silica particles, the amount of aluminum atoms present throughout the hollow silica particles (i.e., the entire particle including the particle surface and interior) (i.e., the aluminum atom content in the hollow silica particles) is 120 to 50,000 ppm / silica particle in terms of Al2O3 per 1 g of the hollow silica particles. For example, 300 to 20,000 ppm / silica particle, or 500 to 20,000 ppm / silica particle, or 500 to 10,000 ppm / silica particle, or 500 to 5,000 ppm / silica particle, or 500 to 1,000 ppm / silica particle. 00 ppm / silica particle. In this specification, the amount of aluminum atoms present throughout the hollow silica particles and the amount of aluminum atoms present on the surface of the hollow silica particles described below are expressed as "ppm / silica particle" as a unit showing the amount per 1 g of hollow silica particles. The amount of aluminum atoms present throughout the hollow silica particles can be determined by a dissolution method using a hydrofluoric acid solution (also called a hydrofluoric acid solution). Specifically, the hollow silica particles are dissolved in a hydrofluoric acid solution, and the resulting solution is measured and analyzed using an ICP emission spectrometer, whereby the amount of aluminum atoms present throughout the hollow silica particles can be expressed in terms of Al2O3. More specifically, the silica sol is first dried to remove the dispersant, yielding hollow silica particles. 250 mg of the particles are then dissolved in a hydrofluoric acid solution (e.g., a mixture of 2.5 ml of nitric acid and 2.5 ml of 38% hydrofluoric acid) to obtain an aqueous solution. The amount of aluminum atoms in the aqueous solution is measured using an ICP emission spectrometer to obtain the aluminum atom content (ppm) converted to Al2O3. This is then divided by the mass of the silica particles to determine the amount of aluminum atoms present in the entire hollow silica particle (Al2O3 (ppm) / silica particle).

[0018] In the aluminum atom-containing hollow silica particles (A) according to the present invention, the aluminum atoms may exist as aluminosilicate. In a preferred embodiment, the hollow silica particles have aluminosilicate formed at least on the particle surface, and may have aluminosilicate formed not only on the particle surface but also inside the hollow silica particles. In this specification, the "particle surface" is defined as a region from which an aluminum compound can be eluted by a leaching method using a mineral acid, as described below, and the "particle interior" refers to a region other than the elutable region, such as the depth of the silica (SiO2)-containing shell of the hollow silica particles or the inner part of the shell (the part in contact with the internal space).

[0019] The leaching method uses an aqueous solution of at least one mineral acid selected from the group consisting of sulfuric acid, nitric acid, and hydrochloric acid to elute aluminum atoms (present as aluminosilicates (hereinafter also referred to as aluminum compounds)) from the surface of the target (hollow) silica particles. The amount of eluted aluminum atoms can be expressed in terms of Al2O3. In this specification, the "silica particle surface" can be defined as the area from which the aluminum compound can be eluted by the leaching method. Specifically, aluminum atoms (present as aluminosilicate) on the surface of (hollow) silica particles are leached (dissolved) in an aqueous solution of at least one mineral acid selected from the group consisting of sulfuric acid, nitric acid, and hydrochloric acid. The aluminum atoms are leached (dissolved) in a structure similar to aluminum salt, aluminum oxide, or aluminum hydroxide. The resulting solution is then measured and analyzed using an ICP atomic emission spectrometer, and the amount of aluminum atoms present on the particle surface can be expressed in terms of Al2O3. Among the above mineral acid aqueous solutions, a leaching (elution) method using a nitric acid aqueous solution is particularly preferred. The nitric acid aqueous solution used for leaching can be used within the pH range of 0.5 to 4.0, 0.5 to 3.0, 0.5 to 2.0, or 1.0 to 1.5, and typically, a nitric acid aqueous solution with a pH of 1.0 can be used. For example, 100 mL of the above nitric acid aqueous solution is added to 1 g of silica, and the mixture is maintained at a temperature of 20 to 70°C or 40 to 60°C for 10 to 24 hours to elute aluminum compounds from the silica particle surfaces. This eluate can be used as a sample for ICP atomic emission spectroscopy. More specifically, the dispersant from the organosilica sol is first removed by evaporation or other methods, and then the organosilica sol is dried at 250°C. The resulting silica gel is then ground to form silica powder. 20 mL of a pH 1.0 nitric acid solution is added to 0.2 g of the silica powder, and the mixture is thoroughly shaken. The mixture is then placed in a thermostatic chamber at 50°C for 17 hours, after which the aluminum atom content in the filtrate obtained by centrifugal filtration is measured using an ICP atomic emission spectrometer, and the aluminum atom content (pp) converted to Al2O3 is calculated. m) is obtained. By dividing this by the mass of the silica powder (powdered silica particles), the amount of aluminum atoms present on the silica particle surface (Al2O3 (ppm) / silica particle) can be determined. For example, the aluminum atom-containing hollow silica particles according to the present invention may have an amount of aluminum atoms present on the surface of the hollow silica particles, calculated as Al2O3, per gram of the hollow silica particles, as measured by a leaching method, of 100 to 20,000 ppm / silica particle, or, for example, 100 to 15,000 ppm / silica particle, or 100 to 10,000 ppm / silica particle, or 100 to 3,000 ppm / silica particle, or 200 to 5,000 ppm / silica particle, or 500 to 5,000 ppm / silica particle, or 500 to 3,000 ppm / silica particle.

[0020] In the present invention, the ratio of the amount of aluminum atoms present on the particle surface to the amount of aluminum atoms present in the entire particle, i.e., the ratio (a) / (b) of the amount of aluminum atoms (Al2O3 equivalent, relative to silica particles) present on the surface of the hollow silica particles obtained by measurement using the above-mentioned leaching method to the amount of aluminum atoms (Al2O3 equivalent, relative to silica particles) present on the entire hollow silica particle obtained by measurement using an aqueous hydrofluoric acid solution, can be, for example, in the range of 0.001 to 1.0, or 0.01 to 1.0, or 0.1 to 1.0, or 0.3 to 1.0, or 0.4 to 1.0.

[0021] The average primary particle diameter of the aluminum atom-containing hollow silica particles according to the present invention can be 20 to 100 nm, for example, 30 to 100 nm, 40 to 100 nm, 40 to 80 nm, or 40 to 70 nm, as determined by observation with a transmission electron microscope (TEM).

[0022] In the hollow silica organosol according to the present invention, the hollow silica particles have an average particle size (DLS average particle size: Z-average particle size, harmonic mean particle size) measured by dynamic light scattering (DLS) of 20 to 150 nm, and preferably ranges from 30 to 150 nm, 40 to 150 nm, 50 to 150 nm, 50 to 120 nm, or 50 to 100 nm. The DLS average particle size represents the average value of the secondary particle size (dispersed particle size), and it can be determined that the larger the DLS average particle size, the more the silica particles in the medium are in an aggregated state. The DLS average particle diameter values ​​are (initial) values ​​before the aforementioned Thermal Stability Test 1 and Thermal Stability Test 2 are conducted. However, since the hollow silica particles in the hollow silica organosol according to the present invention are particles with excellent dispersion stability, the DLS average particle diameter value can be assumed to be substantially within the above-mentioned range even after the above tests.

[0023] The solidity / hollowness of hollow silica particles can be evaluated from the ratio [(c) / (d)] of the specific surface area (c) of hollow silica particles measured by the BET method (nitrogen gas adsorption method) to the specific surface area (d) of hollow silica particles measured by transmission electron microscopy. In other words, when the value of (c) / (d) is close to 1.0, the silica particles are solid silica particles with no space inside the outer shell, and when the value of (c) / (d) is greater than 1.0, the silica particles are hollow silica particles with space inside the outer shell. In the hollow silica particles according to the present invention, the (c) / (d) value can be in the range of, for example, 1.00 to 5.00, or 1.40 to 5.00, or 1.40 to 3.50, or 1.50 to 3.00, or 1.50 to 2.80. In addition, the hollow silica particles according to the present invention have a specific surface area (c) measured by the BET method (nitrogen gas adsorption method) of, for example, 18 to 200 m 2 / g, or 50-160m 2 / g, or 60-160m 2 / g, or 70 to 160 m 2 / g, or 80 to 150 m 2 / g. Furthermore, the specific surface area (d) of hollow silica particles calculated from transmission electron microscope data is, for example, 1 8~136m 2 / g, or 18 to 90 m 2 / g, or 18 to 68 m 2 / g, or 18 to 54 m 2 / g, or 18-27m 2 / g, or 18-23m 2 / g.

[0024] The outer shell of the aluminum atom-containing hollow silica particles according to the present invention can be observed with a transmission electron microscope (TEM). In the hollow silica particles according to the present invention, the thickness of the outer shell as determined by observation with a transmission electron microscope can be, for example, in the range of 3.0 to 15.0 nm, or 3.0 to 12.0 nm, preferably 3.0 to 8.0 nm.

[0025] The aluminum atom-containing hollow silica particles according to the present invention have a number density of silanol groups on the surface of the silica particles of, for example, 0.2 to 6.0 / nm 2 , or 0.5 to 5.0 particles / nm 2 , 0.5~3.0 pieces / nm 2 , 0.5~2.0 pieces / nm 2 , 0.7~2.0 pieces / nm 2 , 1.1~2.0 pieces / nm 2 It can be said that: The number density of silanol groups on the surface of silica particles can be measured, for example, by the Sears method described in "Determination of Specific Surface Area of ​​Colloidal Silica by Titration with Sodium Hydroxide" (GW Sears, Jr., Analytical Chemistry, 28(12), 1981 (1956)).

[0026] The aluminum atom-containing hollow silica particles according to the present invention preferably have a surface charge (negative charge) calculated per 1 g of the hollow silica particles of, for example, 25 to 250 μeq / g, or alternatively, can be in the range of 25 to 150 μeq / g, 25 to 100 μeq / g, 25 to 50 μeq / g, or 25 to 45 μeq / g.

[0027] In addition, the high absolute value of the zeta potential of hollow silica particles in the acidic region causes electrical repulsion, which is desirable from the perspective of dispersibility, and the amount of surface charge of hollow silica particles varies, as one factor, depending on the amount of aluminum atoms (aluminosilicate) present in the hollow silica particles, as described above. For example, if the amount (a) of aluminum atoms present on the surface of the silica particles (equivalent to Al2O3, relative to silica particles) is less than 100 ppm / silica particle, or if the amount (b) of aluminum atoms present on the entire silica particle (equivalent to Al2O3, relative to silica particles) is less than 120 ppm / silica particle, the stability of the hollow silica particles tends to decrease. On the other hand, when (a) is 3000 ppm / silica particle or more, or when (b) is 4000 ppm / silica particle or more, the particle size after doping tends to increase compared to the particle size measured by dynamic light scattering (DLS particle size) before doping with aluminum atoms in the aqueous sol stage.

[0028] The aluminum atom-containing hollow silica particles according to the present invention can have a carbon content measured by elemental analysis in the range of, for example, 0.1% to 10.0% by mass. In elemental analysis, first, a poor solvent and a good solvent are selected for a hollow silica sol in which hollow silica particles to be measured are dispersed, and the hollow silica particles are separated from the organic components not bonded to the hollow silica particles using a centrifuge or the like. The resulting mixture is then dried to remove even the adsorbed water, thereby preparing a measurement sample. The obtained measurement sample of silica particles is measured using an elemental analyzer to obtain the carbon content (%) in the sample.

[0029] The viscosity (25°C) of the hollow silica organosol according to the present invention can be set, for example, in the range of 1.0 to 10.0 mPa·s. This viscosity can be appropriately adjusted with the organic solvent (C) described below. The viscosity (25°C) of the hollow silica organosol according to the present invention can be set in the range of 1 to 500,000 mPa·s. This viscosity can be appropriately adjusted with the organic solvent (C) described below. It can be adjusted.

[0030] The refractive index of the aluminum atom-containing hollow silica particles according to the present invention can be set within the range of, for example, 1.20 to 1.45, or 1.20 to 1.40, or 1.20 to 1.30.

[0031] In the hollow silica organosol according to the present invention, the content of the (A) hollow silica particles can be, for example, 1 to 60 mass % or 5 to 50 mass %, and typically 10 to 40 mass %, based on the total amount of the organosol (100 mass %).

[0032] [(B) A polymer having a molecular weight of 1000 or more, containing an ester, ether, or hydroxy group, and further having an acrylic structure] In the present invention, the component (B) includes a polymer having a molecular weight of 1000 or more, containing an ester, ether, or hydroxy group, and further having an acrylic structure.

[0033] A preferred example of the component (B) is a polymer having a rotaxane structure in which the molecular weight of the axis molecule is 1000 to 50000. A polymer having a rotaxane structure has, for example, a configuration in which a rod-shaped axis molecule passes through the ring of a ring-shaped molecule. For example, a polymer can be produced by using α-cyclodextrin molecules as ring-shaped molecules and polyethylene glycol molecules as rod-shaped molecules, with adamantane structures at both ends of the polyethylene glycol molecules that prevent the α-cyclodextrin molecules from detaching. A preferred embodiment of the polymer is one in which hydroxypropyl groups are introduced into the hydroxy groups of α-cyclodextrin molecules, the hydroxy groups of the hydroxypropyl groups are modified with polycaprolactone, and a radical-reactive functional group such as a (meth)acrylic group is introduced into the terminal of the modified polycaprolactone. Examples of such polymers include the Cerm Super Polymer SM / SA series (trade name) manufactured by ASM Corporation. Examples of polymers having such a rotaxane structure include polymers having an axis weight-average molecular weight of about 10,000 to 20,000 and an overall molecular weight (weight average) of about 100,000 to 400,000.

[0034] In the hollow silica organosol according to the present invention, the content of the (B) polymer can be, for example, 1 to 99% by mass, or 30 to 70% by mass, based on the total amount of the organosol (100% by mass). In the hollow silica organosol according to the present invention, the blending ratio (mass ratio) of (A) hollow silica particles to (B) polymer can be set to 1:99 to 70:30.

[0035] [Component (C): Organic Solvent] The hollow silica organosol according to the present invention contains an organic solvent as component (C). In the present invention, the organic solvent as component (C) is contained in a proportion of 0.001% by mass or more and 90% by mass or less based on the total amount (100% by mass) of the hollow silica organosol.

[0036] Examples of the organic solvent of component (C) include alcohols, ketones, ethers, esters, and amides. More specifically, examples include alcohols having 1 to 10 carbon atoms, ketones having 1 to 10 carbon atoms, ethers having 1 to 10 carbon atoms, esters having 1 to 10 carbon atoms, amides, and glycols. The number of carbon atoms mentioned above means the total number of carbon atoms contained in the compound such as the alcohol.

[0037] The alcohol having 1 to 10 carbon atoms includes an aliphatic alcohol, which may be a primary alcohol, a secondary alcohol, or a tertiary alcohol. Furthermore, polyhydric alcohols such as dihydric alcohols and trihydric alcohols may also be used as these alcohols. is. Examples of the monohydric primary alcohol include methanol, ethanol, 1-propanol, 1-butanol, and 1-hexanol. Examples of the monohydric secondary alcohol include 2-propanol, 2-butanol, cyclohexanol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. The monohydric tertiary alcohol includes, for example, tert-butyl alcohol. Examples of the dihydric alcohol (glycol) include methanediol, ethylene glycol, propylene glycol, and diethylene glycol. The trihydric alcohol includes glycerin.

[0038] The ketone having 1 to 10 carbon atoms is preferably an aliphatic ketone, such as acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, or methyl cyclopentanone.

