# US 9,039,828 B2 · Process for producing silica-based fine particle dispersion sols, silica-based fine particle dispersion sol, coating composition containing the dispersion sol, curable coating film, and substrate having the curable coating film

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- Number: US 9,039,828 B2
- Document ID: US9039828B2
- Status: Granted
- Kind: B2
- Application number: 13/379,878
- Filed: 2010-06-15
- Published: 2012-05-03
- Granted: 2015-05-26
- Earliest claimed: 2009-06-24
- Assignees: JGC Catalysts and Chemicals Ltd.
- Applicants: Yoichi Ishihara; Hiroyasu Nishida
- Inventors: Yoichi Ishihara; Hiroyasu Nishida
- Web page: https://patentgrep.com/patent/US9039828B2

## CPC

- C09D 7/62: modified by treatment with other compounds
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- C01B 33/141: Preparation of hydrosols or aqueous dispersions
- C01B 33/145: Preparation of hydroorganosols, organosols or dispersions in an organic medium
- C09C 1/3054: {Coating}
- C09D 7/67: {Particle size smaller than 100 nm}
- C09D 133/00: Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D 163/00: Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D 167/00: Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain (based on polyester-amides C09D177/12; based on polyester-imides C09D179/08); Coating compositions based on derivatives of such polymers
- C09D 175/04: Polyurethanes
- C09D 179/04: Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D 183/02: Polysilicates
- C09D 183/04: Polysiloxanes
- C09D 183/14: in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms (C09D183/10 takes precedence)
- C01P 2004/32: Spheres
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- C08G 77/58: Metal-containing linkages
- C08K 3/36: Silica
- C08K 9/02: Ingredients treated with inorganic substances
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C09C: TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES (treatment of materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone C04B14/00, C04B18/00, C04B20/00); PREPARATION OF CARBON BLACK {; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS}
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

Provided are silica-based fine particle dispersion sols, processes for producing the sols, coating compositions containing the dispersion sol, curable coating films obtained from the coating composition, and substrates having the coating film. A process includes (1) mixing an aqueous aluminate solution to an alkaline silica sol which contains water-dispersible silica fine particles in a given ratio; (2) heating the mixture liquid obtained in the step (1) to 60 to 200° C. and stirring the mixture liquid at the temperature for 0.5 to 20 hours; and (3) contacting the mixture liquid obtained in the step (2) with a cation exchange resin to remove by ion exchange alkali metal ions contained in the mixture liquid and thereby controlling the pH of the mixture liquid to be in the range of 3.0 to 6.0.

## Claims

### Claim 1

A silica-based fine particle dispersion sol which comprises silica-based fine particles having a negative charge on the surface and has a pH in an acidic region from 3.0 to 6.0, wherein the silica-based fine particles are chain particles having an average particle diameter in the range of 5 to 50 nm as calculated by the equation (L +D)/2 wherein L is the longitudinal length and D is the lateral length measured with respect to a transmission electron micrograph, and the surface of the silica-based fine particles which has been modified with aluminum comprises a composite oxide of silica-alumina, and the amount of the modification by aluminum is in the range of 0.05×10−6 to 2.0×10−6 mol/m2 in terms of Al2O3 per unit surface area of the silica-based fine particles.

### Claim 2 (depends on 1)

The silica-based fine particle dispersion sol according to claim 1, wherein the silica-based fine particles are spherical particles having an average particle diameter in the range of 5 to 50 nm as measured by a BET method.

### Claim 3 (depends on 1)

The silica-based fine particle dispersion sol according to claim 1, wherein when the pH of the dispersion sol is 5.0, the amount of the negative charge on the surface of the silica-based fine particles is in the range of 0.5 to 1.1 μeq/m2 per specific surface area of the silica-based fine particles.

### Claim 4 (depends on 1)

The silica-based fine particle dispersion sol according to claim 1, wherein at least part of aluminum that has modified the surface of the silica-based fine particles is in the form of a silica/alumina composite oxide represented by Formula (I) below:

### Claim 5 (depends on 1)

The silica-based fine particle dispersion sol according to claim 1, wherein the solid concentration in the dispersion sol is in the range of 5 to 60% by weight.

### Claim 6 (depends on 1)

The silica-based fine particle dispersion sol according to claim 1, wherein when the total content of the silica-based fine particles as solids contained in the dispersion sol and the silicon compound as a solute in the dispersion sol is 30% by weight in terms of oxide (SiO2), the haze of the dispersion sol is in the range of 0.5 to 20%.

### Claim 7 (depends on 1)

The silica-based fine particle dispersion sol according to claim 1, wherein the dispersion medium is water and/or at least one organic compound selected from alcohols including methanol, ethanol, butanol, propanol and isopropyl alcohol, ethers including ethylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether, and ketones including methyl ethyl ketone and γ-butyrolactone.

### Claim 8

A silica-based fine particle dispersion sol which comprises silica-based fine particles having a negative charge on the surface and has a pH in an acidic region from 3.0 to 6.0, wherein the surface of the silica-based fine particles which has been modified with aluminum comprises a composite oxide of silica-alumina, and the amount of the modification by aluminum is in the range of 0.05×10−6 to 2.0×10−6 mol/m2 in terms of Al2O3 per unit surface area of the silica-based fine particles, wherein at least part of aluminum that has modified the surface of the silica-based fine particles is in the form of a silica/alumina composite oxide represented by Formula (I) below:

### Claim 9 (depends on 8)

The silica-based fine particle dispersion sol according to claim 8, wherein the silica-based fine particles are spherical particles having an average particle diameter in the range of 5 to 50 nm as measured by a BET method.

### Claim 10 (depends on 8)

The silica-based fine particle dispersion sol according to claim 8, wherein when the pH of the dispersion sol is 5.0, the amount of the negative charge on the surface of the silica-based fine particles is in the range of 0.5 to 1.1 μeq/m2 per specific surface area of the silica-based fine particles.

### Claim 11 (depends on 8)

The silica-based fine particle dispersion sol according to claim 8, wherein the solid concentration in the dispersion sol is in the range of 5 to 60% by weight.

### Claim 12 (depends on 8)

The silica-based fine particle dispersion sol according to claim 8, wherein when the total content of the silica-based fine particles as solids contained in the dispersion sol and the silicon compound as a solute in the dispersion sol is 30% by weight in terms of oxide (SiO2), the haze of the dispersion sol is in the range of 0.5 to 20%.

### Claim 13 (depends on 8)

The silica-based fine particle dispersion sol according to claim 8, wherein the dispersion medium is water and/or at least one organic compound selected from alcohols including methanol, ethanol, butanol, propanol and isopropyl alcohol, ethers including ethylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether, and ketones including methyl ethyl ketone and γ-butyrolactone.