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WO2011090085A1 - Particules colloïdales d'oxyde de cérium modifiées et procédé de production de ces dernières - Google Patents

Particules colloïdales d'oxyde de cérium modifiées et procédé de production de ces dernières Download PDF

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Publication number
WO2011090085A1
WO2011090085A1 PCT/JP2011/050898 JP2011050898W WO2011090085A1 WO 2011090085 A1 WO2011090085 A1 WO 2011090085A1 JP 2011050898 W JP2011050898 W JP 2011050898W WO 2011090085 A1 WO2011090085 A1 WO 2011090085A1
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Prior art keywords
silica
colloidal particles
sol
group
antimony pentoxide
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PCT/JP2011/050898
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English (en)
Japanese (ja)
Inventor
博和 加藤
欣也 小山
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0004—Preparation of sols
    • B01J13/0039—Post treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C09C3/063—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/62—Coated
    • A61K2800/621—Coated by inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/651—The particulate/core comprising inorganic material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other

Definitions

  • the present invention relates to a silica-stannic oxide or silica-5 having a primary particle diameter of 1 to 3 nm, the outer surface of which is a cerium oxide colloidal particle (A) having a primary particle diameter of 4 to 60 nm.
  • the present invention also provides a water solubility of 0.002 to 12 mass% of the surface-hydrophobized cerium oxide colloidal particles (D) having an organosilicon compound bonded to the surface of the modified cerium oxide colloidal particles (C).
  • the present invention relates to a hydrophobic organic solvent-dispersed sol and a method for producing the same.
  • Cerium oxide has a high UV absorption ability and is widely applied to UV shielding glass for automobiles, sun protection cosmetics, UV absorbing coating compositions for plastics, and the like. Since these members that are used with an ultraviolet absorbing function are usually required to be transparent to visible light, when applying ceric oxide, fine particles, particularly the primary particle diameter is 100 nm or less. The colloidal particles are preferred. As a sol in which colloidal particles of cerium oxide are dispersed, a crystalline cerium oxide sol having a particle diameter of 30 nm is known (see Patent Document 1).
  • the phosphorus antioxidant used for preventing discoloration of the resin is easily decomposed by the action of various components coexisting in the resin composition.
  • a phosphorus-based antioxidant When a phosphorus-based antioxidant is applied to a cerium oxide sol as in Patent Document 2, the decomposition product may impair the dispersion stability of the cerium oxide sol in the resin composition.
  • the blending of was restricted.
  • organic antioxidants absorb ultraviolet rays and oxidize and alter themselves, their antioxidant effect is not semi-permanent, and light resistance is not always sufficient for applications exposed to ultraviolet rays for a long time. I can't say that.
  • a silica-based composite colloid comprising cerium oxide colloidal particles composed of silica-stannic oxide or silica-antimony pentoxide without using a phosphorus-based antioxidant that causes decomposition by the components of the resin composition.
  • cerium oxide colloidal particles having good light resistance to ultraviolet rays and their aqueous sol or hydrophilic organic solvent-dispersed sol or surface hydrophobized cerium oxide colloidal particles of 0.002 to 12% by mass It has been found that a hydrophobic organic solvent-dispersed sol having a water solubility of 1 to 5 can be provided.
  • the present invention provides, as a first aspect, silica-oxide oxide having a cerium oxide colloidal particle (A) having a primary particle diameter of 4 to 60 nm as a nucleus and an outer surface thereof having a primary particle diameter of 1 to 3 nm.
  • A cerium oxide colloidal particle
  • the modified ceric oxide colloidal particles according to the first aspect wherein the amine compound is at least one compound selected from the group consisting of primary amines, secondary amines and tertiary amines.
  • a hydrophilic organic solvent-dispersed sol of the modified ceric oxide colloidal particles (C) according to the first aspect or the second aspect is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, acetone, tetrahydrofuran, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol mono
  • the hydrophilic organic solvent-dispersed sol according to the fourth aspect which is at least one compound selected from the group consisting of ethyl ether, dipropylene glycol, propylene glycol monomethyl ether and propylene glycol monoethyl ether,
  • surface hydrophilic organic solvent-dispersed sol according to the fourth aspect which is at least one compound selected from the group consisting of e
  • the organosilicon compound is Formula (I) (R 1 ) a (R Three ) b Si (OR 2 ) 4- (a + b) (I) (However, R 1 And R 3 Each represents an alkyl group or halogenated alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group or halogenated aryl group having 6 to 8 carbon atoms, or an epoxy group, It represents an organic group having an acryloyl group, a methacryloyl group, a mercapto group, an amino group or a cyano group, and is bonded to a silicon atom by a Si—C bond.
  • the surface hydrophobized cerium oxide colloidal particles (D) according to the sixth aspect which are at least one compound selected from the group consisting of organic silicon compounds represented by the following formula:
  • the hydrophobic organic solvent having a water solubility of 0.002 to 12% by mass comprises a ketone, an ester, a hydrocarbon, a halogenated hydrocarbon, and a polyoxyalkylene dicarboxylic acid alkyl ester. It has a water solubility of 0.002 to 12 mass% of the surface-hydrophobized cerium oxide colloidal particles (D) according to any one of the ninth to eleventh aspects, which is at least one compound selected from the above.
  • the hydrophobic organic solvent having a water solubility of 0.002 to 12% by mass is methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, methyl methacrylate, diisopropyl ether, toluene, triethylene glycol. It consists of di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH), tetraethylene glycol diheptanoate (4G7) and tetraethylene glycol di-2-ethylhexanoate (4GO).
  • a method for producing an aqueous sol of modified cerium oxide colloidal particles (C) comprising: (A) Step: An amine compound having a molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) is 0.1 to 1.0.
  • an alkali stannate aqueous solution or an alkali antimonate aqueous solution and an alkali silicate aqueous solution are mixed so that the mass ratio is 0.1 to 10, and then a cation present in the aqueous solution is removed to remove a primary of 1 to 3 nm.
  • An aqueous sol of silica-stannic oxide composite colloidal particles having a particle diameter or silica-based composite colloidal particles composed of silica-antimony pentoxide is prepared, and then M / (Si By adding an amine compound having a molar ratio of Jamaica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) of 0.10 to 1.0, 1 to 3 nm Silica-based composite colloidal particles having a primary particle size of silica-stannic oxide or silica-antimony pentoxide and having a silica / stannic oxide or silica / antimony pentoxide mass ratio of 0.1 to 10
  • the cerium colloidal particles (A) are used as nuclei and the outer surface thereof is coated with the silica-based composite colloidal particles (B ′), and the silica-based composite colloidal particles (B ′) of the cerium oxide colloidal particles (A) are coated.
  • the molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) to the silica-based composite colloidal particles (B ′) is 0.001 to 0.00.
  • the mass ratio of silica / stannic oxide or silica / antimony pentoxide is 0.1 to 10 and M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M
  • (C) a method for producing an aqueous sol
  • a method for producing a hydrophilic organic solvent-dispersed sol of modified cerium oxide colloidal particles (C) comprising: (A) Step: An amine compound having a molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) is 0.1 to 1.0.
  • an alkali stannate aqueous solution or an alkali antimonate aqueous solution and an alkali silicate aqueous solution are mixed so that the mass ratio is 0.1 to 10, and then a cation present in the aqueous solution is removed to remove a primary of 1 to 3 nm.