[0039] The ether having 1 to 10 carbon atoms is preferably an aliphatic ether, such as dimethyl ether, ethyl methyl ether, diethyl ether, tetrahydrofuran, or 1,4-dioxane.

[0040] As the ester having 1 to 10 carbon atoms, an aliphatic ester can be preferably used, for example, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl 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, etc.

[0041] Examples of the amide include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and tetramethylurea.

[0042] [Component (D): reactive monomer, Component (E): polymer] The hollow silica organosol according to the present invention may further contain at least one of (D) a reactive monomer and (E) a polymer. The polymers listed above as the component (B) are excluded from the polymer (E).

[0043] Examples of the reactive monomer of the component (D) include (meth)acrylic compounds, (meth)polyfunctional acrylates, vinyl structure-containing compounds (vinyl-containing compounds, divinyl-containing compounds, allyl compounds, diallyl-containing compounds, styrene, ethylene, propylene, and cyclic olefin-containing compounds), isocyanate compounds, isothiocyanate compounds, epoxy compounds, diamine-containing compounds, diol-containing compounds, dicarboxylic acid-containing compounds, disulfonyl chloride-containing compounds, dithiol-containing compounds, disulfide-containing compounds, ester structure-containing compounds (tetracarboxylic acid anhydrides, lactone ring-containing compounds, lactide-containing compounds, etc.), bismaleimides, fluorine-containing compounds, and at least one silane compound selected from the group consisting of compounds represented by formula (1) and formula (2) described below (component (C) described below). Furthermore, examples of the polymer of component (E) include polymers containing, as a monomer component, at least one monomer selected from the various compounds listed above as the reactive monomer of component (D). These (D) reactive monomers and (E) polymers are preferably reactive monomers / polymers that are liquid at 25°C or have a viscosity of 50,000 mPa·S or less at 25°C in order to form a sol having a fluid liquid state. Furthermore, if the (D) reactive monomer or (E) polymer is a solid, gas, or has high viscosity, the form and viscosity can be adjusted to be suitable for incorporation into the organosol using the aforementioned (C) organic solvent.

[0044] Examples of the reactive monomer of component (D) include compounds having a radically polymerizable group, a cationically polymerizable group, or an anionically polymerizable group in the molecule, or polymerizable compounds having an ethylenically unsaturated bond in the molecule, polymerizable compounds having an epoxy ring, polymerizable compounds having an oxetane ring, and polymerizable compounds having a vinyl ether structure.

[0045] Examples of the reactive monomer are shown below. Examples of (meth)acrylic compounds include monomers having a carboxylic acid such as acrylic acid or methacrylic acid, methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, isononyl acrylate, 2-methoxyethyl acrylate, isobornyl acrylate, phenyl acrylate, 3-hydroxyphenyl acrylate, 4-hydroxyphenyl acrylate, 2-phenoxyethyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isobutyl methacrylate, isononyl methacrylate, 2-methoxyethyl methacrylate, and isobornyl acrylate. Examples of the monomer include monomers having an ester structure typified by methacrylate, phenyl methacrylate, 3-hydroxyphenyl methacrylate, 4-hydroxyphenyl methacrylate, 2-phenoxyethyl methacrylate, benzyl methacrylate, 2-(dimethylamino)ethyl acrylate-benzyl chloride quaternary salt, and 9-anthrylmethyl methacrylate, and monomers having an ester structure typified by N-phenylacrylamide, N,N-dimethylacrylamide, acryloylmorpholine, N-(2-hydroxyethyl)acrylamide, N-isopropylacrylamide, N,N-diethylacrylamide, and N-[3-(dimethylamino)propyl]acrylamide methyl chloride quaternary salt. In addition, examples of polyfunctional (meth)acrylates include 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, neopentyl glycol diacrylate, 2-hydroxy-3-methacrylpropyl acrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polytetramethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, ethoxylated bisphenol A diacrylate, and trimethylolpropane triacrylate. Examples of the acrylate include methacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated glycerin triacrylate, tris-(2-acryloxyethyl)isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol polyacrylate, and polypentaerythritol polyacrylate, as well as compounds in which the acrylate moiety is methacrylate. Examples of the allyl compound include allyl alcohol, allyl chloride, allyl ether, allyl glycidyl ether, allyl carboxylic acid, allyl amine, allyl isopropyl acetyl urea, and allyl acid. Examples of the isocyanate compound include aromatic isocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, and p-phenylene diisocyanate; hexamethylene diisocyanate; Examples of the isocyanate include aliphatic isocyanates such as xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexyl, dicyclohexylmethane diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate. Examples of isothiocyanates include allyl isothiocyanate, sulforaphane, benzyl isothiocyanate, p-hydroxybenzyl isothiocyanate, gevarin, iperin, and phenethyl isothiocyanate.

[0046] Examples of epoxy compounds include 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxy Cyclohexane carboxylate, trimethylolethane triglycidyl ether, triglycidyl-p-aminophenol, tetraglycidyl metaxylenediamine, tetraglycidyl diaminodiphenylmethane, tetraglycidyl-1,3-bisaminomethylcyclohexane, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, bisphenol-S diglycidyl ether, pentaerythritol tetraglycidyl ether, resorcinol diglycidyl ether, phthalate diglycidyl ester , neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetrabromobisphenol-A diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, pentaerythritol diglycidyl ether, hydrogenated bisphenol-A diglycidyl ether, tris-(2,3-epoxypropyl) isocyanurate, 1-{2,3-di(propionyloxy)}-3,5-bis(2,3-epoxypropyl)-1,3,5-triazine-2,4,6·(1H,3H,5H )-trione, 1,3-bis{2,3-di(propionyloxy)}-5-(2,3-epoxypropyl)-1,3,5-triazine-2,4,6·(1H,3H,5H)-trione, monoallyl diglycidyl isocyanurate, diglycerol polydiglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis(2,3-epoxypropoxyperfluoroisopropyl)cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, 1,6-Hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, adipic acid diglycidyl ether, o-phthalic acid diglycidyl ether, dibromophenyl glycidyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylolperfluorohexane diglycidyl ether, 4,4'-bis(2,3-epoxypropoxyperfluoroisopropyl)diphenyl ether, 2,2-bis(4-glycidyloxyphenyl)propane, 3,4-epoxycyclohexylmethyl-3',4' ... Examples of epoxy compounds include cyclohexane carboxylate, 3,4-epoxycyclohexyloxirane, 2-(3,4-epoxycyclohexyl)-3',4'-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxy-bis(3,4-epoxycyclohexylmethane), 4',5'-epoxy-2'-methylcyclohexylmethyl-4,5-epoxy-2-methylcyclohexane carboxylate, ethylene glycol-bis(3,4-epoxycyclohexane carboxylate), bis-(3,4-epoxycyclohexylmethyl)adipate, and bis(2,3-epoxycyclopentyl)ether. Other examples include liquid bisphenol A epoxy compounds, liquid bisphenol F epoxy compounds, 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexane carboxylate, and tris(2,4-epoxypropyl)isocyanurate.

[0047] Examples of diamine-containing compounds include diamines such as ethylenediamine, putrescine, cadaverine, hexamethylenediamine, and paraphenylenediamine.

[0048] Examples of diol-containing compounds include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, dipropylene glycol, glycerin, diglycerin, sorbitan, sorbitol, maltitol, glucose, and sucrose.

[0049] Examples of dicarboxylic acid-containing compounds include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. Acid anhydrides of these compounds are also included, such as acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, etc.

[0050] Disulfonyl chloride-containing compounds include 1,3-benzenedisulfonyl chloride.

[0051] Examples of dithiol-containing compounds include 2,3-dimercapto-1-propanol, sodium 2,3-dimercapto-1-propanesulfonate, and 2,5-dimercapto-1,3,4-thiadiazole.

[0052] Examples of disulfide-containing compounds include dimethyl disulfide, allyl disulfide, and diphenyl disulfide.

[0053] Divinyl-containing compounds include divinylbenzene and the like.

[0054] Diallyl-containing compounds include diallyldimethylammonium chloride.

[0055] Examples of the styrene include styrene-based compounds, such as styrene, 3-acetoxy-5-hydroxystyrene, 4-acetoxystyrene, 3,5-bis(trifluoromethyl)styrene, p-bromostyrene, and p-chlorostyrene.

[0056] Examples of the tetracarboxylic acid anhydride include 3,3'-4,4'-biphenyltetracarboxylic acid dianhydride, 4,4'-biphthalic acid anhydride, cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride, and 1,4,5,8-naphthalenetetracarboxylic acid dianhydride.

[0057] Examples of bismaleimides include 4,4'-bismaleimide diphenylmethane, phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, and 1,6'-bismaleimide-(2,2,4-trimethyl)hexane.

[0058] Examples of vinyl-containing compounds include vinyl acetate, methyl vinyl ketone, vinyl chloride, and vinylidene chloride.

[0059] Examples of lactone ring-containing compounds include beta propiolactone, gamma butyrolactone, delta valerolactone, alpha viron, and coumarin.

[0060] Examples of lactide-containing compounds include L-lactide and D-lactide.

[0061] Examples of the fluorine-containing compound include trifluoroethanol, 2,2,2-trifluoroethyl methacrylate, and trifluoromethyltrimethylsilane.

[0062] Examples of the cyclic olefin-containing compound include cyclobutene, cyclopentene, cyclohexene, cycloheptene, 1,3-cyclohexanediene, 1,4-cyclohexadiene, and 1,5-cyclooctadiene.

[0063] Examples of ethylene include ethylene-based compounds such as ethylene, propylene, and butylene.

[0064] [(F) Silane Compound] The hollow silica organosol of the present invention may further contain a silane compound, which is the following component (F). The silane compound of the component (F) can be at least one silane compound selected from the group consisting of compounds represented by the following formulas (1) and (2). [ka]

[0065] In the above formula (1), R 1 are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si-C bond, or a combination of these groups; R 2 are groups or atoms bonded to the silicon atom, which independently represent an alkoxy group, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; a represents an integer of 1 to 3. In the definition of the groups of the silane compound in this specification, the term "independently of each other" means that multiple groups can each independently represent a group defined as an alternative. For example, in formula (1), R 1 If there are two or more (a is 2 to 3), multiple R 1 may be the same group (for example, all methyl groups), or may be a combination of different groups (for example, when a is 2, a methyl group and a phenyl group, or a methyl group and a (meth)acryloylpropyl group, etc.).

[0066] In the above formula (2), R 3 are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si-C bond, or a combination of these groups; R 4are groups or atoms bonded to the silicon atom, which independently represent an alkoxy group, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; Y is a group or atom bonded to the silicon atom, and is an alkylene group, an NH group, or an oxygen atom. represents b represents an integer of 1 to 3, and c represents an integer of 0 or 1.

[0067] In the above formula, examples of the alkyl group include a linear or branched alkyl group having 1 to 18 carbon atoms and a cyclic alkyl group having 3 to 10 carbon atoms. Examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a cyclo ...2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a cyclopentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group ethyl-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 ethyl, 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-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-i-propylcyclopropyl, 2-i-propylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,Examples of the alkyl group include, but are not limited to, 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl groups, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups.

[0068] The halogenated alkyl group is an alkyl group substituted with one or more halogen atoms, and specific examples of such alkyl groups include the same as those mentioned above. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the halogenated alkyl group include, but are not limited to, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1,1-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a 2-chloro-1,1,2-trifluoroethyl group, a pentafluoroethyl group, a 3-bromopropyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,2,3,3,3-hexafluoropropyl group, a 1,1,1,3,3,3-hexafluoropropan-2-yl group, a 3-bromo-2-methylpropyl group, a 4-bromobutyl group, and a perfluoropentyl group.

[0069] Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms, such as ethenyl (vinyl), 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-1-ethenyl, 1 ... n-propylethenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl- Examples of alkyl groups include, but are not limited to, a 2-propenyl group, a 1-i-propylethenyl group, a 1,2-dimethyl-1-propenyl group, a 1,2-dimethyl-2-propenyl group, a 1-cyclopentenyl group, a 2-cyclopentenyl group, a 3-cyclopentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, a 1-methyl-1-pentenyl group, a 1-methyl-2-pentenyl group, a 1-methyl-3-pentenyl group, a 1-methyl-4-pentenyl group, a 1-n-butylethenyl group, a 2-methyl-1-pentenyl group, and a 2-methyl-2-pentenyl group.

[0070] The aryl group may be, for example, an aryl group having 6 to 30 carbon atoms, such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-pyrenyl group, or a 2-pyrenyl group.

[0071] Examples of the organic group having an epoxy group include a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, and a 2-(3,4-epoxycyclohexyl)ethyl group. The (meth)acryloyl group refers to both an acryloyl group and a methacryloyl group. Examples of organic groups having a (meth)acryloyl group include a methacryloyloxymethyl group, an acryloyloxymethyl group, a methacryloyloxyethyl group, an acryloyloxyethyl group, a 3-methacryloyloxypropyl group, and a 3-acryloyloxypropyl group. The methacryloyloxy group and the acryloyloxy group are also referred to as a methacryloxy group and an acryloxy group. Examples of the organic group having a mercapto group include an ethyl mercapto group, a 3-mercaptopropyl group, a butyl mercapto group, a hexyl mercapto group, an octyl mercapto group, and a mercaptophenyl group. Examples of the organic group having an amino group include an aminomethyl group, a 2-aminoethyl group, a 3-aminopropyl group, an N-2-(aminoethyl)-3-aminopropyl group, an N-(1,3-dimethyl-butylidene)aminopropyl group, an N-phenyl-3-aminopropyl group, an N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group, a dimethylaminoethyl group, and a dimethylaminopropyl group. An example of the organic group having a ureido group is a 3-ureidopropyl group. An example of the organic group having a polyether group is a polyetherpropyl group having an alkoxy group. A specific example of the silane compound having an organic group having a polyether group is a compound represented by (CHO)SiCH(OCH)OCH, where n is 1 to 100 or 1 to 10. Examples of the organic group having a carboxy group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, and a carboxybutyl group. The above-mentioned protected carboxy group means a carboxy group protected by a protecting group used in ordinary organic synthesis reactions. The above-mentioned carboxy group generating group means a group in which a carboxy group is esterified or amidated with alcohols, amines, etc. Specific examples of compounds containing a protected carboxy group and an organic group having a carboxy group generating group (i.e., silane compounds represented by formula (1) and formula (2) having these groups) include carboxy groups, Examples of suitable silane coupling agents include silane coupling agents having a carboxylic acid ester structure. Silane coupling agents containing an organic group containing a carboxylic acid ester group include compounds in which the ester moiety is an alkyl ester, aryl ester, or arylalkyl ester. For example, the alkyl group of the ester moiety may be a linear or branched alkyl group having 1 to 10 carbon atoms, the aryl group may be an aryl group having 6 to 40 carbon atoms, and the arylalkyl group may be a structure in which an alkylene group having 1 to 10 carbon atoms is bonded to an aryl group having 6 to 40 carbon atoms. Examples of the structure of the ester moiety include a methyl carboxylate structure, a t-butyl carboxylate structure, and a benzyl carboxylate structure. In addition, in the silane coupling agent, the carboxylic acid ester moiety and the alkoxysilyl group may be linked by an alkylene group, a specific example of which is an alkylene group having 1 to 10 carbon atoms that may contain a heteroatom. Examples of heteroatoms include nitrogen atoms and oxygen atoms, such as an -NH- group and an -O- group. In the silane coupling agent, the carboxylic acid ester moiety is hydrolyzed to form a carboxylic acid. Therefore, when a silane coupling agent contains a nitrogen atom as a heteroatom, it becomes an amino acid due to the presence of a carboxyl group and an amino group upon hydrolysis, and therefore the silane coupling agent can be used as an amino acid generator. For example, the product name X-88-475, manufactured by Shin-Etsu Chemical Co., Ltd., represented by formula (1-1), can be used. [ka] Examples of the organic group having an imide group include an N-succinimidyl group. Examples of the organic group having a cyano group include a cyanoethyl group and a 3-cyanopropyl group.

