WO2011090085A1

WO2011090085A1 - Modified cerium oxide colloid particles and manufacturing method for same

Info

Publication number: WO2011090085A1
Application number: PCT/JP2011/050898
Authority: WO
Inventors: 博和加藤; 欣也小山
Original assignee: 日産化学工業株式会社
Priority date: 2010-01-19
Filing date: 2011-01-19
Publication date: 2011-07-28
Also published as: TW201139535A; JP2013056780A

Abstract

Disclosed are cerium oxide colloid particles which exhibit excellent light resistance and which are formed by coating cerium oxide colloid particles with silica-based composite colloid particles of silica-stannic oxide or silica antimony pentoxide. Cerium oxide colloid particles (A) having a primary particle diameter of 4-60 nm serve as the core, and the outer surface of the particles is coated with silica-based composite colloid particles (B) which are formed from silica antimony pentoxide or silica-stannic oxide having a primary particle diameter of 1-3 nm, the silica/stannic oxide or the silica/antimony pentoxide mass ratio is 0.1-10, and wherein amine compounds having an M/(silica+stannic oxide) or M/(silica+antimony pentoxide) (wherein M represents an amine compound) mole ratio of 0.001- 0.08 are connected. The resulting modified cerium oxide colloid particles (C) have a cerium oxide colloid particles (A) to silica-based composite colloid particles (B) mass ratio ((A)/(B)) of 1-50.

Description

Modified ceric oxide colloidal particles and method for producing the same

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. Made of antimony oxide and having a mass ratio of silica / stannic oxide or silica / antimony pentoxide of 0.1 to 10 and M / (silica + stannic oxide) or M / (silica + antimony pentoxide) ( Wherein M represents an amine compound) and is coated with a silica-based composite colloidal particle (B) to which an amine compound having a molar ratio of 0.001 to 0.08 is bonded, and the cerium oxide colloidal particle (A) 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) and their aqueous sols or their hydrophilic organics Medium is a dispersion sol and a process for their preparation.
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).
In addition, when a cerium oxide sol is applied to resin compositions such as plastics and paints, a phosphorous antioxidant is applied to the cerium oxide sol as a method to improve the coloring phenomenon of the resin accompanying the alteration of the cerium oxide. Has been proposed (see Patent Document 2).

JP-A-1-148710 JP 7-62139 A

The phosphorus antioxidant used for preventing discoloration of the resin is easily decomposed by the action of various components coexisting in the resin composition. 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. There was a drawback that the blending of was restricted.
In addition, since such 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.