  • An aqueous sol of silica-stannic oxide composite colloidal particles having a particle diameter or silica-based composite colloidal particles composed of silica-antimony pentoxide is prepared, and then M / (Si By adding an amine compound having a molar ratio of Jamaica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) of 0.10 to 1.0, 1 to 3 nm Silica-based composite colloidal particles having a primary particle size of silica-stannic oxide or silica-antimony pentoxide and having a silica / stannic oxide or silica / antimony pentoxide mass ratio of 0.1 to 10
  • the cerium colloidal particles (A) are used as nuclei and the outer surface thereof is coated with the silica-based composite colloidal particles (B ′), and the silica-based composite colloidal particles (B ′) of the cerium oxide colloidal particles (A) are coated.
  • the molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) to the silica-based composite colloidal particles (B ′) is 0.001 to 0.00.
  • the mass ratio of silica / stannic oxide or silica / antimony pentoxide is 0.1 to 10 and M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M
  • an alkali stannate aqueous solution or an alkali antimonate aqueous solution and an alkali silicate aqueous solution are mixed so that the mass ratio is 0.1 to 10, and then a cation present in the aqueous solution is removed to remove a primary of 1 to 3 nm.
  • An aqueous sol of silica-stannic oxide composite colloidal particles having a particle diameter or silica-based composite colloidal particles composed of silica-antimony pentoxide is prepared, and then M / (Si By adding an amine compound having a molar ratio of Jamaica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) of 0.10 to 1.0, 1 to 3 nm Silica-based composite colloidal particles having a primary particle size of silica-stannic oxide or silica-antimony pentoxide and having a silica / stannic oxide or silica / antimony pentoxide mass ratio of 0.1 to 10
  • the cerium colloidal particles (A) are used as nuclei and the outer surface thereof is coated with the silica-based composite colloidal particles (B ′), and the silica-based composite colloidal particles (B ′) of the cerium oxide colloidal particles (A) are coated.
  • the molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) to the silica-based composite colloidal particles (B ′) is 0.001 to 0.00.
  • the mass ratio of silica / stannic oxide or silica / antimony pentoxide is 0.1 to 10 and M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M
  • An eighteenth aspect is the hydrophilic organic according to the sixteenth aspect or the seventeenth aspect, in which the amine compound is at least one compound selected from the group consisting of a primary amine, a secondary amine, and a tertiary amine.
  • the hydrophilic organic solvent is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, acetone, tetrahydrofuran, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl.
  • a method for producing a hydrophilic organic solvent-dispersed sol according to the sixteenth aspect or the seventeenth aspect, which is at least one compound selected from the group consisting of ether, dipropylene glycol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether As a 20th viewpoint, A method for producing a hydrophobic organic solvent-dispersed sol of surface-hydrophobized cerium oxide colloidal particles (D) comprising: (A) Step: An amine compound having a molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) is 0.1 to 1.0.
  • an alkali stannate aqueous solution or an alkali antimonate aqueous solution and an alkali silicate aqueous solution are mixed so that the mass ratio is 0.1 to 10, and then a cation present in the aqueous solution is removed to remove a primary of 1 to 3 nm.
  • An aqueous sol of silica-stannic oxide composite colloidal particles having a particle diameter or silica-based composite colloidal particles composed of silica-antimony pentoxide is prepared, and then M / (Si By adding an amine compound having a molar ratio of Jamaica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) of 0.10 to 1.0, 1 to 3 nm Silica-based composite colloidal particles having a primary particle size of silica-stannic oxide or silica-antimony pentoxide and having a silica / stannic oxide or silica / antimony pentoxide mass ratio of 0.1 to 10
  • the cerium colloidal particles (A) are used as nuclei and the outer surface thereof is coated with the silica-based composite colloidal particles (B ′), and the silica-based composite colloidal particles (B ′) of the cerium oxide colloidal particles (A) are coated.
  • the molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) to the silica-based composite colloidal particles (B ′) is 0.001 to 0.00.
  • the mass ratio of silica / stannic oxide or silica / antimony pentoxide is 0.1 to 10 and M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (provided that M
  • the surface hydrophobized ceric oxide according to the twentieth aspect in which the amine compound is at least one compound selected from the group consisting of a primary amine, a secondary amine class, and a ter
  • the hydrophilic organic solvent is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, acetone, tetrahydrofuran, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol mono Hydrophobic organic solvent which is at least one compound selected from the group consisting of ethyl ether, dipropylene glycol, propylene glycol monomethyl ether and propylene glycol monoethyl ether, and has a water solubility of 0.002 to 12% by mass Is methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl a
  • cerium oxide colloidal particles (A) having a primary particle diameter of 4 to 60 nm according to the present invention are used as a core, and the outer surface thereof is silica-stannic oxide or silica-pentoxide having a primary particle diameter of 1 to 3 nm.
  • silica / stannic oxide or silica / antimony pentoxide of 0.1 to 10 and M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (provided that M represents an amine compound) and is coated with silica-based composite colloidal particles (B) bound with an amine compound having a molar ratio of 0.001 to 0.08, and the cerium oxide colloidal particles (A)
  • the modified cerium oxide colloidal particles (C) having a mass ratio (A) / (B) of 1 to 50 with respect to the silica-based composite colloidal particles (B) have excellent light resistance, and inorganic ultraviolet rays.
  • the aqueous sol or hydrophilic organic solvent dispersion sol of the modified ceric oxide colloidal particles (C) has good compatibility with various hydrophilic resins, and a resin composition excellent in light resistance can be obtained.
  • the solvent-dispersed sol has good compatibility with various monomers or resins, can impart a UV-absorbing ability to various monomers, and can obtain a resin composition excellent in light resistance.
  • the present invention relates to a silica-stannic oxide or silica-5 having a primary particle diameter of 1 to 3 nm, the outer surface of which is a cerium oxide colloidal particle (A) having a primary particle diameter of 4 to 60 nm.
  • M represents an amine compound
  • B silica-based composite colloidal particle
  • A The modified ceric oxide colloidal particles (C) having a mass ratio (A) / (B) of 1 to 50 with respect to the silica-based composite colloidal particles (B).
  • the primary particle diameter of the modified cerium oxide colloidal particles (C) is 5 to 70 nm, and can be measured by observation with a transmission electron microscope.
  • the cerium oxide colloidal particles (A) serving as nuclei have a primary particle diameter of 4 to 60 nm.
  • the primary particle diameter can be measured by observation with a transmission electron microscope.
  • the cerium oxide colloidal particles (A) serving as nuclei can be produced by a known method. For example, after reacting a cerium salt with an alkaline substance in an aqueous medium under an inert gas atmosphere to form a cerium hydroxide suspension, the suspension is subjected to oxygen at a temperature of 10 to 95 ° C. under atmospheric pressure.
  • a method of obtaining an aqueous sol of colloidal cerium oxide particles by injecting a gas containing oxygen to oxidize, or reacting cerium carbonate and hydrogen peroxide in an aqueous medium containing a quaternary ammonium carbonate,
  • a method of obtaining an aqueous sol of ceric oxide colloidal particles through a step of heating at 60 to 110 ° C. and a step of hydrothermal treatment at 110 to 250 ° C. can be mentioned.