[0072] The alkoxy group may be an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, and the like, but is not limited to these.

[0073] The acyloxy group is a group derived by removing a hydrogen atom from the carboxy group (—COOH) of a carboxylic acid compound, and specific examples thereof include acyloxy groups having 2 to 10 carbon atoms, such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, an n-butylcarbonyloxy group, an i-butylcarbonyloxy group, an s-butylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, a 1-methyl-n Examples of alkyl groups include, but are not limited to, a 1-butylcarbonyloxy group, a 2-methyl-n-butylcarbonyloxy group, a 3-methyl-n-butylcarbonyloxy group, a 1,1-dimethyl-n-propylcarbonyloxy group, a 1,2-dimethyl-n-propylcarbonyloxy group, a 2,2-dimethyl-n-propylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, an n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, and a 2-methyl-n-pentylcarbonyloxy group.

[0074] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0075] Examples of the alkylene group include alkylene groups derived from the alkyl groups described above. Specific examples thereof include, but are not limited to, linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene, and branched alkylene groups such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene.

[0076] A specific example of the silane compound represented by the formula (1) is a silane compound represented by the following formula (3). [ka]

[0077] In the above formula (3), R 5 are groups bonded to a silicon atom, and each independently represent an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an organic group having a (meth)acryloyl group, an alkenyl group, or a carboxyl group-generating group and bonded to a silicon atom via a Si-C bond, or a combination of these groups; R 6 are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group having 1 to 3 carbon atoms, or a combination of these groups. d represents an integer of 1 to 3. Specific examples of these groups include those mentioned above, and examples of the alkyl group having 1 to 3 carbon atoms include the alkyl groups having 1 to 3 carbon atoms mentioned above as specific examples of the alkyl group.

[0078] Furthermore, specific examples of the silane compound represented by the formula (1) include the silane compound represented by the following formula (4). [ka]

[0079] In the above formula (4), R 7 and R 8 are groups bonded to a silicon atom, each independently representing an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an organic group having a (meth)acryloyl group and bonded to a silicon atom via a Si-C bond; R 9 are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group having 1 to 3 carbon atoms, or a combination of these groups. Specific examples of these groups include those mentioned above, and examples of the alkyl group having 1 to 3 carbon atoms and the aryl group having 6 to 10 carbon atoms include the alkyl group having 1 to 3 carbon atoms and the aryl group having 6 to 10 carbon atoms among the specific examples of the alkyl group and aryl group mentioned above.

[0080] Furthermore, specific examples of the silane compounds represented by the above formulas (1) and (2) include compounds that can form trimethylsilyl groups on the surfaces of silica particles. Examples of such compounds include compounds represented by the following formulas (1-2), (2-1) and (2-2). [ka] In the above formula (1-1), R 12 is an alkoxy group, such as a methoxy group or an ethoxy group. Silane compounds represented by the above formulas (1-2), (2-1) and (2-2) can be silane compounds manufactured by Shin-Etsu Chemical Co., Ltd.

[0081] The aluminum atom-containing hollow silica particles (A) according to the present invention may be particles whose surfaces are at least partially coated with the silane compound of the component (F). In the present invention, "coated with a silane compound" refers to an embodiment in which the surface of a silica particle is coated with a silane compound, and also includes an embodiment in which a silane compound is bonded to the surface of a silica particle. The "embodiment in which the surface of the silica particles is coated with a silane compound" may refer to an embodiment in which at least a portion of the surface of the silica particles is coated with a silane compound, i.e., it includes an embodiment in which the silane compound covers a portion of the surface of the silica particles and an embodiment in which the silane compound covers the entire surface of the silica particles. This embodiment does not require bonding between the silane compound and the surface of the silica particles. Furthermore, "an embodiment in which a silane compound is bonded to the surface of a silica particle" means an embodiment in which a silane compound is bonded to at least a portion of the surface of a silica particle, i.e., an embodiment in which the silane compound is bonded to a portion of the surface of a silica particle, an embodiment in which the silane compound is bonded to a portion of the surface of a silica particle and covers at least a portion of the surface, and even an embodiment in which the silane compound is bonded to the entire surface of a silica particle and covers the entire surface. That is, the silane compound of the component (F) can function as a surface modifier for the aluminum atom-containing hollow silica particles (A).

[0082] The hollow silica particles at least partially coated with a silane compound can be obtained, for example, by adding a silane compound to a hollow silica sol and then heat-treating the mixture at 10 to 95°C for approximately 0.1 to 20 hours. The amount of silane compound added relative to the hollow silica particles (solid content) in the hollow silica sol can be, for example, a mass ratio of silane compound / hollow silica particles of 0.1 to 10.0. The hollow silica sol used to treat hollow silica particles with a silane compound is a sol containing an aqueous or organic solvent as a dispersion medium, and is distinct from the sol containing the polymer of component (B) described above. In one embodiment, the hollow silica particles (A) according to the present invention have a surface area of ​​1 nm 2The particles may be those whose surfaces are coated with the silane compound of component (F) or those whose surfaces are bonded to the silane compound of component (F) at a ratio of 0.1 to 10 particles per 1 nm of the surface of the hollow silica particles. 2 The amount can be set so that the number of silicon atoms in the silane compound is, for example, about 0.1 to 10, or about 0.1 to 6, per unit area.

[0083] The treatment (reaction) of silica particles with the silane compound proceeds by the reaction between silanol groups generated by hydrolysis of the silane compound and hydroxyl groups (silanol groups) on the surface of the silica particles. The hydrolysis requires the presence of water. When the silica sol is an aqueous solvent sol, the aqueous solvent is necessary. In the case of an organic solvent sol in which the aqueous medium is replaced with an organic solvent, the aqueous solvent is necessary. The water remaining in the organic solvent can play this role. For example, water present in the organic solvent at 0.01 to 1% by mass can be used for hydrolysis.

[0084] The hydrolysis can be carried out with or without a catalyst. If the silica particle surface is on the acidic side (pH less than 7), hydrolysis can be carried out without a catalyst. A catalyst may also be used. Examples of usable hydrolysis catalysts include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases. Examples of metal chelate compounds used as hydrolysis catalysts include triethoxymono(acetylacetonato)titanium and triethoxymono(acetylacetonato)zirconium. Examples of organic acids that can serve as hydrolysis catalysts include acetic acid and oxalic acid. Examples of inorganic acids that can be used as hydrolysis catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Examples of organic bases that can be used as hydrolysis catalysts include pyridine, pyrrole, piperazine, and quaternary ammonium salts. Examples of inorganic bases that can serve as hydrolysis catalysts include ammonia, sodium hydroxide, and potassium hydroxide.

[0085] [Basic compounds] The hollow silica organosol according to the present invention may further contain a basic compound, which can adjust the pH of the organosol and the amount of surface charge. By adjusting the type and amount of the basic compound to be added, it is possible to adjust the surface charge amount of the (A) hollow silica particles to any desired surface charge amount. For example, by adding a basic compound, the surface charge amount of the hollow silica particles (A) in the hollow silica organosol of the present invention, i.e., the surface charge amount (negative charge amount) calculated per gram of hollow silica particles, can be adjusted to 25 to 250 μeq / g, or 25 to 150 μeq / g, 25 to 100 μeq / g, 25 to 50 μeq / g, or 25 to 45 μeq / g. Furthermore, the pH of the hollow silica organosol of the present invention can be adjusted to, for example, 7 to 10 by adding a basic compound.

[0086] The basic compound may be either an inorganic base or an organic base, and may contain, for example, an amine, or an amine and ammonia. The amine may be added and contained in an amount 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.

[0087] Examples of the amine include aliphatic amines and aromatic amines, with aliphatic amines being preferred. At least one amine selected from the group consisting of primary, secondary, and tertiary amines having 1 to 10 carbon atoms can be used. The amine is water-soluble and is at least one amine selected from the group consisting of primary, secondary, and tertiary amines having 1 to 10 carbon atoms.

[0088] Examples of primary amines include monomethylamine, monoethylamine, monopropylamine, monoisopropylamine, monobutylamine, monoisobutylamine, monosecbutylamine, monotertbutylamine, monomethanolamine, monoethanolamine, monopropanolamine, monoisopropanolamine, monobutanolamine, monoisobutanolamine, monosecbutanolamine, and monotertbutanolamine. Examples of secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, N-methylethylamine, N-ethylisobutylamine, dimethanolamine, diethanolamine, dipropanolamine, diisopropanolamine, N-methanolethylamine, N-methylethanolamine, N-ethanolisobutylamine, and N-ethylisobutanolamine. Examples of tertiary amines include trimethylamine, triethylamine, tripropylamine, triisopropylamine, diisopropylethylamine, tributylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, trimethanolamine, triethanolamine, tripropanolamine, triisopropanolamine, tributanolamine, triisobutanolamine, tri-sec-butanolamine, tri-tert-butanolamine, tripentylamine, 3-(dimethylamino)ethyl acrylate, 2-(dimethylamino)ethyl acrylate, 2-(dimethylamino)ethyl methacrylate, 2-(diethylamino)ethyl acrylate, and 2-(diethylamino)ethyl methacrylate. The water solubility of the amine is preferably 80 g / L or more, or 100 g / L or more. Among these, primary amines and secondary amines are preferred, with secondary amines being more preferred due to their low volatility and high solubility, such as diisopropylamine and diethanolamine. Diisopropylethylamine, a tertiary amine, is also preferably used.

[0089] The pH of the hollow silica organosol according to the present invention can be adjusted from acidic to alkaline. The pH can be set to 1 to less than 7 on the acidic side, and to 7 or more and 13 or less on the alkaline side. Adjustment to acidic is carried out by adding an inorganic or organic acid, and adjustment to alkaline is carried out by adding an inorganic or organic base (e.g., the basic compounds mentioned above).

[0090] Furthermore, when measuring the pH of a hollow silica organosol in an embodiment that does not contain (B) a polymer, i.e., in an embodiment of an organic solvent sol containing (A) hollow silica particles and (C) an organic solvent, the pH can be the pH when the organic solvent sol and an equal mass of pure water are mixed at a ratio of 1:1. The pH is measured in the embodiment of an organic solvent sol that can be mixed with water, and when the solvent is subsequently replaced with a hydrophobic organic solvent, the pH is measured in advance at the stage of a hydrophilic organic solvent sol such as methanol, or the pH is measured after adding a hydrophilic organic solvent to the hydrophobic solvent sol. For example, when the dispersion medium is a hydrophilic organic solvent such as methanol sol or propylene glycol monomethyl ether sol, the pH can be measured using a solution prepared by mixing pure water and the sol in a mass ratio of 1:1. When the dispersion medium is a hydrophobic organic solvent such as methyl ethyl ketone sol, the pH can be measured using a solution prepared by mixing pure water, methanol, and methyl ethyl ketone sol in a mass ratio of 1:1:1.

[0091] [Method for producing hollow silica organosol] The hollow silica sol of the present invention is produced by a process comprising ultrafiltration, heating under reduced pressure, or heating under normal pressure to replace a water-dispersed silica sol containing aluminum atom-containing hollow silica particles with an organic solvent.

[0092] First, the water-dispersed silica sol containing aluminum atom-containing hollow silica particles can be produced by the following steps. (i) step: preparing an aqueous sol containing hollow silica particles; Step (ii): A step of adding an aluminum compound to the aqueous sol prepared in step (i) in a proportion of 0.0001 to 0.5 g, calculated as Al2O3, per 1 g of hollow silica particles, and maintaining the mixture at 40 to 260°C for 0.1 to 24 hours to obtain an aluminum atom-containing hollow silica aqueous sol.

[0093] The hollow silica particles constituting the aqueous sol containing hollow silica particles (also referred to as hollow silica aqueous sol) prepared in step (i) have an outer shell containing silica and have a space inside the outer shell. Note that the "hollow silica particles" prepared in step (i) are, so to speak, raw material hollow silica particles, and are distinguished from the aluminum atom-containing hollow silica particles described above, i.e., they are aluminum atom-free hollow silica particles (however, the inclusion of aluminum atoms at an impurity level is permitted). The raw material hollow silica particles are obtained by forming a silica-based shell on the surface of a core portion, called a template, in an aqueous dispersion medium, and then removing the core portion (template). The template can be made of an organic material (e.g., hydrophilic organic resin particles such as polyethylene glycol, polystyrene, or polyester) or an inorganic material (e.g., hydrophilic inorganic compound particles such as calcium carbonate or sodium aluminate). The aqueous sol containing hollow silica particles as the raw material prepared in step (i) can be any of a non-hydrothermally treated hollow silica aqueous sol, a hydrothermally treated hollow silica aqueous sol, or a mixture thereof. The non-hydrothermally treated hollow silica aqueous sol is an aqueous sol of silica particles treated in an aqueous medium via heating at a temperature below 100°C, for example, from 20°C to less than 100°C, or from 40°C to less than 100°C, or from 50°C to less than 100°C. The hydrothermally treated silica aqueous sol is an aqueous sol of silica particles treated in an aqueous medium via heating at a temperature of from 100°C to 240°C, or from 110°C to 240°C. The raw material hollow silica aqueous sol (non-hydrothermally treated hollow silica aqueous sol, hydrothermally treated hollow silica aqueous sol, or a mixture thereof) can be in a form in which the raw material hollow silica particles in the aqueous sol contain aluminum atoms in the process (ii) described below, specifically in a form in which aluminosilicate sites are formed on the outer shells of the hollow silica particles. Because aluminosilicate sites can retain alkali metals, the raw material hollow silica aqueous sol can be selected so that aluminum atoms are present on the surface of the raw material hollow silica particles at a rate of 120 to 50,000 ppm / silica particle in terms of Al2O3 (per gram of hollow silica particles) as measured by the aforementioned leaching method.

[0094] In step (ii), an aluminum compound is added to the (raw material) hollow silica aqueous sol prepared in step (i) above, followed by heating and maintaining to obtain an aluminum atom-containing hollow silica aqueous sol. In this step, the aluminum compound acts on (i.e., impregnates) the raw material hollow silica particles from the outside, causing aluminum atoms to be present on the surfaces of the hollow silica particles, i.e., forming aluminosilicate sites at least on the surfaces of the particles.

[0095] When an aluminum compound is applied (impregnated) from the outside after the formation of the (raw material) hollow silica particles, there are two methods: one is to subject the hollow silica particles before impregnation to a hydrothermal treatment in advance, thereby increasing the density of the outer shell, and then impregnate the hollow silica particles with the aluminum compound by heat treatment; and the other is to impregnate hollow silica particles that have not been subjected to a hydrothermal treatment in advance with the aluminum compound by heat treatment. In either the former method or the latter method, it is preferable to impregnate the hollow silica particles with the aluminum compound so that the amount of aluminum atoms (in terms of Al2O3) present throughout the hollow silica particles is in the specific ratio described above, as measured by the dissolution method using the hydrofluoric acid aqueous solution described above.