In the present invention, 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. By coating with particles, 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.
That is, 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. Composed of distinous 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 M / (silica + Antimony pentoxide) (wherein M represents an amine compound) 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 ceric oxide Modified cerium oxide colloidal particles (C) having a mass ratio (A) / (B) of 1 to 50 of the colloidal particles (A) to the silica-based composite colloidal particles (B),
As a second aspect, 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. (C),
As a third aspect, an aqueous sol of the modified ceric oxide colloidal particles (C) according to the first aspect or the second aspect,
As a fourth aspect, a hydrophilic organic solvent-dispersed sol of the modified ceric oxide colloidal particles (C) according to the first aspect or the second aspect,
As a fifth aspect, 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 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,
As a sixth aspect, surface hydrophobized cerium oxide colloidal particles (D) in which an organosilicon compound is bonded to the surface of the modified cerium oxide colloidal particles (C) described in the first aspect or the second aspect,
As a seventh aspect, a hydrophilic organic solvent-dispersed sol of surface hydrophobized ceric oxide colloidal particles (D) according to the sixth aspect,
As an eighth aspect, 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 The hydrophilic organic solvent-dispersed sol according to the seventh 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,
As a ninth aspect, a hydrophobic organic solvent-dispersed sol having a water solubility of 0.002 to 12% by mass of the surface-hydrophobized ceric oxide colloidal particles (D) according to the sixth aspect,
As a tenth aspect, the surface-hydrophobized cerium oxide colloidal particles (6) according to the sixth aspect, wherein the mass ratio of the organosilicon compound to the modified cerium oxide colloidal particles (C) is 0.01 to 0.50. D) a hydrophobic organic solvent-dispersed sol having a water solubility of 0.002 to 12% by mass,
As an eleventh aspect,
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. ² Represents an alkyl group having 1 to 8 carbon 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, and a + b is 0, 1 or 2 Represents an integer. ) And / or
Formula (II)
[(R ^Four ) _c Si (OX) _3-c ] ₂ Y (II)
(However, R ^Four 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 an alkylene group having 1 to 20 carbon atoms. , C represents an integer of 0 or 1. 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:
As a twelfth aspect, 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. Hydrophobic organic solvent dispersion sol,
As a thirteenth aspect, 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). The water solubility of 0.002 to 12 mass% of the surface hydrophobized ceric oxide colloidal particles (D) according to any one of the ninth to eleventh aspects, which is at least one compound selected from the group Hydrophobic organic solvent dispersion sol having.
As the 14th viewpoint,
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. A step of obtaining an aqueous sol of silica-based composite colloidal particles (B ′) comprising stabilized silica-stannic oxide or silica-antimony pentoxide, comprising silica / stannic oxide or silica / antimony pentoxide First, 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 Rica + 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 step of stabilizing B ′),
(B) step: a step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C ′), wherein the aqueous sol of ceric oxide colloidal particles (A) having a primary particle diameter of 4 to 60 nm, The aqueous sol of silica-based composite colloidal particles (B ′) obtained in the step (a) is mixed so that the mass ratio of (A) / (B ′) is 1 to 50, and the second oxidized oxide is mixed. 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. ) A ratio of mass ratio (A) / (B ′) to 1 to 50,
Step (c): A step of cation exchange of the aqueous sol of the modified cerium oxide colloidal particles (C ′) obtained in the step (b), wherein the silica-based composite colloidal particles (C Removing the amine compound bound to '); and
Step (d): A step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C), wherein the aqueous sol of modified ceric oxide colloidal particles (C ′) obtained in the step (c) 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. A silica-stannic oxide or silica-antimony pentoxide having a primary particle size of 1 to 3 nm with the addition of an amine compound of 08 and using the cerium oxide colloidal particles (A) as nuclei 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 The silica-based composite colloidal particles (B) coated with silica-based composite colloidal particles (B) to which an amine compound having a molar ratio of 0.001 to 0.08 is bonded. A step of adjusting the mass ratio (A) / (B) to 1 to 50 with respect to the composite colloidal particles (B);
A method for producing an aqueous sol of the modified ceric oxide colloidal particles (C) according to the third aspect, comprising:
As a fifteenth aspect, the modified ceric oxide colloidal particles according to the fourteenth aspect, wherein the amine compound is at least one compound selected from the group consisting of a primary amine, a secondary amine, and a tertiary amine. (C) a method for producing an aqueous sol,
As the 16th viewpoint,
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. A step of obtaining an aqueous sol of silica-based composite colloidal particles (B ′) comprising stabilized silica-stannic oxide or silica-antimony pentoxide, comprising silica / stannic oxide or silica / antimony pentoxide First, 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 Rica + 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 step of stabilizing B ′),
(B) step: a step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C ′), wherein the aqueous sol of ceric oxide colloidal particles (A) having a primary particle diameter of 4 to 60 nm, The aqueous sol of silica-based composite colloidal particles (B ′) obtained in the step (a) is mixed so that the mass ratio of (A) / (B ′) is 1 to 50, and the second oxidized oxide is mixed. 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. ) A ratio of mass ratio (A) / (B ′) to 1 to 50,
Step (c): A step of cation exchange of the aqueous sol of the modified cerium oxide colloidal particles (C ′) obtained in the step (b), wherein the silica-based composite colloidal particles (C ') The step of removing the amine compound bound to