  • the aqueous sol of the cerium oxide colloidal particles (A) used in the present invention can be used in the range of pH 3 to 11, preferably pH 8 to 11, more preferably pH 9 to 10.
  • Silica-based composite colloidal particles (B) made of silica-stannic oxide or silica-antimony pentoxide covering the surface of the core cerium oxide colloidal particles (A) have a primary particle diameter of a transmission electron microscope. Observation is 1 to 3 nm, and the mass ratio of silica / stannic oxide or silica / antimony pentoxide is 0.1 to 10, and M / (silica + stannic oxide) or M / (silica + Antimony pentoxide) (where M represents an amine compound) is an amine compound having a molar ratio of 0.001 to 0.08.
  • the silica-based composite colloidal particles (B) are composed of silica-stannic oxide or silica-antimony pentoxide having a primary particle size of 1 to 3 nm as a precursor thereof, and silica / stannic oxide or silica / penta
  • the mass ratio of antimony oxide is 0.1 to 10
  • the molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) is 0.1.
  • An aqueous sol of silica-based composite colloidal particles (B ′) stabilized with an amine compound of 1 to 1.0 is produced.
  • the modified cerium oxide colloidal particles (C) of the present invention are obtained by adding the aqueous sol to the aqueous sol of the cerium oxide colloidal particles (A), and the surface of the cerium oxide colloidal particles (A). After the silica-based composite colloidal particles (B ′) are coated on the surface, the amine compound for stabilization is removed by cation exchange, and then suitable for stabilizing the modified cerium oxide colloidal particles (C). It is obtained by binding the amine compound to the surface.
  • the amount of the amine compound suitable for stabilizing the modified cerium oxide colloidal particles (C) is M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M is an amine compound).
  • the molar ratio is 0.001 to 0.08.
  • the present invention Hydrophobic organic solvent dispersion sol of modified cerium oxide colloidal particles (C) or hydrophobic organic solvent dispersion sol having a water solubility of 0.05 to 12% by mass of surface hydrophobized cerium oxide colloidal particles (D) This is not preferable because of insufficient dispersion stability.
  • the modified cerium oxide of the organosilicon compound represented by the general formula (I) and / or the general formula (II) is used. This is not preferable because it hinders binding to the surface of the colloidal particles (C).
  • the aqueous sol of silica-based composite colloidal particles (B ′) composed of silica-stannic oxide or silica-antimony pentoxide can be produced by a known method (for example, Japanese Patent Publication No. 50-40119). For example, it can be obtained by mixing an alkali silicate aqueous solution with an alkali stannate aqueous solution or an alkali antimonate aqueous solution, then removing the cation with a cation exchange resin, and then adding an amine compound.
  • the amine compound is adsorbed on the surface of the silica-based composite colloidal particles (B ′) composed of silica-stannic oxide or silica-antimony pentoxide, and also present by being dissolved in an aqueous sol dispersion medium. It is presumed that the dispersion stability of the colloidal particles (B ′) is maintained.
  • the colloidal solution obtained by mixing the alkali silicate aqueous solution and the alkali stannate aqueous solution or the alkali antimonate aqueous solution and then removing the cation with a cation exchange resin does not add an amine compound or the amount of the amine compound added.
  • the gel loses stability upon standing for several hours. Can not be used.
  • the addition amount of the amine compound is 0.1 to 1.0 as a molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound). Is an amount sufficient to maintain the dispersion stability of the aqueous sol of the silica-based composite colloidal particles (B ′).
  • alkali silicate aqueous solution a sodium silicate aqueous solution or a potassium silicate aqueous solution can be used.
  • alkali stannate aqueous solution a sodium stannate aqueous solution can be preferably used.
  • alkali antimonate aqueous solution a potassium antimonate aqueous solution is preferably used.
  • amine compound used in the present invention at least one compound selected from the group consisting of primary amines, secondary amines and tertiary amines can be used.
  • primary amines include methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, amylamine, allylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cyclopropylamine, cyclopropylamine, Examples include butylamine, cyclopentylamine and cyclohexylamine.
  • Examples of the secondary amine include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, N-ethyl-1,2-dimethylpropylamine, diamylamine and diallylamine.
  • Examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, and triallylamine.
  • the aqueous sol of the modified cerium oxide colloidal particles (C) of the present invention includes an aqueous sol of the cerium oxide colloidal particles (A) and silica-stannic oxide or silica having a primary particle diameter of 1 to 3 nm.
  • the molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) to the silica-based composite colloidal particles (B ′) is 0.001 to It can be obtained by adding an amine compound that is 0.08.
  • the primary particle diameter of the modified cerium oxide colloidal particles (C) is 5 to 70 nm and can be measured by observation with a transmission electron microscope.
  • the average particle size by dynamic light scattering method is 10 to 100 nm.
  • the solid content concentration of the aqueous sol of the modified ceric oxide colloidal particles (C) is 0.5 to 50% by mass, preferably 5 to 50% by mass as the total metal oxide concentration.
  • the solid content concentration of the aqueous sol can be higher than 50% by mass as required.
  • the hydrophilic organic solvent dispersion sol of the modified cerium oxide colloidal particles (C) of the present invention is obtained by replacing the dispersion medium of the aqueous sol of the modified cerium oxide colloidal particles (C) with a hydrophilic organic solvent.
  • the hydrophilic organic solvent sol of the modified cerium oxide colloidal particles (C) has an average particle diameter of 10 to 100 nm by a dynamic light scattering method, and the solid content concentration of the hydrophilic organic solvent sol is a total metal oxide.
  • the concentration is 0.5 to 50% by mass, preferably 5 to 50% by mass.
  • the solid content concentration of the hydrophilic organic solvent sol can be higher than 50% by mass as required.
  • the hydrophilic organic solvent used in the present invention is an organic solvent uniformly mixed with water, and the content of water in the organic phase when water and the organic solvent are mixed at 20 ° C. to form two phases.
  • This content is referred to as “water solubility of organic solvent” refers to an organic solvent having a content exceeding 12% by mass.
  • Specific examples of the hydrophilic organic solvent include methanol, ethanol, propanol, isopropanol, butanol (water solubility 20% by mass), isobutanol (water solubility 44.1% by mass), acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide.
  • the hydrophilic organic solvent dispersion sol of the surface-hydrophobized cerium oxide colloidal particles (D) of the present invention is the modified cerium oxide colloid to the hydrophilic organic solvent dispersion sol of the modified cerium oxide colloidal particles (C).
  • organosilicon compounds represented by the following general formula (I) and / or general formula (II) or their hydrolysates so that the mass ratio to the particles (C) is 0.01 to 0.5
  • At least one selected compound was added, and the cerium oxide colloidal particles (D) in which the organosilicon compound was bonded to the surface of the modified cerium oxide colloidal particles (C) were dispersed in the hydrophilic organic solvent. It is a sol.
  • the hydrophobic organic solvent dispersion sol having a water solubility of 0.002 to 12% by mass of the surface-hydrophobized ceric oxide colloidal particles (D) of the present invention is the modified ceric oxide colloidal particles (C).
  • the hydrophilic organic solvent-dispersed sol is represented by the following general formula (I) and / or general formula (II) so that the mass ratio with respect to the modified cerium oxide colloidal particles (C) is 0.01 to 0.50.