[0096] The aluminum compound used in step (ii) can be added in an amount of 0.0001 to 0.5 g, 0.001 to 0.1 g, or 0.001 to 0.05 g calculated as Al2O3 per 1 g of hollow silica particles in the hollow silica aqueous sol. The heating temperature in step (ii) is 40 to 260°C, or 50 to 260°C, or 60 to 240°C. In the case of non-hydrothermal treatment, the heating temperature can be 40 to less than 100°C, or 50 to less than 100°C, or 60 to less than 100°C, and in the case of hydrothermal treatment, the heating temperature is 100 to 260°C. or 150 to 240°C. The heating time in step (ii) can be in the range of 0.1 to 48 hours, or 0.1 to 24 hours, or 0.1 to 10 hours, or 1 to 10 hours. Incidentally, whether the aluminum compound is impregnated into the hollow silica particles to form an aluminosilicate and thereby achieve the desired amount of aluminum atoms present depends in part on the treatment temperature in step (ii), and it is essential to carry out the heat treatment within the above temperature range.

[0097] Specific examples of the aluminum compound include at least one aluminum compound selected from the group consisting of aluminates, aluminum alkoxides, and hydrolysates thereof. Examples of the aluminates include sodium aluminate, potassium aluminate, calcium aluminate, magnesium aluminate, ammonium aluminate, and amine aluminate. Examples of the aluminum alkoxides include aluminum isopropoxide and aluminum butoxide. Among these, aluminates such as sodium aluminate are preferably used.

[0098] The aluminum compound can be added to the hollow silica aqueous sol in the form of a solid or an aqueous solution, and is preferably added in the form of an aqueous solution. When the aluminum compound is added to the hollow silica aqueous sol in the form of an aqueous solution, the concentration of the aluminum compound in the aqueous solution can be in the range of 0.01 to 20% by mass, 0.1 to 10% by mass, or 0.5 to 5% by mass. The aluminum compound can be added while stirring the hollow silica aqueous sol. The addition may be completed before the heating, may be started before the heating and completed during the heating, or may be continued throughout the entire heating period.

[0099] The aqueous sol containing the aluminum atom-containing hollow silica particles may be subjected to a step of adding sulfuric acid to the aqueous sol and maintaining the sol at a predetermined temperature (a so-called leaching step) in order to dissolve into the solution the aluminum atom-containing components that have not been doped on the surface or inside of the hollow silica particles and the metal impurities contained in the particles. This step may be carried out by, for example, adding sulfuric acid in a proportion of about 1 ppm to 5000 ppm relative to the mass of the particles in the sol, and then maintaining the sol at 5 to 100°C for 0.1 to 48 hours. If necessary, the method may include a step of contacting the aqueous sol containing aluminum atom-containing hollow silica particles with a cation exchange resin before or after the addition of sulfuric acid and holding at a predetermined temperature in order to remove metal-containing components remaining in the system, metal-containing components eluted into the liquid by the addition of sulfuric acid, and impurity basic components such as counter ion components eluted by the added sulfuric acid and affecting the stability of the sol.

[0100] The water-dispersed silica sol containing the aluminum atom-containing hollow silica particles thus obtained can be subjected to a step of substituting an organic solvent by ultrafiltration, heating under reduced pressure, or heating under normal pressure. Examples of the organic solvent include those listed above in [(C) Organic Solvent]. The pressure reduction conditions can be about 10 to 600 Torr, and the heating conditions can be about 30 to 200°C. The conversion from an aqueous sol to a hydrophobic organic solvent sol can be achieved by solvent-substituting the aqueous medium with a hydrophilic organic solvent (such as an alcohol), followed by further solvent-substituting with a hydrophobic organic solvent, and water may remain during this process. For example, the residual moisture content in an alcohol sol of aluminum-atom-containing hollow silica particles can be about 0.1 to 3.0% by mass, or about 0.1 to 1.0% by mass, and the residual moisture content in an organic solvent sol of aluminum-atom-containing hollow silica particles (the dispersion medium is an organic solvent other than alcohol) can be about 0.01 to 0.5% by mass.

[0101] Before or after the step of replacing with the organic solvent, a step of treating the surfaces of the aluminum atom-containing hollow silica particles with at least one silane compound selected from the group consisting of compounds represented by formula (1) and formula (2) can be further carried out. As described above in [(F) Silane Compound], this step may be carried out by adding the silane compound to an aqueous sol or organic solvent sol containing aluminum atom-containing hollow silica particles, followed by heating and stirring at 10°C to 95°C for approximately 0.1 to 20 hours. The step of adding the silane compound and heating and stirring may be carried out multiple times.

[0102] Furthermore, before or after the step of adding the silane compound and heating and stirring, a step of adding a basic compound to increase the pH by 0.1 to 7 may be included. The basic compound to be added may be either an organic base or an inorganic base, and those listed above under [Basic Compound] may be used.

[0103] In the method for producing hollow silica organosol of the present invention, the silane compound addition / heating and stirring step (a step of treating the surfaces of aluminum atom-containing hollow silica particles with a silane compound) and the basic compound addition step (pH increase step) are optional, and the organic solvent substitution step, silane compound addition / heating and stirring step, and pH increase step can be performed in any order, or in combination multiple times. For example, after the step of adding the silane compound and heating and stirring, and / or after the step of increasing the pH, the step of replacing with an organic solvent by ultrafiltration / heating under reduced pressure / heating under normal pressure may be carried out.Furthermore, after the step of increasing the pH, the step of adding the silane compound and heating and stirring may be carried out, and then the step of replacing with an organic solvent by ultrafiltration / heating under reduced pressure / heating under normal pressure may be carried out.However, the combination of these steps is not limited.

[0104] The organic solvent dispersion sol containing aluminum atom-containing hollow silica particles obtained by solvent substitution as described above can be mixed with the aforementioned (B) polymer, and optionally with the (D) component and / or the (E) component added thereto to obtain the hollow silica organosol according to the present invention. When mixing the (B) polymer, as well as the (D) reactive monomer and (E) polymer, the (C) organic solvent can be further added as needed to achieve uniform mixing and dispersion of the components. After achieving uniform mixing and dispersion, the (C) organic solvent can be distilled off as needed to prepare a sol having a predetermined concentration of the (C) component.

[0105] Specific procedures for dissolving the (B) polymer in an organic solvent dispersion sol containing the aluminum atom-containing hollow silica particles (hereinafter referred to as the organic solvent dispersion sol) and the (B) polymer include, for example, a method in which the (B) polymer is directly added to the organic solvent dispersion sol and stirred to dissolve the (B) polymer in the organic solvent sol, or a method in which the (B) polymer is first dissolved in an organic solvent that is miscible (soluble or compatible) with the organic solvent dispersion sol, the resulting mixture is added to the organic solvent dispersion sol, and stirred to dissolve the (B) polymer in the organic solvent sol. These procedures may be repeated multiple times, and cooling or heating may be performed during addition and stirring. If necessary, the organic solvent may be removed or reduced by heating under reduced pressure or the like (the organic solvent may remain). Furthermore, when these components are added and stirred, a polymerization inhibitor (such as 4-methoxyphenol) may be blended into the sol. That is, the hollow silica organosol according to the present invention may be in an embodiment that contains a polymerization inhibitor.

[0106] Examples of the polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, benzoquinone, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert- butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.), nitrosophenylhydroxyamine aluminum salts, diphenylnitrosamine, etc. For example, p-methoxyphenol can be contained in the hollow silica sol, and the content of the polymerization inhibitor is preferably 0.00001 to 5% by mass relative to the hollow silica particles (solid content). One type of polymerization inhibitor may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

[0107] [Resin composition] The present invention also covers a resin composition containing the hollow silica organosol and an organic resin material or a polysiloxane resin. In the resin composition, the aluminum atom-containing hollow silica particles (component (A)) can be, for example, 1% to 70% by mass, the polymer (component (B)) can be, for example, 1% to 99% by mass, and the organic resin material can be, for example, 0% to 99% by mass, out of the total solid content (100% by mass). The solid content of the resin composition refers to all components other than the solvent. When the (D) reactive monomer or (E) polymer is contained, these and the organic resin material may be the same or different. When the (D) reactive monomer or (E) polymer is contained, the proportion of the organic resin material (99% to 10% by mass) in the total solid content also includes the content of the (D) reactive monomer or (E) polymer. The resin composition according to the present invention may also include the above-mentioned polymerization inhibitor.

[0108] The organic resin material may be, for example, a thermosetting or photocurable resin material (curable resin), such as, but not limited to, a styrene-based resin, an epoxy-based resin, a thioepoxy resin, a novolac-based resin, a cyanate-based resin, a phenol-based resin, an acrylic-based resin, a maleimide-based resin, a polyester-based resin, a urethane-based resin, a polyurea resin, a polyimide-based resin, a polyamide-based resin, a polyamic acid resin, a polyhydroxyimide resin, a polybenzoxazole resin, a polybenzimidazole resin, a polybenzothiazole resin, a polyhydroxyamide resin, a polyhydroxyazomethine resin, a polyether-based resin, a polybenzoxazine resin, a polytetrafluoroethylene-based resin, a cycloolefin polymer-based resin, an unsaturated polyester-based resin, a vinyltriazine-based resin, a polyphenylene sulfide-based resin, a crosslinkable polyphenylene oxide-based resin, a curable polyphenylene ether-based resin, and a condensation-based resin.

[0109] Examples of organic resin materials are shown below. Examples of styrene-based resins include polystyrene, expanded polystyrene, AS resin (styrene-acrylonitrile copolymer), MS resin (styrene-methyl methacrylate copolymer), and ABS resin (styrene-acrylonitrile-butadiene resin). Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, aliphatic type epoxy resins, and glycidylamine type epoxy resins. The thioepoxy resins include polymers obtained using bis(2,3-epithiopropyl) sulfide, bis(2,3-epithiopropyl) disulfide, 1,3-bis(β-epithiopropylthio)cyclohexane, 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3-bis(β-epithiopropylthiomethyl)cyclohexane, 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, and 2-(2-β-epithiopropylthioethylthio)-1,3-bis(β-epithiopropylthio)propane, and further include polyisocyanates. It can be obtained by copolymerizing a carboxylate compound or a polythiol compound. Examples of novolac resins include phenol novolac resins, bisphenol A novolac resins, and cresol novolac resins. Cyanate-based resins include cyanate ester resins produced from cyanic acid and bisphenol A.

[0110] Examples of phenolic resins include novolak resins obtained from phenol and formaldehyde using an acid catalyst, and resol resins obtained using an alkali catalyst. Examples of acrylic resins include polymethyl methacrylate, polyacrylic acid esters obtained by copolymerizing methyl methacrylate, methyl methacrylate, styrene, or the like, sodium polyacrylate obtained by copolymerizing sodium acrylate, methyl acrylate, vinyl acetate, or the like, polyacrylonitrile obtained by copolymerizing acrylonitrile, methyl acrylate, methyl methacrylate, or the like, and polyacrylamide obtained by hydrolyzing acrylonitrile. Examples of the maleimide resin include maleimide-modified epoxy resin, epoxy-modified bismaleimide resin, and thiol-modified bismaleimide resin. Examples of polyester resins include aliphatic polyesters obtained by polycondensation or ring-opening polymerization, such as polycaprolactone (PCL), polylactic acid (PLA), polyhydroxybutyrate (PHB), polyglycolic acid (PGA), and polyethylene adipate (PEA); semi-aromatic polyesters obtained by polycondensation, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polytrimethylene terephthalate (PTT); and aromatic polyesters obtained by polycondensation, such as polyester (LCP) of 4-hydroxybenzoic acid and 6-hydroxynaphthalene-2-carboxylic acid, and polyester (PAR) of bisphenol A and phthalic acid.

[0111] Examples of urethane-based resins include acrylic urethane resins that are made by combining a polyol as a base agent with a polyisocyanate as a curing agent, and that contain an acrylic polyol as a base agent. The polyurea resin may be a resin obtained by reacting an isocyanate with a polyamine. As the polyimide resin, a resin obtained by the reaction of a carboxylic acid anhydride with a diamine is used, and examples of condensation polymerization type polyimides include pyromellitic acid type polyimide resins, biphenyltetracarboxylic acid type polyimide resins, and benzophenonetetracarboxylic acid type polyimide resins. Examples of addition type polyimides include bismaleimide type polyimide resins, nadic acid-terminated polyimide resins, and acetylene-terminated polyimide resins. Polyamide resins are linear polymers formed by amide bonds, and may be synthesized by ring-opening polymerization of omega amino acids or by condensation polymerization of diamines and dicarboxylic acids. Examples of such resins include nylon, which contains an aliphatic skeleton, and aramid, which contains only an aromatic skeleton. As the polyamic acid resin, polyamic acid can be used as an intermediate polymer of acid anhydride and diamine for synthesizing polyimide resin.

[0112] The polyhydroxyimide resin may be a photosensitive polyimide resin having a hydroxyamide group or a hydroxyimide group. The polybenzoxazole resin may be a thermosetting resin having a benzoxazole ring. The polybenzimidazole resin is a polybenzoazole containing benzimidazole as a repeating unit, such as polybenzoxazole or polybenzothiazole. The polyhydroxyazomethine resin includes a polyhydroxyazomethine resin having azomethine as a linking moiety. Polyether resins are produced by reacting diisocyanates with glycols or diamines. Examples of suitable resins include engineering plastics such as polyether ether ketone (PEEK), polyether ketone (PEK), and polyether sulfone (PES).

[0113] The polybenzoxazine resin is formed by reacting phenol and bisphenol A with formaldehyde and an aromatic amine, and can be cured by, for example, thermal ring-opening polymerization. Examples of polytetrafluoroethylene resins include Teflon (registered trademark), which is a polymer of tetrafluoroethylene. Examples of cycloolefin polymer resins include addition copolymers of norbornenes, hydrogenated ring-opening metathesis polymers of norbornenes, transannular polymers of alkylidenenorbornenes, addition polymers of norbornenes, hydrogenated 1,2- and 1,4-unpolymerized polymers of cyclopentadiene, and ring-opening polymers of conjugated dienes. Examples of unsaturated polyester resins include resins obtained by dissolving polyester obtained by the condensation reaction of maleic anhydride and glycol in styrene or methyl methacrylate and then heat-curing the polyester.

[0114] An example of the vinyl triazine resin is a resin obtained by polymerizing 2-vinyl-4,6-diamino-1,3,5-triazine. Examples of polyphenylene sulfide resins include resins having a linear structure in which benzene rings and sulfur atoms are alternately bonded. Examples of crosslinkable polyphenylene oxide resins include polymer alloys of polyphenylene ether, which is a heat-resistant polyether resin polymerized with 2,6-dimethylphenylene oxide, and polystyrene. Condensation resins include, in addition to the above-mentioned polyamide resins and polyester resins, starch, phenol resins, urea resins, melamine resins, polycarbonate resins, and the like.

[0115] Among the above resins, polysiloxane resins can be obtained by hydrolysis of a silane compound followed by dehydration condensation. This hydrolysis and condensation can be carried out under the hydrolysis conditions of the silane compound (C) described above.

[0116] Silane compounds can be produced by combining tetrafunctional silanes (silane compounds having four hydrolyzable groups), trifunctional silanes (silane compounds having three hydrolyzable groups and one organic group), bifunctional silanes (silane compounds having two hydrolyzable groups and two organic groups), and monofunctional silanes (silane compounds having one hydrolyzable group and three organic groups). For example, polysiloxane resins can be produced by combining tetrafunctional silanes and trifunctional silanes.

[0117] Examples of tetrafunctional silanes include tetraethoxysilane and tetramethoxysilane, with tetraethoxysilane being particularly preferred.

[0118] Examples of trifunctional silanes include alkyl silanes such as methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, and decyltrimethoxysilane; Aryl silanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyltrimethoxysilane, and phenylmethyltriethoxysilane; vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Epoxy silanes such as glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; styryl silanes such as p-styryltrimethoxysilane; methacrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic silanes such as 3-acryloxypropyltrimethoxysilane; amine-based silanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N,N-dimethylaminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; Isocyanurate silanes such as tris-(trimethoxysilylpropyl) isocyanurate and diallyl(trimethoxysilylpropyl) isocyanurate; ureido-based silanes such as 3-ureidopropyltrialkoxysilane; mercapto-based silanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; Examples include isocyanate-based silanes such as 3-isocyanatepropyltriethoxysilane.

[0119] Examples of polysiloxane resins include polysiloxane resins obtained by copolymerizing tetraethoxysilane, methyltrimethoxysilane, and phenyltrimethoxysilane, and polysiloxane resins obtained by copolymerizing diallyl(trimethoxysilylpropyl)isocyanurate, tetraethoxysilane, methyltrimethoxysilane, and N,N-dimethylaminopropyltrimethoxysilane. The weight-average molecular weight of these linear or spherical polysiloxane resins can be set in the range of 1,000 to 100,000, or 1,000 to 5,000.

[0120] Furthermore, the resin composition of the present invention may contain various curing agents as needed, such as an amine-based curing agent, an acid anhydride-based curing agent, a radical generator-based curing agent (thermal radical generator, photoradical generator), an acid generator-based curing agent (thermal acid generator, photoacid generator), or a base generator (thermal base generator, photobase generator). Furthermore, the resin composition of the present invention may contain conventional additives as needed. Examples of such additives include surfactants (leveling agents), pigments, colorants, thickeners, adhesion promoters, sensitizers, antifoaming agents, coating property improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light resistance stabilizers, etc.), plasticizers, dissolution promoters, fillers, antistatic agents, development inhibitors (diazonaphthoquinone, etc.), etc. These additives may be used alone or in combination of two or more. The resin composition can be cured (composite material) by, for example, applying it to a substrate or filling it into a predetermined mold or the like and then heating, irradiating it with light, or a combination thereof.

[0121] More specifically, examples of the organic resin material (curable resin) include resins having functional groups such as epoxy groups or (meth)acryloyl groups, and isocyanate-based resins. For example, photocurable polyfunctional acrylates can be preferably used.

[0122] Examples of the polyfunctional acrylate include polyfunctional acrylates having difunctional, trifunctional, tetrafunctional, or higher functional groups in the molecule, such as neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetraacrylate, and the like. dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Examples of these polyfunctional acrylates include compounds represented by the following formula: [ka] [ka] [ka] [ka]

[0123] When the organic resin material is a thermosetting resin material, the thermosetting agent can be added in the range of 0.01 to 50 phr or 0.01 to 10 phr to the resin containing a functional group such as an epoxy group or a (meth)acryloyl group, and 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, to the functional group such as an epoxy group or a (meth)acryloyl group. The equivalent of the thermosetting agent to the curable resin is expressed as the equivalent ratio of the thermosetting agent to the functional group.

[0124] Examples of the thermal curing agent include phenolic resins, amine-based curing agents, polyamide resins, imidazoles, polymercaptans, acid anhydrides, thermal radical generators, thermal acid generators, etc. In particular, thermal radical generator-based curing agents, acid anhydride-based curing agents, and amine-based curing agents are preferred. Although these thermosetting agents can be used by dissolving them in a solvent even if they are solid, evaporation of the solvent contained in the resin composition reduces the density of the cured product and creates pores, resulting in reduced strength and reduced water resistance. Therefore, it is preferable that the curing agent itself is liquid at room temperature and normal pressure.

[0125] Examples of the phenol resin include phenol novolac resin and cresol novolac resin. Examples of the amine-based curing agent 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, menthylenediamine, isophoronediamine, diaminodicyclohexylmethane, 1,3-diaminomethylcyclohexane, xylenediamine, metaphenylenediamine, and diaminodiphenylmethane. Examples of the diaminodiphenylmethane include diaminodiphenylmethane, diaminodiphenyl sulfone, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and diethyltoluenediamine. Of these, liquid diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthenediamine, isophoronediamine, diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and diethyltoluenediamine can be preferably used. The polyamide resin is produced by condensing, for example, a dimer acid with a polyamine, and includes polyamide amines having a primary amine and a secondary amine in the molecule. Examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and epoxyimidazole adduct. The polymercaptan may be, for example, one in which a mercaptan group is present at the end of a polypropylene glycol chain or one in which a mercaptan group is present at the end of a polyethylene glycol chain, and is preferably a liquid polymercaptan.

[0126] As the acid anhydride curing agent, the anhydride of the compound having a plurality of carboxyl groups in one molecule is preferred.Specific examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride (methylnadic anhydride, methylhimic anhydride), hydrogenated methylnadic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, chlorendic anhydride, etc. Among these, methyltetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride (methylnadic anhydride, methylhimic anhydride), hydrogenated methylnadic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methylhexahydrophthalic anhydride, and a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, which are liquid at room temperature and pressure, are preferred. These liquid acid anhydrides have a viscosity of about 10 mPa·s to 1000 mPa·s when measured at 25°C.

[0127] Examples of the thermal radical generator include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylpropionate)dimethyl, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, and benzoyl peroxide. These compounds are available from Tokyo Chemical Industry Co., Ltd.

[0128] Examples of the thermal acid generator include sulfonium salts and phosphonium salts. Of these, sulfonium salts are preferably used, and examples thereof include compounds represented by the following formulae (C-1) and (C-2). [ka] In the above formula, R represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, and is particularly preferably an alkyl group having 1 to 12 carbon atoms.

[0129] In addition, a curing aid can be used in combination with the heat curing agent as appropriate. Examples of the curing aid include organic phosphorus compounds such as triphenylphosphine and tributylphosphine, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and methyltriphenylphosphonium diethyl phosphate, and quaternary ammonium salts such as 1,8-diazabicyclo(5,4,0)undecane-7-ene, salts of 1,8-diazabicyclo(5,4,0)undecane-7-ene and octylic acid, zinc octylate, and tetrabutylammonium bromide. These curing aids can be contained in a ratio of 0.001 to 0.1 parts by mass per part by mass of the heat curing agent.

[0130] The thermosetting resin composition can be obtained in the form of a thermosetting varnish by mixing the organic resin material (curable resin), the curing agent, and optionally the curing aid. Mixing can be carried out in a reaction vessel using a stirring blade or a kneader. The mixing is carried out by a heated mixing method at a temperature of 60°C to 100°C for 0.5 to 1 hour. The obtained thermosetting resin composition is a thermosetting composition, and its viscosity can be adjusted to an appropriate level depending on the intended use, such as for use as a liquid encapsulant. The thermosetting resin composition can be used for partial encapsulation of any desired location by casting, potting, dispensing, printing, or other methods, i.e., the composition can be used as a transparent encapsulant for LEDs and the like. Furthermore, a liquid thermosetting resin composition using an epoxy resin as the organic resin material can be directly mounted on an LED or the like in its liquid state using the method described above, followed by drying and curing to obtain a cured epoxy resin product. The thermosetting resin composition is applied to a substrate or the like and heated at a temperature of 80 to 200° C. to obtain a cured product (composite material).

[0131] When the resin 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 to the resin containing a functional group such as an epoxy group or a (meth)acryloyl group. For example, the photocuring agent (photoradical generator, photoacid generator) can be contained in a ratio of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, to the functional group such as an epoxy group or a (meth)acryloyl group. The equivalent of the photocuring agent to the curable resin material is expressed as the equivalent ratio of the photocuring agent to the functional group.

[0132] The photoradical generator is not particularly limited as long as it generates radicals directly or indirectly upon irradiation with light. Examples of photoradical generators (also referred to as photoradical polymerization initiators) include imidazole compounds, diazo compounds, bisimidazole compounds, N-arylglycine compounds, organic azide compounds, titanocene compounds, aluminate compounds, organic peroxides, N-alkoxypyridinium salt compounds, and thioxanthone compounds.

[0133] Examples of the diazo compound include 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzeneborofluoride, 1-diazo-4-N,N-dimethylaminobenzene chloride, and 1-diazo-4-N,N-diethylaminobenzeneborofluoride. Examples of the bisimidazole compound include 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetrakis(3,4,5-trimethoxyphenyl)1,2'-bisimidazole and 2,2'-bis(o-chlorophenyl)4,5,4',5'-tetraphenyl-1,2'-bisimidazole. Examples of the organic azide compound include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, 4,4'-diazidochalcone, 4,4'-diazidodiphenyl sulfide, and 2,6-bis(4'-azidobenzal)-4-methylcyclohexanone. Examples of the titanocene compound 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-di ... Examples of such a bis(methylcyclopentadienyl)-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-pyrrol-1-yl)-phenyl). Other examples of photoradical generators include 1,3-di(tert-butyldioxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(tert-butyldioxycarbonyl)benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone.

[0134] These photoradical generators (photoradical polymerization agents) are available, for example, under the trade name Irgacure TPO manufactured by BASF (the component is 2,4,6-trimethylbenzoyldiphenylphosphine oxide, a compound represented by the following formula (c1-1-1)), under the trade name Omnirad819 manufactured by IGM RESINS (the component is bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, a compound represented by the following formula (c1-1-2)), and under the trade name Irgacure 184 manufactured by IGM RESINS (the component is 1-hydroxycyclohexylphenyl ketone, a compound represented by the following formula (c1-1-3)). [ka]

[0135] The photoacid generator is not particularly limited as long as it generates an acid directly or indirectly upon irradiation with light. Specific examples of the photoacid generator include triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivative compounds, onium salts such as iodonium salts, sulfonium salts, phosphonium salts and selenium salts, metallocene complexes, and iron arene complexes.

[0136] In the onium salt used as the photoacid generator, examples of the iodonium salt include diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium mesylate, bis(p-tert-butylphenyl)iodonium tosylate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, and bis(p-tert-butylphenyl)iodonium bromide. bis(alkylphenyl)iodonium salts such as bis(4-t-butylphenyl)iodonium tetrafluoroborate, bis(p-tert-butylphenyl)iodonium chloride, bis(p-chlorophenyl)iodonium chloride, bis(p-chlorophenyl)iodonium tetrafluoroborate, and further bis(4-t-butylphenyl)iodonium hexafluorophosphate; alkoxycarbonylalkoxy-trialkylaryliodonium salts (for example, 4-[(1-ethoxycarbonyl-ethoxy)phenyl]-(2,4,6-trimethylphenyl)iodonium hexafluorophosphate); bis(alkoxyaryl)iodonium salts (for example, bis(alkoxyphenyl)iodonium salts such as (4-methoxyphenyl)phenyliodonium hexafluoroantimonate); can be done. Examples of the sulfonium salts include triphenylsulfonium salts such as triphenylsulfonium chloride, triphenylsulfonium bromide, tri(p-methoxyphenyl)sulfonium tetrafluoroborate, tri(p-methoxyphenyl)sulfonium hexafluorophosphonate, tri(p-ethoxyphenyl)sulfonium tetrafluoroborate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, and triphenylsulfonium hexafluorophosphate; bis[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluorophosphate, and (4-methoxyphenyl)diphenylsulfonium hexafluoroantimonate. Examples of the phosphonium salt include triphenylphosphonium chloride, triphenylphosphonium bromide, tri(p-methoxyphenyl)phosphonium tetrafluoroborate, tri(p-methoxyphenyl)phosphonium hexafluorophosphonate, tri(p-ethoxyphenyl)phosphonium tetrafluoroborate, 4-chlorobenzenediazonium hexafluorophosphate, and benzyltriphenylphosphonium hexafluoroantimonate. Examples of the selenium salt include selenium salts such as triphenylselenium hexafluorophosphate. Examples of metallocene complexes include (η5 or η6-isopropylbenzene)(η5-cyclopentadienyl)iron(II) hexafluorophosphate.

[0137] Furthermore, compounds represented by the following formulae (A-1) to (A-10) and compounds represented by the following formulae (B-1) to (B-57) can be used as photoacid generators. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0138] Among these photoacid generators, sulfonium salt compounds and iodonium salt compounds are preferred. The anion species thereof is CF3SO3 - , C4F9SO3 - , C8F 17 SO3 - , camphorsulfonate anion, tosylate anion, BF4 - , PF6 - , AsF6 - and SbF6 - In particular, anion species such as phosphorus hexafluoride and antimony hexafluoride, which exhibit strong acidity, are preferred.

[0139] The photocurable resin composition is applied to a substrate to form a coating film, and the coating film is cured by irradiating it with light to obtain a coating (cured product). Heating may also be performed before or after light irradiation. Examples of methods for applying the resin composition include flow coating, spin coating, spray coating, screen printing, casting, bar coating, curtain coating, roll coating, gravure coating, dipping, and slit coating. The thickness of the coating film can be selected from a range of about 0.01 μm to 10 mm depending on the application of the cured product. For example, when used as a photoresist, it can be about 0.05 to 10 μm (particularly 0.1 to 5 μm), when used as a printed wiring board, it can be about 5 μm to 5 mm (particularly 100 to 1 mm), and when used as an optical thin film, it can be about 0.1 to 100 μm (particularly 0.3 to 50 μm).

[0140] When a transparent coating is to be obtained, it is desirable that the visible light transmittance of the coating is 80% or more, or 90% or more, typically 90% to 96%.

[0141] When a photoacid generator is used, the light used to irradiate or expose the coating film may be, for example, gamma rays, X-rays, ultraviolet light, or visible light, and is usually visible light or ultraviolet light, particularly ultraviolet light (UV). Curing by UV irradiation can be applied to materials (devices) that are sensitive to heat. The wavelength of the light is, for example, 150 to 800 nm, preferably 150 to 600 nm, and more preferably about 150 to 400 nm. The amount of irradiation light varies depending on the thickness of the coating film, but is, for example, 2 to 20,000 mJ / cm. 2 , preferably 5 to 5,000 mJ / cm 2 The light source can be selected depending on the type of light to be exposed, and for example, in the case of ultraviolet light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a deuterium lamp, a halogen lamp, or laser light (helium-cadmium laser, excimer laser, etc.) can be used. Such light irradiation causes the curing reaction of the resin composition to proceed.

[0142] When using the thermal acid generator described above, or when using a photoacid generator, the coating film is heated as needed after light irradiation, for example, at 60 to 350° C., preferably about 100 to 300° C. The heating time can be selected within a range of 3 seconds or more (for example, about 3 seconds to 5 hours), for example, 5 seconds to 2 hours, preferably about 20 seconds to 30 minutes, and usually about 1 minute to 3 hours (for example, about 5 minutes to 2.5 hours).

[0143] Furthermore, when forming a pattern or an image (for example, when producing a printed wiring board), the coating film formed on the substrate may be subjected to pattern exposure, which may be performed by scanning with laser light or by irradiating with light through a photomask. The non-irradiated areas (unexposed parts) generated by such pattern exposure are developed (or dissolved) with a developer to form a pattern or an image.