  • the organosilicon compound used in the present invention is Formula (I) (R 1 ) a (R 3 ) b Si (OR 2 ) 4- (a + b) (I) (However, R 1 and R 3 are each an alkyl group having 1 to 8 carbon atoms or a halogenated alkyl group, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, or a halogenated aryl group.
  • R 2 represents carbon An alkyl group having 1 to 8 atoms or an alkoxyalkyl group or an acyl group having 2 to 8 carbon atoms; a and b each represents an integer of 0, 1 or 2; a + b represents an integer of 0, 1 or 2; And / or general formula (II) [(R 4 ) c Si (OX) 3-c ] 2 Y (II) (Wherein R 4 represents an alkyl group having 1 to 5 carbon atoms, X represents an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 8 carbon atoms, and Y represents 1 to 20 carbon atoms) Is an at least one compound selected from the group consisting of an organosilicon compound represented by (2) and
  • organosilicon compound represented by the general formula (I) examples include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraacetoxysilane, and methyltrimethoxysilane.
  • Methyltriethoxysilane methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycine Sidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxyethyl Trimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇
  • organosilicon compound represented by the general formula (I) used in the present invention methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane and hydrolysates thereof are particularly preferable.
  • hydrolyzate of the organosilicon compound represented by the above general formula (I) is a compound in which part or all of R 2 in the formula is substituted with a hydrogen atom.
  • hydrolysates of organosilicon compounds represented by general formula (I) can be used alone or in combination of two or more.
  • organosilicon compound represented by the general formula (II) examples include methylene bismethyldimethoxysilane, ethylene bisethyldimethoxysilane, propylene bisethyldiethoxysilane, butylene bismethyldiethoxysilane, and hexamethyldisilazane. It is done. These can be used alone or in combination of two or more.
  • the hydrolyzate of the organosilicon compound represented by the general formula (II) is a compound in which a part or all of X in the formula is substituted with a hydrogen atom. These hydrolysates of organosilicon compounds represented by the general formula (II) can be used alone or in combination of two or more.
  • the hydrophobic organic solvent having a water solubility of 0.002 to 12% by mass is not uniformly mixed with water, but is mixed with water at 20 ° C. to form two phases in the organic phase.
  • the water content is 0.002 to 12% by mass.
  • the hydrophobic organic solvent include methyl ethyl ketone (water solubility 9.9% by mass), methyl isobutyl ketone (water solubility 1.8% by mass), cyclohexanone (water solubility 8% by mass), and ethyl acetate (water solubility 2.
  • the method for producing an aqueous sol of the modified cerium dioxide colloidal particles (C) of the present invention is a method including the following steps (a) to (d).
  • a method for producing an aqueous sol of modified cerium oxide colloidal particles (C) comprising: (A) Step: An amine compound having a molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) is 0.1 to 1.0.
  • an alkali stannate aqueous solution or an alkali antimonate aqueous solution and an alkali silicate aqueous solution are mixed so that the mass ratio is 0.1 to 10, and then a cation present in the aqueous solution is removed to remove a primary of 1 to 3 nm.
  • An aqueous sol of silica-stannic oxide composite colloidal particles having a particle diameter or silica-based composite colloidal particles composed of silica-antimony pentoxide is prepared, and then M / (Si By adding an amine compound having a molar ratio of Jamaica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) of 0.10 to 1.0, 1 to 3 nm Silica-based composite colloidal particles having a primary particle size of silica-stannic oxide or silica-antimony pentoxide and having a silica / stannic oxide or silica / antimony pentoxide mass ratio of 0.1 to 10
  • the cerium colloidal particles (A) are used as nuclei and the outer surface thereof is coated with the silica-based composite colloidal particles (B ′), and the silica-based composite colloidal particles (B ′) of the cerium oxide colloidal particles (A) are coated.
  • An amine compound having a molar ratio of 0.001 to 0.08 is added, the cerium oxide colloidal particles (A) are used as nuclei,
  • silica-stannic oxide or silica-antimony pentoxide Have a diameter Consisting of silica-stannic oxide or silica-antimony pentoxide and having a mass ratio of silica / stannic oxide or silica / antimony pentoxide of 0.1 to 10 and M / (silica + stannic oxide) or Covered with silica-based composite colloidal particles (B) to which an amine compound having a molar ratio of M / (silica + antimony pentoxide) (where M represents an amine compound) is 0.001 to 0.08, and A step of adjusting the mass ratio (A) / (B) of the cerium oxide colloidal particles (A) to the silica-based composite colloidal particles (B) to be 1 to 50.
  • a sodium stannate aqueous solution or a potassium stannate aqueous solution can be used as the alkali stannate aqueous solution, preferably a sodium stannate aqueous solution.
  • a sodium antimonate aqueous solution a sodium antimonate aqueous solution, a potassium antimonate aqueous solution or an amine antimonate aqueous solution can be used, and a sodium antimonate aqueous solution is preferred.
  • a sodium silicate aqueous solution or a potassium silicate aqueous solution can be used as the alkali silicate aqueous solution.
  • An alkali stannate aqueous solution or an alkali antimonate aqueous solution and an alkali silicate aqueous solution are mixed so that the mass ratio of silica / stannic oxide or silica / antimony pentoxide is 0.1 to 10, and is present in the aqueous solution. Cations are removed with a cation exchange resin.
  • An alkali stannate aqueous solution or an alkali antimonate aqueous solution and an alkali silicate aqueous solution are prepared by being measured so that the mass ratio of silica / stannic oxide or silica / antimony pentoxide is 0.1 to 10 and dissolved in water. Is done.
  • the solid content concentration of the aqueous solution is preferably 1 to 12% by mass as (silica + stannic oxide) or (silica + antimony pentoxide).
  • Cations are removed from the prepared aqueous solution using a cation exchange resin.
  • the cation exchange resin is preferably a hydrogen-type strongly acidic cation exchange resin.
  • Amberlite (registered trademark) 120B can be packed in a column and used.
  • a silica system comprising silica-stannic oxide or silica-antimony pentoxide having a primary particle diameter of 1 to 3 nm.
  • Composite colloidal particles are produced.
  • silica-based composite colloidal particle Since this silica-based composite colloidal particle is poor in stability and gels in a few hours if left standing, it is necessary to quickly stabilize it by adding an amine compound after cation exchange.
  • the mass ratio of distin or silica / antimony pentoxide is 0.1 to 10, and M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound)
  • M aqueous sol of silica-based composite colloidal particles (B ′) composed of silica-stannic oxide or silica-antimony pentoxide stabilized with an amine compound having a molar ratio of 0.1 to 1.0. is there.
  • the solid content concentration of the obtained aqueous sol is 0.1 to 10% by mass as (silica + stannic oxide) or (silica + antimony pentoxide).
  • the amount of the amine compound suitable for stabilizing the silica-based composite colloidal particles composed of silica-stannic oxide or silica-antimony pentoxide produced by the cation exchange is M / (silica + stannic oxide) or M
  • the molar ratio of / (silica + antimony pentoxide) (wherein M represents an amine compound) is 0.1 to 1.0.
  • the added amount of the amine compound is less than 0.1 as a molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound)
  • the mixture is left for several hours. This is not preferable because it loses stability and gels.
  • the addition amount of the amine compound exceeds 1.0 as a molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound), the amine The compound is present in excess and is not efficient.