[0144] The developer used for development may be an alkaline aqueous solution or an organic solvent. Examples of the alkaline aqueous solution include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine. The alkaline aqueous solution (alkaline developer) is usually an aqueous solution of 10% by mass or less, and preferably an aqueous solution of 0.1 to 3.0% by mass. Furthermore, alcohols and surfactants can be added to the developer, and each of these is preferably 0.05 to 10 parts by mass per 100 parts by mass of the developer. Among these, a 0.1 to 2.38% by mass aqueous solution of tetramethylammonium hydroxide can typically be used. In addition, the organic solvent used as the developer may be a common organic solvent, such as acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, ethyl lactate, cyclohexanone, etc., and these may be used alone or in combination. In particular, propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, etc. are preferably used as the developer.

[0145] An adhesion promoter can be added to the resin composition for the purpose of improving adhesion to the substrate after development. Examples of the adhesion promoter include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane, silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole, vinyltrichlorosilane, and 3-chloropropyltrimethoxysilane. Examples of adhesion promoters include silanes such as 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-(N-piperidinyl)propyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. One of the above adhesion promoters can be used alone, or two or more can be used in combination. The amount of these adhesion promoters added is typically 18% by mass or less, for example, 0.0008 to 9% by mass, or for example, 0.04 to 9% by mass, based on the total solids content (100% by mass) of the resin composition.

[0146] The resin composition may also contain a sensitizer. Usable sensitizers include, for example, anthracene, phenothiazene, perylene, thioxanthone, and benzophenone thioxanthone. Sensitizing dyes include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, and pyrylium salt dyes. Anthracene sensitizers are particularly preferred. When used in combination with a cationic curing catalyst (a radiation-sensitive cationic polymerization initiator), sensitivity is dramatically improved. Furthermore, since these sensitizers also have the ability to initiate radical polymerization, selecting these sensitizers can simplify the catalyst species used in hybrid systems that combine cationic and radical curing systems. Specific anthracene compounds that are effective include dibutoxyanthracene and dipropoxyanthraquinone. The amount of these sensitizers added can be, for example, 0.01 to 20 mass %, or for example, 0.01 to 10 mass %, based on the total amount (100 mass %) of solids in the resin composition.

[0147] As described above, the resin composition according to the present invention can be either thermosetting or photosetting, i.e., it can be photocured or thermoset using a photoradical generator, a thermal radical generator, a photoacid generator, or a thermal acid generator. When a photoacid generator or a thermal acid generator is used, for example, when an epoxy resin is selected as the organic resin material, it is possible to avoid using commonly used epoxy curing agents (e.g., amines or acid anhydrides), or if such agents are used, their content can be extremely reduced, resulting in good storage stability of the resin composition.

[0148] In addition, surfactants (leveling agents) that can be blended into the resin composition (thermosetting / photocurable) of the present invention include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and silicone surfactants. When a surfactant (leveling agent) is used, its blending amount can be in the range of 0.01 to 5 phr or 0.01 to 1 phr relative to the organic resin material.

[0149] Examples of anionic surfactants that can be used in the present invention include sodium and potassium salts of fatty acids, alkylbenzene sulfonates, higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, α-sulfofatty acid esters, α-olefin sulfonates, monoalkyl phosphate esters, and alkanesulfonates. Examples of the alkylbenzenesulfonate include sodium salts, potassium salts, and lithium salts of alkylbenzenesulfonic acid, and more specific examples include sodium alkylbenzenesulfonate having 10 to 16 carbon atoms, alkylbenzenesulfonic acid having 10 to 16 carbon atoms, and sodium alkylnaphthalenesulfonate. Examples of the higher alcohol sulfate salts include sodium dodecyl sulfate (sodium lauryl sulfate) having 12 carbon atoms, triethanolamine lauryl sulfate, and triethanolammonium lauryl sulfate. Examples of the polyoxyethylene alkyl ether sulfate include polyoxyethylene alkyl ether sulfates. Examples of suitable styrenated phenyl ethers include sodium styrenated phenyl ether sulfate, ammonium polyoxyethylene styrenated phenyl ether sulfate, sodium polyoxyethylene decyl ether sulfate, ammonium polyoxyethylene decyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, and sodium polyoxyethylene oleyl cetyl ether sulfate. Examples of the α-olefin sulfonate include sodium α-olefin sulfonate. Examples of the alkanesulfonates include sodium 2-ethylhexyl sulfate.

[0150] Examples of cationic surfactants that can be used in the present invention include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, and amine salt-based agents. The alkyltrimethylammonium salt is a quaternary ammonium salt, which is a compound having a chloride ion or a bromide ion as a counter ion. Examples include dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, coconut alkyltrimethylammonium chloride, and alkyl(C16-18)trimethylammonium chloride. The dialkyldimethylammonium salt is a compound having two lipophilic main chains and two methyl groups. Examples include bis(hydrogenated tallow)dimethylammonium chloride. Examples include didecyldimethylammonium chloride, dicocoalkyldimethylammonium chloride, dihydrogenated tallow alkyldimethylammonium chloride, and dialkyl(C14-18)dimethylammonium chloride. The alkyldimethylbenzylammonium salt is a quaternary ammonium salt having one lipophilic main chain, two methyl groups, and a benzyl group, and examples thereof include alkyl(C8-18)dimethylbenzylammonium chloride (benzalkonium chloride). The amine salt agent is a compound in which the hydrogen atom of ammonia is substituted with one or more hydrocarbon groups, and examples thereof include N-methylbishydroxyethylamine fatty acid ester hydrochloride.

[0151] Examples of amphoteric surfactants that can be used in the present invention include N-alkyl-β-alanine type alkylamino fatty acid salts, alkylcarboxybetaine type alkylbetaines, and N,N-dimethyldodecylamine oxide type alkylamine oxides. Examples of these include lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, and lauryl dimethylamine oxide.

[0152] Nonionic surfactants that can be used in the present invention include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl 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 the polyoxyethylene alkyl ether include polyoxyethylene dodecyl ether (polyoxyethylene lauryl ether), polyoxyalkylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyalkylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene behenyl ether, polyoxyethylene-2-ethylhexyl ether, and polyoxyethylene isodecyl ether. Examples of the polyoxyethylene alkylphenyl ether include polyoxyethylene styrenated phenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkylphenyl ether, and polyoxyethylene alkylphenyl ether. Examples thereof include diethylene distyrenated phenyl ether and polyoxyethylene tribenzyl phenyl ether. Examples of the alkyl glucoside include decyl glucoside and lauryl glucoside. Examples of the polyoxyethylene fatty acid ester include polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyethylene glycol distearate, polyethylene glycol dioleate, and polypropylene glycol dioleate. Examples of the sorbitan fatty acid esters include sorbitan monocaprylate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monosesquioleate, and ethylene oxide adducts thereof. Examples of the polyoxyethylene sorbitan fatty acid esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan triisostearate. Examples of the fatty acid alkanolamide include coconut oil fatty acid diethanolamide, beef tallow fatty acid diethanolamide, lauric acid diethanolamide, and oleic acid diethanolamide. Further examples of nonionic surfactants include polyoxyalkyl ethers or polyoxyalkyl glycols such as polyoxyethylene polyoxypropylene glycol and polyoxyethylene fatty acid esters, polyoxyethylene hydrogenated castor oil ether, sorbitan fatty acid ester alkyl ether, and alkyl polyglucosides.

[0153] The silicone surfactant is a compound having a repeating unit containing a siloxane bond in the main chain, and for example, a compound having a weight-average molecular weight in the range of 500 to 50,000 can be used in the present invention. These may be so-called modified silicone surfactants having a structure in which organic groups are introduced into the side chain and / or terminal of a polysiloxane. Examples of the organic groups that can be introduced into the side chain and / or terminal include amino groups, epoxy groups, alicyclic epoxy groups, carbinol groups, mercapto groups, carboxy groups, aliphatic ester groups, aliphatic amide groups, and polyether groups. Specific examples of silicone surfactants that can be used in the present invention include, for example, trade names Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), Silwet 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, ​​and L-765. Examples of suitable polyether-modified silicones include L-7001 (manufactured by Dowsil), L-8500, and L-8610 (manufactured by Momentive Performance Materials), KP-341, KF-6001, and KF-6002 (manufactured by Shin-Etsu Silicones Co., Ltd.), and BYK307, BYK323, and BYK330 (manufactured by BYK-Chemie). For example, a polyether-modified silicone under the trade name of L-7001 (manufactured by Dowsil) can be suitably used.

[0154] Applies to The hollow silica organosol according to the present invention, and in particular a resin composition containing the organosol, can be used in a variety of applications, including semiconductor device materials, semiconductor element materials, semiconductor resist materials, insulating film materials, copper-clad laminate materials, printed circuit board materials, printing plate materials, printing ink materials, pigments, paints, and sealants. The materials are suitable for use in applications such as materials for semiconductor devices, hard coat materials, 3D printing materials, anti-reflective film materials, materials for automotive parts, materials for electronic parts, mechanical element parts, adhesive materials, materials for batteries, materials for power generation, materials for imparting electrostatic charge, materials for imparting conductivity, materials for imparting powder fluidity, materials for cosmetics, flexible wiring materials, materials for liquid crystal displays, materials for organic EL displays, materials for micro LED displays, materials for QD-EL displays, flexible display materials, antenna materials, optical wiring materials, and sensing materials.

[0155] For example, thermosetting materials and photocurable materials using resin compositions containing the hollow silica organosol of the present invention have characteristics such as transparency and small shrinkage upon curing, and can be used for coating and bonding electronic components, optical components (anti-reflection coatings), and precision mechanical components. For example, it can be used to bond mobile phone and camera lenses, optical elements such as light-emitting diodes (LEDs) and semiconductor lasers (LDs), liquid crystal panels, biochips, camera lenses and prisms, magnetic components in hard disks for computers, CD and DVD player pickups (the part that captures the optical information reflected from the disc), speaker cones and coils, motor magnets, circuit boards, electronic components, and internal engine parts for automobiles. It can also be used as a hard coating material (coating material) for surface protection of automobile bodies, lamps, electrical appliances, building materials, plastics, etc., and can be applied to, for example, automobile and motorcycle bodies, headlight lenses and mirrors, plastic lenses for eyeglasses, mobile phones, game consoles, optical films, ID cards, etc. Examples of ink materials for printing on metals such as aluminum and plastics include credit cards, membership cards, switches for electrical appliances and office equipment, printing ink for keyboards, and inkjet printer ink for CDs, DVDs, etc. Other applications include the creation of complex three-dimensional hardened objects in combination with 3D CAD, photolithography for producing models of industrial products, coating of optical fibers, adhesion, optical waveguides, thick-film resists, etc. The composition can also be suitably used as an insulating resin for electronic materials such as anti-reflection films, semiconductor encapsulation materials, adhesives for electronic materials, printed wiring board materials, interlayer insulating film materials, and encapsulation materials for power modules, as well as an insulating resin for use in high-voltage equipment such as generator coils, transformer coils, and gas-insulated switchgears. [Example]

[0156] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0157] The raw materials used in the examples and comparative examples, namely, hollow silica aqueous sol, silane compound, base (pH adjuster), organic solvent, and polymer, are as follows.

[0158] (Raw material: hollow silica aqueous sol) Water-dispersed silica sol A: Product name HKT-A20-40D (average primary particle diameter by TEM: 40 nm, outer shell thickness: 5 nm, specific surface area by BET method (C) 125 m 2 / g, specific surface area (D) by TEM: 68 m 2 / g, refractive index 1.3, manufactured by Ningbo Dilato, water-dispersed silica sol of hollow silica particles, average particle size by DLS method: 47 nm, amount of aluminum atoms present in the entire hollow silica particle is less than 1 ppm / silica particle in terms of Al2O3) (Silane compound (surface modifier, silanes manufactured by Shin-Etsu Chemical Co., Ltd.)) HMDS: Hexamethyldisiloxane MPMDMS: 3-methacryloxypropylmethyldimethoxysilane (base) DiPA: Diisopropylamine (organic solvent) MeOH: Methanol MEK: Methyl ethyl ketone AN: Acetone HX: Hexane (Polymer, manufactured by ASM Co., Ltd.) Polymer with rotaxane structure: Product name SM2400C (axis molecular weight: 20,000)

[0159] According to the following methods, the physical properties of the above water-dispersed silica sol, the silica sols prepared in the Examples and Comparative Examples, and the silica sols and silica particles during the silica sol production process were evaluated.

[0160] (Measurement of solid content (silica particles) concentration in silica sol) The solid content (silica particle) concentration of the water-dispersed silica sol and the organic solvent-dispersed silica sol was calculated by placing the silica sol in a crucible, heating to remove the solvent, calcining at 1000°C, and weighing the resulting calcination residue to calculate the solid content concentration (silica particle concentration) (% by mass). As will be described later, the sols prepared in the examples contain sulfuric acid, amines for pH adjustment, and the like, but the organic components such as amines are almost completely lost through volatilization / thermal decomposition after the calcination, and the amounts of these components, including sulfuric acid, added are very small, so the concentration calculated by the above method can be treated as the hollow silica particle concentration in the silica sol. (Measurement of solid content (silica particles + rotaxane) concentration in silica sol) Furthermore, regarding the solid content (hollow silica particles + rotaxane) concentration of the rotaxane-dispersed silica sol prepared in the examples, these silica sols were placed in a crucible, heated to remove the solvent, and then calcined at 250°C. The resulting calcination residue was weighed to calculate the solid content concentration (mass%).

[0161] (pH measurement of silica sol) The pH of the water-dispersed silica sol was measured at 23°C using a pH meter (manufactured by DKK Toa Corporation, product name: MM-43X). The pH of the organic solvent-dispersed silica sol was measured at 25°C using a pH meter (manufactured by Toa DKK Corporation, product name: MM-43X) on a liquid obtained by mixing the organic solvent-dispersed silica sol and pure water in a mass ratio of 1:1 when the organic solvent serving as the dispersion medium was methanol (MeOH), or on a liquid obtained by mixing the organic solvent-dispersed silica sol, MeOH, and pure water in a mass ratio of 1:1:1 when the organic solvent was methyl ethyl ketone (MEK).

[0162] (Measurement of viscosity of silica sol) The viscosity of the water-dispersed silica sol, the organic solvent-dispersed silica sol, or the silica sol during the silica particle production process was measured at 25° C. using an Ostwald viscometer (manufactured by Shibata Scientific Co., Ltd.).

[0163] (Specific surface area value by nitrogen adsorption method (S N2 ) Measurement The specific surface area (S) of silica particles in water-dispersed silica sol was measured by nitrogen adsorption. N2 ) was measured by removing water-soluble cations in the water-dispersed silica sol with an H-type cation exchange resin (Dow Chemical Company, trade name: Amberlite IR-120B), and then drying the silica sol at 290°C to prepare a measurement sample. This was then measured by the BET single-point method using a nitrogen adsorption specific surface area measuring device (trade name: Monosorb, manufactured by Quantachrome Instruments Japan LLC) with a mixed gas of 30% N2 (nitrogen) and 70% He (helium) as the carrier gas. The specific surface area (S) of silica particles in organic solvent-dispersed silica sols was measured by nitrogen adsorption. N2 ) was measured by the BET single-point method using a measurement sample (silica particles (powder) heated at 150°C) obtained in the below-described (Measurement of carbon content (Cp) by elemental analysis of hollow silica particles).

[0164] (Number density of silanol groups on the surface of hollow silica particles) The number density of silanol groups on the surface of hollow silica particles was measured by the Sears method, which was performed with reference to the description in "Determination of Specific Surface Area of ​​Colloidal Silica by Titration with Sodium Hydroxide" (GW Sears, Jr., Analytical Chemistry, 28(12), 1981 (1956)). The target hollow silica sol was adjusted with pure water and 0.1 mol / L hydrochloric acid to a solids (silica particle) concentration of 1% by mass and a pH of 3 to 3.5, and this was used as a measurement sample. The obtained measurement sample was titrated with a 0.1 mol / L aqueous sodium hydroxide solution, and the number density of silanol groups on the hollow silica particle surface was calculated using the following formula. ρ = (A × f × 6022) ÷ (C × S) In the above formula, ρ, A, f, C, and S are respectively ρ: silanol group density (number / nm 2 ), A: Drop volume (mL) of 0.1 mol / L sodium hydroxide aqueous solution at pH 4-9, f: Factor of 0.1 mol / L sodium hydroxide aqueous solution, C: Mass of silica particles (g), S: Specific surface area of ​​silica particles measured by nitrogen adsorption method (m 2 / g).

[0165] (Measuring average particle size by DLS method (particle size by dynamic light scattering)) The average particle size measured by DLS (average particle size measured by dynamic light scattering: Z-average particle size) was measured using a dynamic light scattering particle size analyzer (manufactured by Malvern Panalytical, product name: Zetasizer Nano). 0.1 g of the target silica sol was dispensed into a glass cell with a 10 mm optical path length, and the same solvent as the dispersion medium of the silica sol was added to obtain a silica sol with a silica particle concentration adjusted to a count rate of 200 to 400 kcps when the attenuator was set to 7. For example, in Example 1 described below, water, MeOH, or MEK was added to obtain a silica sol with a silica particle concentration adjusted to a count rate of 200 to 400 kcps when the attenuator was set to 7. The prepared silica sol was placed in the cell so that the liquid level was approximately 1 cm above the bottom of the cell, and the dynamic light scattering particle size (Z-average particle size, harmonic mean particle size) of the silica particle sol was measured using the attenuator 7.

[0166] (Measurement of average primary particle size using a TEM (transmission electron microscope)) The particles in the silica sol were photographed using a transmission electron microscope (manufactured by JEOL Ltd., product name JEM-F200), and 300 randomly selected particles were binarized using an automatic image processing analyzer (manufactured by Nireco Corporation, product name LUZEX' AP). The diameter of the projected area converted into a circle was measured as the average primary particle diameter (HEYWOOD diameter). (Specific surface area converted from TEM (transmission electron microscope)) The specific surface area of ​​the hollow silica particles converted from TEM (transmission electron microscope) was calculated using the average primary particle diameter measured by the transmission electron microscope above, converted into spherical particles, using the following formula. Specific surface area (m) converted from TEM (transmission electron microscope) 2 / g) = 2720 / Average primary particle size by TEM (nm)

[0167] (Measurement of the amount of aluminum (B) present in the entire hollow silica particle / Dissolution method) A precisely weighed amount of hollow silica sol was dried, and 250 mg of the resulting particles were dissolved in 2.5 ml of nitric acid (Kanto Chemical Co., Inc., product name: nitric acid 1.38, purity 60.0%) and 2.5 ml of 38% hydrofluoric acid (Tama Chemicals Co., Ltd., product name: hydrofluoric acid) to obtain an aqueous solution. The amount of aluminum in the resulting aqueous solution was measured using an ICP-OES analyzer (Rigaku Corporation, product name: CIROS120 EOP), and the amount of aluminum present in the entire hollow silica particles was calculated as the amount per 1 g of hollow silica particles in terms of Al2O3 (Al2O3 (ppm) / silica particle).

[0168] (Measurement of the amount of aluminum (A) present on the surface of hollow silica particles / Leaching method) The cations in the silica sol were removed using H-type cation exchange resin, and the solvent was removed by heating. The dried product was then crushed in a mortar and further treated at 250°C for 2 hours to obtain a powder. 0.2 g of the resulting powder was placed in a polypropylene container (50 mL PP sampler bottle) containing 20 mL of 0.1 mol / L (N / 10) nitric acid solution and manually shaken 100 times per minute. Next, the mixture was sonicated for 10 minutes in an ultrasonic cleaner (manufactured by AS ONE, product name: ASU CLEANER ASU-10M) to obtain a mixture in which the powder and nitric acid solution had fully blended. The mixture was then placed in a 50°C thermostatic chamber and held for 17 hours. The mixture was then cooled to room temperature, placed in a centrifugal ultrafiltration filter (product name Amicon Ultra-15, molecular weight cutoff 10,000), and centrifuged (temperature: 5°C, rotation speed: 5000 rpm, time: 30 minutes). The amount of aluminum in the filtrate was measured using an ICP emission spectrometer, and the amount of aluminum present on the surface of the hollow silica particles was converted to Al2O3 and calculated as the amount per 1 g of hollow silica particles (Al2O3 (ppm) / silica particle).

[0169] (Measurement of surface charge of hollow silica particles) The silica sol was added to 10 mL of methanol to obtain a solids (silica particles) concentration of 0.5% by mass, which was used as a measurement sample. Using a particle charge meter (Voyt Turbo, product name PCD-06) and a 0.001 mol / L (N / 1000) DADMAC solution (Voyt Turbo) as a standard cation titrant, the titration value was measured until the streaming potential of the measurement sample reached zero. The titration value was divided by the mass of solids (silica particles) contained in the measurement sample, and the resulting value converted to the surface charge (μeq / g) per 1 g of hollow silica particles was determined. DADMAC stands for poly(diallyldimethylammonium chloride).

[0170] (Measurement of carbon content (Cp) by elemental analysis of hollow silica particles) Four milliliters of the silica sol obtained in the example was placed in a 42-ml pear-shaped settling tube (manufactured by Thermo Fisher Scientifics, trade name: Nalgene Oak Ridge), and 4 ml of MEK and 20 ml of hexane were added. The mixture was left to stand for 5 minutes to induce cloudiness, separation, or precipitation due to aggregation. The mixture was then centrifuged (temperature: 5°C, rotation speed: 20,000 rpm, time: 30 minutes) using a centrifuge (manufactured by Tomy Seiko Co., Ltd., trade name: Suprema 21 High-Speed ​​Refrigerated Centrifuge) and the supernatant was removed. Four milliliters of acetone was then added, and the resulting precipitate was redissolved using a test tube mixer (As One Corporation, trade name: MVM-10). 20 mL of hexane was then added. The mixture was then centrifuged and the supernatant was removed. 4 ml of acetone was then added, and the resulting precipitate was redissolved using a test tube mixer. 20 mL of hexane was then added. The mixture was then centrifuged and the supernatant was removed. The resulting precipitate (mixture) was vacuum dried (temperature: 60°C, pressure: -0.1 MPa), and the resulting powder was pulverized in a mortar for 10 minutes to obtain silica particles (powder). The resulting silica particles were heated at 150°C to remove adsorbed water, and a measurement sample was prepared. The carbon content (Cp: mass%) of the silica particles (measurement sample) was measured using an elemental analyzer (PerkinElmer, model name: Elemental Analyzer 2400II).

[0171] (Measurement of carbon content and unbound silane content (Ct) of hollow silica particles) The solvent of the silica sol obtained in the examples was heated at 150°C to remove the dispersant and adsorbed water, and a measurement sample was prepared. The measurement sample was measured using an elemental analyzer (manufactured by PerkinElmer, model name: Elemental Analyzer 2400II) to determine the total amount (Ct: mass%) of the carbon content of the hollow silica particles in the measurement sample (Cp) and the amount of carbon not contained in the particles (so-called unbonded) (derived from the silane compound, which is a surface modifier, also referred to as the unbonded silane content).

[0172] (Measurement of refractive index of hollow silica particles) Measurement was carried out according to the following steps 1) to 3). 1) Preparation of varnish containing aqueous sol of hollow silica particles 20.00 g of 3-glycidoxypropyltrimethoxysilane (manufactured by Momentive, trade name SILQUEST A-187T) was weighed into a plastic container, 18.57 g of methanol and 4.57 g of 0.01 N hydrochloric acid solution were added, and the mixture was stirred at room temperature for 5 hours. 6.00 g of a previously prepared methanol solution of aluminum 2,4-pentanedionate (Al(acac)3) (10% by weight Al(acac)3) was added as a curing agent, and the mixture was stirred for 10 minutes to prepare a partial hydrolyzate of 3-glycidoxypropyltrimethoxysilane (GPS) (concentration: 43% by weight). The prepared partial hydrolyzate of GPS, water, methanol, and 0.25 g of a methanol solution (10 mass% L-7604) of a leveling agent (DOWSIL trade name L-7604) were weighed into a brown bottle so that the total amount was 25.00 g, the final solvent composition was water / methanol = 9 / 1 by weight, and the amount of hollow silica particles in the hollow silica aqueous sol was 50 phr, 100 phr, or 150 phr, and the mixture was stirred at room temperature for 30 minutes to prepare a varnish containing hollow silica particles in the hollow silica aqueous sol (solid concentration: 4 mass%, hollow silica amount: 50 phr, 100 phr, or 150 phr). 2) Preparation of hollow silica particle-containing membrane Approximately 1 mL of the hollow silica particle aqueous sol-containing varnish (silica particle content: 50 phr, 100 phr, or 150 phr) obtained in step 1 was dropped onto a UV-O3-treated Si substrate and uniformly spread on the Si substrate using a spin coater (Mikasa Co., Ltd., product name Opticoat MS-B100) under the following conditions: ramp to 200 rpm over 2 seconds, 200 rpm x 10 seconds, then ramp to 800 rpm over 2 seconds, 800 rpm x 5 seconds, and then ramp down to 0 rpm over 5 seconds. The resulting film was then baked on a hot plate at 80°C for 5 minutes and then heat-treated in an oven at 120°C for 1 hour to prepare a hollow silica particle-containing film (hollow silica content: 50 phr, 100 phr, or 150 phr). 3) Measurement of the refractive index of hollow silica particle blended film and calculation of the refractive index of hollow silica particles The refractive index of the hollow silica particle-blended films obtained in 2) (hollow silica blending amount: 50 phr, 100 phr, or 150 phr) was measured using an ellipsometer (product name: Multi-Angle Spectroscopic Ellipsometer VASE, manufactured by J.A. Woollam Japan, Inc.). The refractive index of a film containing no hollow silica particles, prepared in the same manner using only the partial hydrolyzate of GPS, was also measured. The measured refractive index of the blended film was plotted against the blending amount of hollow silica particles, and the refractive index of the hollow silica particles was determined by extrapolating so that the blending amount of hollow silica particles was 100 mass%.

[0173] (Measurement of the amount of sulfuric acid in the water-dispersed silica sol (hereinafter referred to as the amount of sulfuric acid in the system)) The target water-dispersed silica sol was diluted 10 times with pure water, and the amount of sulfuric acid (ppm) in the system was measured by ion chromatography using an anion analyzer (trade name Dionex ICS-2100, manufactured by Thermo Scientific). .

[0174] (Measurement of moisture content) The amount of water contained in the target sol was measured by Karl Fischer titration using a Karl Fischer moisture meter (manufactured by Kyoto Electronics Manufacturing Co., Ltd., trade name: MKA-610).

[0175] (Measurement of the amount of methanol (MeOH)) The amount of methanol (MeOH) contained in the target sol was measured using a gas chromatograph (manufactured by Shimadzu Corporation, product name: GC-2014s) under the conditions described below. Column: 3mm x 1m glass column Filler: Polar Pack Q Column temperature: 130-230°C (heating rate: 8°C / min) Carrier: N240mL / min Detector: FID Injection volume: 1μL Internal standard: acetonitrile.

[0176] (Example 1) Preparation of rotaxane-dispersed silica sol of aluminum atom-containing hollow silica particles Step 1-1: 1856 g of water-dispersed silica sol A (HKT-A20-40D (Ningbo Dilato Co., Ltd., product name)) was placed in a 3 L plastic container and stirred at 650 rpm using a mechanical stirrer equipped with a glass stirring blade. While stirring, 32.2 g of a sodium aluminate aqueous solution diluted to a concentration of 1.0 mass% (calculated as Al2O3) was added dropwise over 1 minute, and the mixture was stirred at the same rotation speed for 30 minutes. 643.6 g of purified water was then added, and the mixture was stirred for an additional 10 minutes to obtain a mixture. Next, 2502 g of this mixture was placed in a 3 L stainless steel autoclave container and heated at 150°C for 5 hours while stirring at 80 rpm, and then cooled to below 50°C. To 1700 g of the obtained heat-treated water-dispersed silica sol, 1.51 g of an 8.2% aqueous sulfuric acid solution was added dropwise, and the mixture was stirred at room temperature at 800 rpm for 1 hour to obtain a sulfuric acid-added heat-treated water-dispersed silica sol. Next, the obtained sulfuric acid-added heat-treated water-dispersed silica sol was passed through a 200 mL column-packed cation exchange resin (H-type Amberlite (trade name) IR-120B, harmonic mean diameter 0.6 to 0.8 mm, Organo Corporation) at a space velocity (SV) of 5 / hour to obtain a water-dispersed silica sol of aluminum atom-containing hollow silica particles. The resulting water-dispersed silica sol was then heated at 80°C for 10 hours, cooled to 30°C or below, and then passed through a column of cation exchange resin (H-type Amberlite (trade name) IR-120B) at a space velocity (SV) of 5 / hour to obtain a water-dispersed silica sol of aluminum atom-containing hollow silica particles. The resulting aqueous dispersion of aluminum-containing hollow silica particles had a pH of 2.7 and a sulfuric acid content of 67 ppm. The solids content (silica particles) was 14.8% by mass, the viscosity was 1.6 mPa·s, the average particle size measured by DLS was 51 nm, the amount of aluminum atoms present in the entire hollow silica particles was 701 ppm / SiO2 in terms of Al2O3, and the surface charge per gram of hollow silica particles was 29 μeq / g. Then, 1000 g of the obtained water-dispersed silica sol of aluminum atom-containing hollow silica particles was placed in a 2 L recovery flask. The pressure was reduced to 580 Torr using a rotary evaporator, and the solvent (dispersion medium) was replaced with methanol (MeOH) while heating to 120°C. Methanol was then added to adjust the concentration, yielding a 20 mass% MeOH-dispersed silica sol of aluminum atom-containing hollow silica particles. The physical properties of the obtained silica sol dispersed in MeOH were as follows: average primary particle diameter by TEM: 40 nm; specific surface area (D) by TEM: 68 m 2 / g, refractive index 1.3, BET specific surface area (C) 125m 2 / g, shell thickness 5 nm, pH 3.1, average particle size by DLS method 73 nm, viscosity 1.1 mPa·s, water content 1.3 mass%, solid content (silica particle) concentration 19.4 mass%, number density of silanol groups on the hollow silica particle surface 1.4 / nm 2 It was.