  • step (b) an aqueous sol of cerium oxide colloidal particles (A) having a primary particle size of 4 to 60 nm, and silica / stannic oxide or silica / antimony pentoxide obtained in step (a).
  • the molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) is 0.1 to 10.
  • An aqueous sol of silica-based composite colloidal particles (B ′) composed of silica-stannic oxide or silica-antimony pentoxide stabilized with an amine compound having a mass ratio of (A) / (B ′ ) Are mixed so as to be 1 to 50, whereby the surface of the ceric oxide colloidal particles (A) is coated with the silica-based composite colloidal particles (B ′). ' It can be obtained in the aqueous sol.
  • the amine compound at least one compound selected from the group consisting of primary amines, secondary amines and tertiary amines is used.
  • the primary amine class include methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, amylamine, allylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cyclopropylamine, Examples include cyclobutylamine, cyclopentylamine, and cyclohexylamine.
  • Examples of the secondary amine class include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, N-ethyl-1,2-dimethylpropylamine, diamylamine and diallylamine.
  • Examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, and triallylamine.
  • the solid content concentration of the aqueous sol of the ceric oxide colloidal particles (A) is preferably 0.5 to 30% by mass.
  • the aqueous sol of the ceric oxide colloidal particles (A) can be used in the range of pH 3 to 11, preferably pH 8 to 11, more preferably pH 9 to 10.
  • the pH of the aqueous sol of the cerium oxide colloidal particles (A) can be adjusted with an alkali component as necessary.
  • alkali component used for the adjustment examples include alkali metal hydroxides such as lithium, sodium and potassium, alkaline earth metal hydroxides such as calcium, magnesium and strontium, ammonia, ethylamine, triethylamine, isopropylamine, n -Alkylamines such as propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, alkanolamines such as monoethanolamine and triethanolamine, and quaternary ammonium hydroxides.
  • alkali metal hydroxides such as lithium, sodium and potassium
  • alkaline earth metal hydroxides such as calcium, magnesium and strontium
  • ammonia ethylamine, triethylamine
  • isopropylamine n -Alkylamines
  • aralkylamines such as benzylamine
  • alicyclic amines such as piperidine
  • alkanolamines such as monoethanol
  • the mixing of the aqueous sol of the ceric oxide colloidal particles (A) and the aqueous sol of the silica-based composite colloidal particles (B ′) obtained in the step (a) is preferably performed with stirring.
  • the mixing of the cerium oxide colloidal particles (A) and the silica-based composite colloidal particles (B ′) is preferably carried out at a mass ratio (A) / (B ′) of 1 to 50.
  • cerium oxide colloidal particles (A) having the silica-based composite colloidal particles (B ′) as the core cannot be sufficiently coated, and the stable hydrophilic organic solvent-dispersed sol or the surface hydrophobized ceric oxide colloid A hydrophobic organic solvent-dispersed sol having a water solubility of 0.05 to 12% by mass of the particles (D) cannot be obtained. Further, 1 is sufficient for the mass ratio, and when it is less than 1, the silica-based composite colloidal particles (B ′) become excessive, which is not efficient.
  • step (c) cation exchange is performed on the aqueous sol of the modified cerium oxide colloidal particles (C ′) obtained in step (b). As a result, the amine compound bonded to the silica-based composite colloidal particles (C ′) is removed. It is preferable to use a hydrogen type strongly acidic cation exchange resin for the cation exchange.
  • M / (silica + second oxide) with respect to the silica-based composite colloidal particles (B ′) is added to the aqueous sol of the modified cerium oxide colloidal particles (C ′) obtained in the step (c).
  • an amine compound having a molar ratio of tin) or M / (silica + antimony pentoxide) (where M represents an amine compound) of 0.001 to 0.08 modified ceric oxide colloidal particles ( C) aqueous sol is obtained.
  • the hydrophilicity of the present invention is not preferable because the dispersion stability of the conductive organic solvent-dispersed sol becomes insufficient.
  • the aqueous sol of the modified cerium oxide colloidal particles (C) has a primary particle diameter of 5 to 70 nm that can be measured by observation with a transmission electron microscope, and an average particle diameter by dynamic light scattering method is 10 nm. To 100 nm.
  • the solid content concentration of the aqueous sol is 0.5 to 50% by mass, preferably 5 to 50% by mass as the total metal oxide concentration.
  • the solid content concentration of the aqueous sol can be higher than 50% by mass as required.
  • the method for producing a hydrophilic organic solvent-dispersed sol of the modified cerium oxide colloidal particles (C) of the present invention is a method including the following step (e) in addition to the above steps (a) to (d).
  • the dispersion medium of the aqueous sol of the modified cerium oxide colloidal particles (C) obtained in the step (d) is replaced with a hydrophilic organic solvent.
  • the hydrophilic organic solvent used in the present invention is an organic solvent that is uniformly mixed with water, and the content of water in the organic phase when water and the organic solvent are mixed at 20 ° C. to form two phases ( This content rate is referred to as “water solubility of organic solvent”) and is an organic solvent exceeding 12% by mass.
  • hydrophilic organic solvent examples include methanol, ethanol, propanol, isopropanol, butanol (water solubility 20% by mass), isobutanol (water solubility 44.1% by mass), acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide. , Acetone, tetrahydrofuran, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dipropylene glycol, propylene glycol monomethyl ether and propylene glycol monoethyl ether.
  • the hydrophilic organic solvent-dispersed sol of the modified ceric oxide colloidal particles (C) has a primary particle diameter of 5 to 70 nm that can be measured by transmission electron microscope observation, and an average by a dynamic light scattering method.
  • the particle diameter is 10 to 100 nm.
  • the solid content concentration of the hydrophilic organic solvent-dispersed sol is 0.5 to 50% by mass, preferably 5 to 50% by mass as the total metal oxide concentration.
  • the solid content concentration of the hydrophilic organic solvent-dispersed sol can be higher than 50% by mass as necessary.
  • the method for producing a hydrophilic organic solvent-dispersed sol of the surface-hydrophobized cerium oxide colloidal particles (D) of the present invention is a method comprising the following step (f) in addition to the steps (a) to (e). .
  • step (f) the hydrophilic organic solvent-dispersed sol obtained in the step (e) Formula (I) (R 1 ) a (R 3 ) b Si (OR 2 ) 4- (a + b) (I) (However, R 1 and R 3 are each an alkyl group having 1 to 8 carbon atoms or a halogenated alkyl group, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, or a halogenated aryl group.
  • R 2 represents carbon An alkyl group having 1 to 8 atoms or an alkoxyalkyl group or an acyl group having 2 to 8 carbon atoms; a and b each represents an integer of 0, 1 or 2; a + b represents an integer of 0, 1 or 2; And / or general formula (II) [(R 4 ) c Si (OX) 3-c ] 2 Y (II) (Wherein R 4 represents an alkyl group having 1 to 5 carbon atoms, X represents an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 8 carbon atoms, and Y represents 1 to 20 carbon atoms) And at least one compound selected from the group consisting of hydrolysates thereof is added to the modified oxidized
  • the hydrophilic organic solvent-dispersed sol of the cerium colloidal particles (C) is at least one selected from the group consisting of the organosilicon compounds represented by the general formula (I) and / or the general formula (II) or their hydrolysates.