[0177] Step 1-2: 230 g of the 20 mass % MeOH-dispersed silica sol of aluminum-atom-containing hollow silica particles obtained in step 1-1 was placed in a 500 mL eggplant-shaped flask. While stirring with a magnetic stirrer, 3.6 g of pure water, 34.5 g of MEK, and 3.3 g of MPMDMS were added, and the mixture was heated to 60°C and maintained for 3 hours. Next, 3.8 g of HMDS was added, and the mixture was heated to 60°C and maintained for 3 hours. DiPA was then added so that the pH was 8.0 to 10.0, and the mixture was heated to 60°C and maintained for 1 hour, thereby obtaining a MeOH-dispersed silica sol of surface-modified hollow silica particles. The silica sol was then placed in a rotary evaporator, and distilled while supplying MEK at a bath temperature of 80°C and a reduced pressure of 550 to 400 Torr. By replacing the dispersion medium from MeOH to MEK, the desired MEK-dispersed silica sol was obtained. The obtained MEK-dispersed silica sol had an average primary particle diameter of 40 nm and a specific surface area (D) of 68 m2 by TEM. 2The results were: / g, refractive index 1.3, average particle size by DLS 64 nm, pH 6.7, viscosity 2.9 mPa s, solid content (silica particle) concentration 31.2 mass%, amount of carbon bonded to silica particles (Cp) 2.0 mass%, amount of carbon and unbonded silane in silica particles (Ct) 3.3 mass%, water content 0.2 mass%, and MeOH content 0.2 mass%. There was no sediment, and the sample showed good dispersibility (dispersed in the dispersion medium without cloudiness or aggregation).

[0178] Step 1-3: A 100 ml eggplant-shaped flask was prepared and charged with 13.0 g of the MEK-dispersed silica sol obtained in step 1-2, 8.0 g of rotaxane (polymer, manufactured by ASM Corporation, product name SM2400C), and 10.0 g of MEK. The flask was then placed in a rotary evaporator and stirred at room temperature of 25°C and 120 rpm for 3 hours. The resulting mixture was evaporated under reduced pressure of 200 to 30 Torr at a bath temperature of 60°C to remove the MEK dispersion medium, yielding a rotaxane-dispersed silica sol. The resulting rotaxane-dispersed silica sol had a solid content (hollow silica particles) of 23.9% by mass and a solid content (hollow silica particles + rotaxane) of 71.1% by mass. The resulting rotaxane-dispersed silica sol was diluted with MEK and its average particle size was measured by DLS. The average particle size was 71 nm, demonstrating good dispersion of the rotaxane.

[0179] (Comparative Example 1) Preparation of rotaxane-dispersed silica sol of aluminum atom-free hollow silica particles 1856 g of water-dispersed silica sol A (HKT-A20-40D (Ningbo Dilato Co., Ltd., trade name)) was placed in a 3 L plastic container, 643.6 g of pure water was added, and the mixture was stirred for 10 minutes at a rotation speed of 650 rpm using a mechanical stirrer equipped with a glass stirring blade. 1700 g of the obtained heat-treated water-dispersed silica sol was then added dropwise with 1.51 g of 8.2% aqueous sulfuric acid solution, and the mixture was stirred at room temperature for 1 hour at a stirring speed of 800 rpm to obtain a water-dispersed silica sol to which sulfuric acid had been added. Next, the obtained sulfuric acid-added heat-treated water-dispersed silica sol was passed through a 200 mL column-packed cation exchange resin (H-type Amberlite (trade name) IR-120B, harmonic mean diameter 0.6 to 0.8 mm, Organo Corporation) at a space velocity (SV) of 5 / hour. The obtained water-dispersed silica sol had a cloudy appearance, and the average particle size measured by DLS was 80 nm, and the particles were aggregated. That is, a water-dispersed silica sol of hollow silica particles not containing aluminum atoms was not obtained, and therefore, it was difficult to replace the dispersion medium, and a MeOH silica sol was not obtained (steps 1-2 and 1-3 of Example 1 could not be performed), and a rotaxane-dispersed sol was not obtained.

Claims

1. A hollow silica organosol containing the following components (A), (B), and (C): A hollow silica organosol containing component (C) in an amount of 0.001% by mass or more and 90% by mass or less based on the total amount (100% by mass) of the organosol: Component (A): aluminum atom-containing hollow silica particles, The amount of aluminum atoms present in the entire hollow silica particle is Al ２ O ３ Converted to 120 to 50,000 ppm / SiO per 1 g of the hollow silica particles ２ hollow silica particles, Component (B): a polymer having a molecular weight of 1,000 or more, containing an ester, ether, or hydroxy group, and further having an acrylic structure; Component (C): organic solvent.

2. 2. The hollow silica organosol according to claim 1, wherein component (B) is a polymer having a rotaxane structure in which a rod-shaped axis molecule passes through a ring of ring-shaped molecules, and the axis molecule has a molecular weight of 1,000 to 50,000.

3. In a thermal stability test 1 in which the hollow silica organosol was kept at 50°C for one week, The hollow silica organosol according to claim 1, which satisfies the following formula (N): Equation (N): 1.3 ≥ (X) １ｗ ) / (X ０ ) ≥ 0.7 However, (X ０ ) indicates the average particle size measured by dynamic light scattering before the thermal stability test 1, and (X １ｗ ) indicates the average particle size determined by dynamic light scattering after thermal stability test 1.

4. In a thermal stability test 2 in which the hollow silica organosol was kept at 50°C for 4 weeks, The hollow silica organosol according to claim 1, which satisfies the following formula (O) and the following formula (P): Equation (O): 1.2 ≥ (X) ４ｗ ) / (X ０ ) ≥ 0.8 However, (X ０ ) indicates the average particle size measured by dynamic light scattering before the thermal stability test 2, and (X ４ｗ ) indicates the average particle size measured by dynamic light scattering after thermal stability test 2; Equation (P): 1.2 ≥ (V) ４ｗ ) / (V ０ ) ≥ 0.8 However, (V ０ ) indicates the viscosity measured at 25°C before the thermal stability test 2, and (V ４ｗ ) indicates the viscosity measured at 25°C after heat stability test 2.

5. 2. The hollow silica organosol according to claim 1, wherein the aluminum-containing hollow silica particles (A) have an average particle size of 20 to 150 nm as determined by dynamic light scattering.

6. 6. The hollow silica organosol according to claim 5, further comprising at least one of a reactive monomer as component (D) and / or a polymer as component (E) (excluding the polymer of component (B)).

7. The hollow silica organosol according to claim 1, wherein the aluminum-containing hollow silica particles (A) satisfy the following (i) to (iv): (i) the thickness of the outer shell of the hollow silica particles is 3 to 8 nm; (ii) the silanol group density on the surface of the hollow silica particles is 0.2 to 6.0 groups / nm ２ That is, (iii) the surface charge amount calculated per 1 g of the hollow silica particles is 25 μeq / g to 200 μeq / g; (iv) The hollow silica particles have a carbon content of 0.1% by mass to 10.0% by mass as determined by elemental analysis.

8. The hollow silica organosol according to claim 1, further comprising the following component (F): Component (F): At least one silane compound selected from the group consisting of compounds represented by the following formulas (1) and (2): 【Chemistry 1】 (In formula (1), R １ are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si—C bond, or a combination of these groups; R ２ are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group having one or more carbon atoms, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; a represents an integer of 1 to 3; In formula (2), R ３ are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si—C bond, or a combination of these groups; R ４ are groups or atoms bonded to the silicon atom, which independently represent an alkoxy group, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; Y is a group or atom bonded to the silicon atom and represents an alkylene group, an NH group, or an oxygen atom; b represents an integer of 1 to 3, and c represents an integer of 0 or 1.

9. The aluminum-containing hollow silica particles (A) have a surface area of ​​1 nm ２ the particles are surface-coated with the silane compound of component (F) or the particles have the silane compound of component (F) bonded to their surfaces at a ratio of 0.1 to 10 particles per 1000 particles; The hollow silica organosol according to claim 8.

10. The hollow silica organosol according to claim 1, further comprising a basic compound.

11. 2. The hollow silica organosol according to claim 1, wherein the organic solvent of component (C) is selected from the group consisting of alcohols, ketones, ethers, esters, and amides.

12. The (D) reactive monomer is (Meth)acrylic compounds, (meth)polyfunctional acrylates, allyl compounds, isocyanate compounds, isothiocyanate compounds, epoxy compounds, diamine-containing compounds, diol-containing compounds, dicarboxylic acid-containing compounds, disulfonyl chloride-containing compounds, dithiol-containing compounds, disulfide-containing compounds, divinyl-containing compounds, diallyl-containing compounds, styrene, tetracarboxylic acid anhydrides, bismaleimides, vinyl-containing compounds, lactone ring-containing compounds , a lactide-containing compound, a fluorine-containing compound, a cyclic olefin-containing compound, ethylene, propylene, or at least one silane compound selected from the group consisting of compounds represented by the following formulas (1) and (2): The hollow silica organosol according to claim 6. 【Chemistry 2】 (In formula (1), R １ are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si—C bond, or a combination of these groups; R ２ are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group having one or more carbon atoms, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; a represents an integer of 1 to 3; In formula (2), R ３ are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si—C bond, or a combination of these groups; R ４ are groups or atoms bonded to the silicon atom, which independently represent an alkoxy group, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; Y is a group or atom bonded to the silicon atom and represents an alkylene group, an NH group, or an oxygen atom; b represents an integer of 1 to 3, and c represents an integer of 0 or 1.

13. The polymer (E) is a polymer containing, as a monomer component, at least one monomer selected from the group consisting of (meth)acrylic compounds, (meth)polyfunctional acrylates, allyl compounds, isocyanate compounds, isothiocyanate compounds, epoxy compounds, diamine-containing compounds, diol-containing compounds, dicarboxylic acid-containing compounds, disulfonyl chloride-containing compounds, dithiol-containing compounds, disulfide-containing compounds, divinyl-containing compounds, diallyl-containing compounds, styrene, tetracarboxylic acid anhydrides, bismaleimides, vinyl-containing compounds, lactone ring-containing compounds, lactide-containing compounds, fluorine-containing compounds, cyclic olefin-containing compounds, ethylene, propylene, and at least one silane compound selected from the group consisting of compounds represented by the following formulas (1) and (2): The hollow silica organosol according to claim 6. 【Transformation 3】 (In formula (1), R １ are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si—C bond, or a combination of these groups; R ２ are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group having one or more carbon atoms, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; a represents an integer of 1 to 3; In formula (2), R ３ are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si—C bond, or a combination of these groups; R ４ are groups or atoms bonded to the silicon atom, which independently represent an alkoxy group, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; Y is a group or atom bonded to the silicon atom and represents an alkylene group, an NH group, or an oxygen atom; b represents an integer of 1 to 3, and c represents an integer of 0 or 1.

14. A resin composition comprising the hollow silica organosol according to claim 1 and an organic resin material or a polysiloxane resin.

15. The organic resin material is selected from the group consisting of styrene-based resins, epoxy-based resins, thioepoxy resins, novolac-based resins, cyanate-based resins, phenol-based resins, acrylic-based resins, maleimide-based resins, polyester-based resins, urethane-based resins, polyurea resins, polyimide-based resins, polyamide-based resins, polyamic acid resins, polyhydroxyimide resins, polybenzoxazole resins, polybenzimidazole resins, polybenzothiazole resins, polyhydroxyamide resins, polyhydroxyazomethine resins, polyether-based resins, polybenzoxazine resins, polytetrafluoroethylene-based resins, cycloolefin polymer-based resins, unsaturated polyester-based resins, vinyl triazine-based resins, polyphenylene sulfide-based resins, crosslinkable polyphenylene oxide-based resins, curable polyphenylene ether-based resins, and condensation-based resins. The resin composition according to claim 14, wherein the organic resin material is at least one selected from the group consisting of styrene-based resins, epoxy-based resins, thioepoxy resins, novolac-based resins, cyanate-based resins, phenol-based resins, acrylic-based resins, maleimide-based resins, polyester-based resins, urethane-based resins, polyurea resins, polyimide-based resins, polyamide-based resins, polyamic acid resins, polyhydroxyimide resins, polybenzoxazole resins, polybenzimidazole resins, polybenzothiazole resins, polyhydroxyamide resins, polyhydroxyazomethine resins, polyether-based resins, polybenzoxazine resins, polytetrafluoroethylene-based resins, cycloolefin polymer-based resins, unsaturated polyester-based resins, vinyl triazine-based resins, polyphenylene sulfide-based resins, crosslinkable polyphenylene oxide-based resins, curable polyphenylene ether-based resins, and condensation-based

16. The resin composition is used for semiconductor device materials, semiconductor element materials, semiconductor resist materials, insulating film materials, copper-clad laminate materials, printed circuit board materials, printing plate materials, printing ink materials, pigments, paints, sealant materials, hard coat materials, 3D printing materials, anti-reflective film materials, in-vehicle part materials, electronic part materials, machine element parts, adhesive materials, battery materials, and developing materials. The resin composition according to claim 14 or 15, which is used for electrical materials, chargeability-imparting materials, conductivity-imparting materials, powder fluidity-imparting materials, cosmetic materials, flexible wiring materials, liquid crystal display materials, organic EL display materials, micro LED display materials, QD-EL display materials, flexible display materials, antenna materials, optical wiring materials, or sensing materials.

17. The hollow silica organosol according to claim 1 or the resin composition according to claim 14, further comprising a polymerization inhibitor.

18. 2. A method for producing hollow silica organosol according to claim 1, comprising the step of substituting an organic solvent for a water-dispersed silica sol containing aluminum atom-containing hollow silica particles by ultrafiltration, heating under reduced pressure, or heating under normal pressure.

19. 19. The method for producing a hollow silica organosol according to claim 18, further comprising, before or after the step of replacing with the organic solvent, a step of adding at least one silane compound selected from the group consisting of compounds represented by formula (1) and formula (2) to the sol containing aluminum atom-containing silica particles, and heating and stirring the mixture at 10°C to 95°C for 0.1 to 20 hours. 【Chemistry 4】 (In formula (1), R １ are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si—C bond, or a combination of these groups; R ２ are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group having one or more carbon atoms, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; a represents an integer of 1 to 3; In formula (2), R ３ are groups bonded to a silicon atom, and each independently represent an alkyl group, a halogenated alkyl group, an alkenyl group, or an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, a polyether group, a carboxy group, a protected carboxy group, a carboxy group-generating group, an imide group, or a cyano group, and which are bonded to a silicon atom via a Si—C bond, or a combination of these groups; R ４ are groups or atoms bonded to the silicon atom, which independently represent an alkoxy group, an acyloxy group, a hydroxy group, or a halogen atom, or a combination of these groups or atoms; Y is a group or atom bonded to the silicon atom and represents an alkylene group, an NH group, or an oxygen atom; b represents an integer of 1 to 3, and c represents an integer of 0 or 1.

20. The hollow silica particle according to claim 19, wherein the step of adding the silane compound and heating and stirring is carried out multiple times. A method for producing organosol.

21. 21. The method for producing a hollow silica organosol according to claim 19, further comprising a step of adding a basic compound to increase the pH by 0.1 to 7 before or after the step of adding the silane compound and heating and stirring.

22. The method for producing a hollow silica organosol according to claim 19 or 20, further comprising a step of replacing the organic solvent with the organic solvent after the step of adding the silane compound and heating and stirring.

23. The method for producing a hollow silica organosol according to claim 21, further comprising a step of replacing the organic solvent with the organic solvent after the pH increasing step.

24. The method for producing a hollow silica organosol according to claim 21, further comprising, after the pH increasing step, a step of adding the silane compound and heating and stirring, and a step of replacing with the organic solvent.

25. 19. The method for producing hollow silica organosol according to claim 18, further comprising the step of adding a polymer having a molecular weight of 1,000 or more, containing an ester, ether, or hydroxy group, and further having an acrylic structure, after the organic solvent substitution step, so that the content of the organic solvent is 0.001% by mass or more and 90% by mass or less based on the total amount (100% by mass) of the organosol.

26. The method for producing a hollow silica organosol according to claim 25, further comprising the step of adding a polymerization inhibitor.

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