  • Hydrolysis of the organosilicon compound represented by the general formula (I) and / or the general formula (II) requires 1 to 4 moles of water with respect to 1 mole of the organosilicon compound. This necessary water may be contained in advance in the hydrophilic organic solvent-dispersed sol, or may be added after the addition of the organosilicon compound. Moreover, you may add the organosilicon compound which hydrolyzed beforehand.
  • the hydrolyzate of the organosilicon compound can be obtained by adding water or an acidic aqueous solution of a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution, or an acetic acid aqueous solution to the organosilicon compound and stirring the mixture.
  • the ripening temperature can be carried out in the range of the boiling point of the hydrophilic organic solvent used from room temperature, and it is preferable to carry out in the vicinity of the boiling point of the hydrophilic organic solvent because the binding rate of the organosilicon compound to the colloidal particles increases.
  • the aging can be performed under atmospheric pressure, and is preferably performed under reflux.
  • the organosilicon compound used in the present invention is particularly preferably methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane or a hydrolyzate thereof. Further, methylene bismethyldimethoxysilane, ethylene bisethyldimethoxysilane, propylene bisethyldiethoxysilane, butylene bismethyldiethoxysilane, and hexamethyldisilazane are preferable.
  • the total metal oxide concentration of the hydrophilic solvent-dispersed sol obtained in the step (f) is 1 to 70% by mass as the total metal oxide concentration of the surface hydrophobized cerium oxide colloidal particles (D), or 5 to 60% by mass.
  • the obtained hydrophilic solvent-dispersed sol has a primary particle diameter of 5 to 70 nm that can be measured by observation with a transmission electron microscope, and an average particle diameter by dynamic light scattering is 10 to 100 nm.
  • step (f) methanol, ethanol, propanol, isopropanol, butanol, isobutanol, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, acetone, tetrahydrofuran, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dipropylene It can be substituted with at least one hydrophilic organic solvent selected from the group consisting of glycol, propylene glycol monomethyl ether and propylene glycol monoethyl ether.
  • the method for producing a hydrophobic organic solvent sol having a water solubility of 0.002 to 12 mass% of the surface-hydrophobized cerium oxide colloidal particles (D) of the present invention is not limited to the steps (a) to (f).
  • the method includes the following step (g).
  • the dispersion medium of the hydrophilic solvent sol of the surface-hydrophobized cerium oxide colloidal particles (D) obtained in the step (f) has a water solubility of 0.002 to 12% by mass.
  • Replace with organic solvent Solvent replacement can be performed by a known method such as an evaporation replacement method, an ultrafiltration membrane method, or a solvent extraction method under normal pressure or reduced pressure.
  • the temperature of the sol when replacing the dispersion medium from a hydrophilic organic solvent to a hydrophobic organic solvent having a water solubility of 0.002 to 12% by mass is from room temperature to 0.002 to 12% by mass. It is carried out in the range of the boiling point of the hydrophobic organic solvent having water solubility. The solvent replacement is performed until the hydrophilic solvent concentration in the sol becomes less than 2% by mass.
  • the hydrophilic organic solvent-dispersed sol obtained in the step (f) has a concentration of the surface hydrophobized ceric oxide colloidal particles (D) contained in the range of 5 to 70% by mass, or 10 to It is preferable to concentrate in advance in the range of 50% by mass.
  • the sol can be concentrated by a known method such as a heat evaporation method or an ultrafiltration method.
  • the total metal oxide concentration of the sol obtained in the step (g) is 1 to 70% by mass, or 5 to 60% by mass as the total metal oxide concentration of the surface hydrophobized ceric oxide colloidal particles (D). is there.
  • the obtained sol has a primary particle diameter of 5 to 70 nm that can be measured by observation with a transmission electron microscope, and an average particle diameter by dynamic light scattering is 10 to 100 nm.
  • the present invention is not limited to these examples.
  • the measuring method of physical properties is shown below.
  • the primary particle diameter of the colloidal particles was observed at an acceleration voltage of 100 kv using a transmission electron microscope JEM-1010 (manufactured by JEOL Ltd.). The observation was performed by carrying a diluted solution of sol on a carbon support film. [Average particle diameter by dynamic light scattering method] The sol was diluted with a dispersion solvent, measured with a submicron particle analyzer N5 (manufactured by Beckman Coulter, Inc.) using the solvent parameters, and calculated by the cumulant method to obtain an average particle size.
  • the average particle diameter of the particles in the sol is observed, and when the particles are aggregated, the average particle diameter of the aggregated particles is observed.
  • Production Example 1 208.2 kg of tetramethylammonium hydrogen carbonate aqueous solution (manufactured by Tama Chemical Industry Co., Ltd., containing 42.0% by mass in terms of tetramethylammonium hydroxide) in a 1 m 3 pressure reactor equipped with a stirring blade. And 37.5 kg of pure water were added. While stirring this aqueous solution, cerium carbonate powder (manufactured by AMR International Corp., containing 50.94% by mass as CeO 2 ) was gradually added to the aqueous solution, and a total of 54.06 kg was added.
  • tetramethylammonium hydrogen carbonate aqueous solution manufactured by Tama Chemical Industry Co., Ltd., containing 42.0% by mass in terms of tetramethylammonium hydroxide
  • the contents were heated to 50 ° C., and 388.6 kg of 7 mass% hydrogen peroxide water was added over 5 hours while maintaining the temperature.
  • the contents were heated to 102 ° C. and aged for 4 hours, followed by hydrothermal treatment at 145 ° C. for 6 hours. What was obtained after this hydrothermal treatment was in the form of a slurry.
  • the slurry after the hydrothermal treatment was washed while gradually adding pure water using an ultrafiltration device, the slurry was peptized to form a sol.
  • the obtained sol was subsequently washed and concentrated with an ultrafiltration device, solid content 5.18% by mass, pH 9.8, conductivity 780 ⁇ S / cm, cerium oxide having an average particle size of 61 nm by dynamic light scattering method 489.6 kg of aqueous sol was obtained. 5 kg of this aqueous cerium oxide sol was sampled, dispersed with an ultrasonic homogenizer (UIP2000), and then washed with gradual addition of pure water using an ultrafiltration device.
  • UIP2000 ultrasonic homogenizer
  • the obtained aqueous solution was passed through a column packed with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B) to obtain an acidic aqueous sol of stannic oxide-silica composite colloidal particles (pH 2.4, SnO 2 contained 0.87 mass%, SiO 2 contained 2.62 mass%, and SiO 2 / SnO 2 mass ratio 3.0) 860 g was obtained.
  • a hydrogen-type cation exchange resin Amberlite (registered trademark) IR-120B
  • the molar ratio of diisopropylamine / (silica + stannic oxide) was 0.21, and the pH was 10.3.
  • colloidal particles having a primary particle diameter of 3 nm or less were observed with a transmission electron microscope.
  • the obtained potassium antimonate silicate aqueous solution (542.6 g) was diluted with pure water (207.4 g) and passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B).
  • antimony oxide - aqueous sol of silica composite colloidal particles (pH 2.1, 0.66% by mass as Sb 2 O 5, containing 1.30% by mass as SiO 2, SiO 2 / Sb 2 O 5 mass ratio 2.0) 754 g was obtained.
  • 4.5 g of diisopropylamine was added to the obtained aqueous sol.
  • the obtained sol was an alkaline aqueous sol of antimony pentoxide-silica composite colloidal particles.
  • the molar ratio of diisopropylamine / (silica + antimony pentoxide) was 0.25 and the pH was 10.3.
  • colloidal particles having a primary particle diameter of 3 nm or less were observed with a transmission electron microscope.
  • Example 1 The alkaline cerium oxide prepared in Production Example 2 was added to the cerium oxide aqueous sol having a solid concentration of 4.5% by mass obtained by adding 336.7 g of pure water to 2330 g of the aqueous cerium oxide sol prepared in Production Example 1. 869 g of an alkaline aqueous sol of tin-silica colloid particles was added and stirred well. Subsequently, the mixture was heated at 95 ° C. for 3 hours to obtain 3404 g of an aqueous sol of modified cerium oxide colloidal particles coated with stannic oxide-silica composite colloidal particles. The total metal oxide concentration of the obtained sol was 4.4% by mass, and the pH was 8.6.
  • the obtained modified aqueous cerium oxide colloidal particle sol was passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and 3421 g of acidic aqueous sol of modified cerium oxide colloidal particles was obtained.
  • the obtained acidic aqueous sol had a total metal oxide concentration of 4.4% by mass and a pH of 2.7.
  • 0.55 g of diisopropylamine was added to the acidic aqueous sol of the modified ceric oxide colloidal particles, and diisopropylamine was bound to the surface of the modified ceric oxide colloidal particles.
  • the molar ratio of diisopropylamine / (silica + stannic oxide) in the sol was 0.013, and the pH was 3.5.
  • the obtained acidic aqueous sol of the modified cerium oxide colloidal particles was concentrated using an ultrafiltration device, and the total metal oxide concentration was 20.5% by mass, the specific gravity was 1.202, the pH was 3.3, and the viscosity was 5. 730 g of an acidic aqueous sol having an average particle diameter of 46 nm by 5 mPa ⁇ s and a dynamic light scattering method was obtained.
  • Example 2 The alkaline cerium oxide prepared in Production Example 2 was added to the cerium oxide aqueous sol having a solid concentration of 4.5% by mass obtained by adding 336.7 g of pure water to 2330 g of the aqueous cerium oxide sol prepared in Production Example 1. 869 g of an alkaline aqueous sol of tin-silica colloid particles was added and stirred well. Subsequently, the mixture was heated at 95 ° C. for 3 hours to obtain 3404 g of an aqueous sol of modified cerium oxide colloidal particles coated with stannic oxide-silica composite colloidal particles. The total metal oxide concentration of the obtained sol was 4.4% by mass, and the pH was 8.6.
  • the obtained modified aqueous cerium oxide colloidal particle sol was passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and 3421 g of acidic aqueous sol of modified cerium oxide colloidal particles was obtained.
  • the obtained acidic aqueous sol had a total metal oxide concentration of 4.4% by mass and a pH of 2.7.
  • 0.7 g of diisobutylamine was added to the acidic aqueous sol of the modified ceric oxide colloidal particles, and diisobutylamine was bound to the surface of the modified ceric oxide colloidal particles.
  • the molar ratio of diisobutylamine / (silica + stannic oxide) in the sol was 0.013, and the pH was 3.5.
  • the obtained acidic aqueous sol of the modified cerium oxide colloidal particles was concentrated using an ultrafiltration device, and concentrated to a total metal oxide concentration of 16.9% by mass.
  • the concentrated aqueous sol is put into an evaporator with an eggplant-shaped flask, and water is distilled off under a reduced pressure of 100 Torr while adding methanol to the sol, whereby a modified ceric oxide colloid in which diisobutylamine is bound to the surface thereof. Particulate methanol sol was obtained.
  • the obtained methanol sol had a total metal oxide concentration of 20.5% by mass, a specific gravity of 0.966, pH 3.6 (diluted with water of the same mass as the sol), a viscosity of 3.5 mPa ⁇ s, and a water content of 1.0% by mass.
  • the average particle size by dynamic light scattering method was 55 nm.
  • Example 3 5.0 g of methyltrimethoxysilane (product name: LS-530, manufactured by Shin-Etsu Silicone Co., Ltd.) was added to 244 g of the methanol sol obtained in Example 2, and silylation was carried out by reflux heating for 5 hours. Silyl groups were bonded to the surface of the modified ceric oxide colloidal particles. Next, methanol was distilled off while adding methyl ethyl ketone (hereinafter also referred to as “MEK”) under a reduced pressure of 140 Torr using an evaporator, so that methanol was replaced with methyl ethyl ketone and the surface was hydrophobicized with a methyldimethoxysilyl group bonded thereto.
  • MEK methyl ethyl ketone
  • a methyl ethyl ketone sol of ceric oxide colloidal particles was obtained.
  • the obtained methyl ethyl ketone sol had a total metal oxide concentration of 20.9% by mass, a specific gravity of 0.988, a viscosity of 2.6 mPa ⁇ s, and an average particle size by dynamic light scattering of 48 nm. In observation with a transmission electron microscope, the primary particle diameter was 12 nm.
  • Example 4 The same procedure as in Example 3 was performed, except that 3.6 g of phenyltrimethoxysilane (product name: KBM-103, manufactured by Shin-Etsu Silicone Co., Ltd.) was used instead of 5.0 g of methyltrimethoxysilane.
  • a methyl ethyl ketone sol of cerium colloid particles was obtained.
  • the obtained methyl ethyl ketone sol had a total metal oxide concentration of 20.5% by mass, a specific gravity of 0.984, a viscosity of 3.0 mPa ⁇ s, and an average particle size by a dynamic light scattering method of 56 nm. In observation with a transmission electron microscope, the primary particle diameter was 12 nm.
  • Example 5 The alkaline cerium pentoxide prepared in Production Example 3 was added to the aqueous cerium oxide aqueous sol having a solid concentration of 4.5% by mass, which was obtained by adding 168.3 g of pure water to 1165 g of the cerium oxide aqueous sol prepared in Production Example 1. Add 754 g of aqueous sol of silica composite colloidal particles and stir well. Subsequently, the mixture was heated at 95 ° C. for 3 hours to obtain 1926 g of an aqueous sol of modified cerium oxide colloidal particles coated with antimony pentoxide-silica composite colloidal particles. The obtained aqueous sol had a total metal oxide concentration of 3.9% by mass and a pH of 8.0.
  • the obtained aqueous sol of the modified cerium oxide colloid particles was passed through a column packed with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and the acidic aqueous solution of the modified cerium oxide colloid particles was obtained. 1939 g of sol was obtained.
  • the obtained acidic aqueous sol had a total metal oxide concentration of 3.8% by mass and a pH of 2.6.
  • 1.5 g of diisobutylamine was added to the acidic aqueous sol of the modified ceric oxide colloidal particles, and diisobutylamine was bound to the surface of the modified ceric oxide colloidal particles.
  • the pH of the sol was 3.7, and the molar ratio of diisobutylamine / (silica + antimony pentoxide) was 0.065.
  • the obtained sol was concentrated using an ultrafiltration device, and concentrated to a total metal oxide concentration of 20.5% by mass.
  • This concentrated sol had a total metal oxide concentration of 20.5% by mass, a specific gravity of 1.208, a pH of 3.5, a viscosity of 6.10 mPa ⁇ s, and an average particle size by dynamic light scattering of 43 nm.
  • Example 6 5.0 g of methyltrimethoxysilane (product name: LS-530, manufactured by Shin-Etsu Silicone Co., Ltd.) was added to 244 g of the methanol sol obtained in Example 2, and silylation was carried out by reflux heating for 5 hours. A methanol sol of surface hydrophobized cerium oxide colloidal particles was obtained by bonding silyl groups to the surface of the modified cerium oxide colloidal particles. Next, the methanol was replaced with isopropanol by distilling off methanol while adding isopropanol (hereinafter also referred to as “IPA”) under a reduced pressure of 100 Torr using an evaporator. A sol was obtained.
  • IPA isopropanol
  • the obtained isopropanol sol had a total metal oxide concentration of 20.5% by mass, a specific gravity of 0.955, a viscosity of 5.2 mPa ⁇ s, and an average particle size by a dynamic light scattering method of 51 nm.
  • Example 7 The same operation as in Example 6 was carried out except that propylene glycol monomethyl ether (hereinafter also referred to as “PGME”) was used instead of isopropanol to obtain a propylene glycol monomethyl ether sol of surface hydrophobized ceric oxide colloidal particles. .
  • the obtained propylene glycol monomethyl ether sol had a total metal oxide concentration of 20.5% by mass, a specific gravity of 1.111, a viscosity of 4.5 mPa ⁇ s, and an average particle size by a dynamic light scattering method of 45 nm.
  • PGME propylene glycol monomethyl ether
  • Comparative Example 1 The alkaline cerium oxide prepared in Production Example 4 was added to the aqueous cerium oxide aqueous sol having a solid concentration of 4.5% by mass by adding 112.2 g of pure water to 776.7 g of the aqueous cerium oxide sol obtained in Production Example 1. 290 g of an aqueous solution containing a silicic acid oligomer was added and stirred sufficiently. Next, the mixture was aged at 95 ° C. for 3 hours to obtain 1165 g of an aqueous sol of modified cerium oxide colloidal particles coated with silica and its oligomer.
  • the obtained aqueous sol of the modified cerium oxide colloidal particles was passed through a column packed with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and the acidic modified cerium oxide colloidal particles 1200 g of an aqueous sol was obtained.
  • the obtained aqueous sol had a total metal oxide concentration of 4.1% by mass and a pH of 8.8.
  • the obtained aqueous sol of the modified cerium oxide colloidal particles was concentrated using an ultrafiltration device, and the total metal oxide concentration was 20.5% by mass, the specific gravity was 1.196, pH 2.7, and the viscosity was 6.5 mPa ⁇ s.
  • 240 g of an aqueous sol having an average particle diameter of 49 nm obtained by a dynamic light scattering method was obtained.
  • Example 2 Methanol substitution was performed in the same manner as in Example 2 except that diisobutylamine was not added to the acidic aqueous sol of cerium oxide colloidal particles, but the sol gelled in the middle of substitution with methanol. Cann't get.
  • Comparative Example 3 The same procedure as in Example 3 was performed except that methyltrimethoxysilane was not added to the methanol sol of the modified cerium oxide colloidal particles in which diisobutylamine was bonded to the surface, but the sol was gelated while being replaced with methyl ethyl ketone. As a result, methyl ethyl ketone sol could not be obtained.
  • the obtained sol was evaluated by the following method.
  • a sol dispersion medium was added so that the total solid content concentration was 20% by mass to prepare a coating composition.
  • the cured film was produced by heating at 150 degreeC for 2 hours using an electric furnace.
  • (3) Evaluation of light resistance The coating composition prepared in (1) above and the cured film prepared in (2) above were irradiated with ultraviolet rays with a 300 W high-pressure mercury lamp (HANDY UV300 manufactured by ORC Manufacturing Co., Ltd.) Light resistance was evaluated. For comparison, a sol obtained by concentrating the cerium oxide aqueous sol obtained in Production Example 1 to 20% by mass was similarly evaluated. Color coordinate values were measured using a color difference meter (TC-1800MK-II, manufactured by Tokyo Denshoku Co., Ltd.), and the color difference value calculated by the following Hunter color difference formula was used as an indicator of light resistance.
  • the modified cerium oxide colloidal particles (C) of the invention of the present application are used as an inorganic ultraviolet absorber having high ultraviolet absorption ability and chemical stability, for automobile ultraviolet shielding glass, sun protection cosmetics, and plastics. Application as an additive component to ultraviolet absorbing coating compositions is expected.

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Abstract

La présente invention concerne des particules colloïdales d'oxyde de cérium qui présentent une excellente résistance à la lumière et qui sont formées au moyen d'un revêtement des particules colloïdales d'oxyde de cérium avec des particules colloïdales de composite à base de silice, formé d'oxyde d'étain-silice ou de pentoxyde d'antimoine-silice. Des particules colloïdales d'oxyde de cérium (A) présentant un diamètre de particule compris entre 4 et 60 nm servent de noyau et la surface externe des particules est recouverte de particules colloïdales de composite à base de silice (B) qui sont formées à partir de pentoxyde d'antimoine-silice ou d'oxyde d'étain-silice présentant un premier diamètre de particule compris entre 1 et 3, le rapport de masse oxyde d'étain-silice ou pentoxyde d'antimoine-silice étant compris entre 0,1 et 10, des composés amine ayant un rapport moléculaire M/(oxyde d'étain+silice) ou M/(pentoxyde d'antimoine+silice) (dans lequel M représente un composé amine) compris entre 0,001 et 0,08 sont couplés. Les particules colloïdales d'oxyde de cérium modifiées résultantes (C) ont un rapport de masse des particules colloïdales d'oxyde cérium (A) particules colloïdales de composite à base de silice (B), ((A)/(B)) compris entre 1 et 50.
PCT/JP2011/050898 2010-01-19 2011-01-19 Particules colloïdales d'oxyde de cérium modifiées et procédé de production de ces dernières Ceased WO2011090085A1 (fr)

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JP6144447B1 (ja) * 2016-02-02 2017-07-05 エム・テクニック株式会社 微粒子分散液の精密改質方法
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JP6144447B1 (ja) * 2016-02-02 2017-07-05 エム・テクニック株式会社 微粒子分散液の精密改質方法
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US11111145B2 (en) 2016-02-02 2021-09-07 M. Technique Co., Ltd. Precise modifying method for fine particle dispersion liquid
CN108430915B (zh) * 2016-02-02 2022-07-26 M技术株式会社 微粒分散液的精密改性方法
JP2022509948A (ja) * 2018-11-19 2022-01-25 ソウルブレイン シーオー．， エルティーディー． Ｕｖａ領域にて光を吸収する日焼け止め組成物、及びその製造方法
CN116713037A (zh) * 2023-04-23 2023-09-08 万华化学集团股份有限公司 一种用于合成四甲基碳酸氢铵的固体催化剂及其制备方法与应用
CN117024925A (zh) * 2023-10-10 2023-11-10 山东龙兴塑膜科技股份有限公司 一种改性聚酯及其在碳带打印用耐高温聚酯薄膜中的应用
CN117024925B (zh) * 2023-10-10 2024-01-05 山东龙兴塑膜科技股份有限公司 一种改性聚酯及其在碳带打印用耐高温聚酯薄膜中的应用

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