Step (d): A step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C), wherein the aqueous sol of modified ceric oxide colloidal particles (C ′) obtained in the step (c) 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. A silica-stannic oxide or silica-antimony pentoxide having a primary particle size of 1 to 3 nm with the addition of an amine compound of 08 and using the cerium oxide colloidal particles (A) as nuclei 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 The silica-based composite colloidal particles (B) coated with silica-based composite colloidal particles (B) to which an amine compound having a molar ratio of 0.001 to 0.08 is bonded. A step of adjusting the mass ratio (A) / (B) to 1 to 50 with respect to the composite colloidal particles (B), and
(E) step: a step of replacing the dispersion medium of the aqueous sol of the modified cerium oxide colloidal particles (C) obtained in the step (d) with a hydrophilic organic solvent,
A method for producing a hydrophilic organic solvent-dispersed sol of the modified ceric oxide colloidal particles (C) according to the fourth aspect, comprising:
As the 17th viewpoint,
A method for producing a hydrophilic solvent-dispersed sol of surface hydrophobized ceric oxide colloidal particles (D),
(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. A step of obtaining an aqueous sol of silica-based composite colloidal particles (B ′) comprising stabilized silica-stannic oxide or silica-antimony pentoxide, comprising silica / stannic oxide or silica / antimony pentoxide First, 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 Rica + 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 step of stabilizing B ′),
(B) step: a step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C ′), wherein the aqueous sol of ceric oxide colloidal particles (A) having a primary particle diameter of 4 to 60 nm, The aqueous sol of silica-based composite colloidal particles (B ′) obtained in the step (a) is mixed so that the mass ratio of (A) / (B ′) is 1 to 50, and the second oxidized oxide is mixed. 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. ) A ratio of mass ratio (A) / (B ′) to 1 to 50,
Step (c): A step of cation exchange of the aqueous sol of the modified cerium oxide colloidal particles (C ′) obtained in the step (b), wherein the silica-based composite colloidal particles (C ') The step of removing the amine compound bound to
Step (d): A step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C), wherein the aqueous sol of modified ceric oxide colloidal particles (C ′) obtained in the step (c) 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. A silica-stannic oxide or silica-antimony pentoxide having a primary particle size of 1 to 3 nm with the addition of an amine compound of 08 and using the cerium oxide colloidal particles (A) as nuclei 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 The silica-based composite colloidal particles (B) coated with silica-based composite colloidal particles (B) to which an amine compound having a molar ratio of 0.001 to 0.08 is bonded. A step of adjusting the mass ratio (A) / (B) to 1 to 50 with respect to the composite colloidal particles (B);
(E) step: replacing the dispersion medium of the aqueous sol of the modified cerium oxide colloidal particles (C) obtained in the step (d) with a hydrophilic organic solvent; and
(F) Step: A step of obtaining a hydrophilic solvent-dispersed sol of surface-hydrophobized cerium oxide colloidal particles (D) in which an organosilicon compound is bonded to the surface of the modified cerium oxide colloidal particles (C), (E) To the hydrophilic organic solvent dispersion sol obtained in the step,
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. ² Represents an alkyl group having 1 to 8 carbon 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, and a + b is 0, 1 or 2 Represents an integer. ) And / or
Formula (II)
[(R ^Four ) _c Si (OX) _3-c ] ₂ Y (II)
(However, R ^Four 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 an alkylene group having 1 to 20 carbon atoms. , C represents an integer of 0 or 1. ) Or at least one compound selected from the group consisting of hydrolysates thereof, and the mass ratio of the organosilicon compound to the modified ceric oxide colloidal particles (C) is 0. A step of making a ratio of .01 to 0.5;
A method for producing a hydrophilic organic solvent-dispersed sol of surface-hydrophobized cerium oxide colloidal particles (D) according to the seventh aspect, comprising:
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. Method for producing solvent-dispersed sol,
As a nineteenth aspect, 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. The 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. A step of obtaining an aqueous sol of silica-based composite colloidal particles (B ′) comprising stabilized silica-stannic oxide or silica-antimony pentoxide, comprising silica / stannic oxide or silica / antimony pentoxide First, 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 Rica + 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 step of stabilizing B ′),
(B) step: a step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C ′), wherein the aqueous sol of ceric oxide colloidal particles (A) having a primary particle diameter of 4 to 60 nm, The aqueous sol of silica-based composite colloidal particles (B ′) obtained in the step (a) is mixed so that the mass ratio of (A) / (B ′) is 1 to 50, and the second oxidized oxide is mixed. 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. ) A ratio of mass ratio (A) / (B ′) to 1 to 50,
Step (c): A step of cation exchange of the aqueous sol of the modified cerium oxide colloidal particles (C ′) obtained in the step (b), wherein the silica-based composite colloidal particles (C ') The step of removing the amine compound bound to
Step (d): A step of obtaining an aqueous sol of the modified cerium oxide colloidal particles (C), wherein the aqueous sol of the modified cerium oxide colloidal particles (C ′) obtained in the step (c) 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. A silica-stannic oxide or silica-antimony pentoxide having a primary particle diameter of 1 to 3 nm with the addition of an amine compound of 08 and using the cerium oxide colloidal particles (A) as nuclei 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) (provided that M The silica-based composite colloidal particles (B) coated with silica-based composite colloidal particles (B) to which an amine compound having a molar ratio of 0.001 to 0.08 is bonded. A step of adjusting the mass ratio (A) / (B) to 1 to 50 with respect to the composite colloidal particles (B);
(E) step: a step of replacing the dispersion medium of the aqueous sol of the modified cerium oxide colloidal particles (C) obtained in the step (d) with a hydrophilic organic solvent,
(F) Step: A step of obtaining a hydrophilic solvent-dispersed sol of surface-hydrophobized cerium oxide colloidal particles (D) in which an organosilicon compound is bonded to the surface of the modified cerium oxide colloidal particles (C), (E) To the hydrophilic organic solvent dispersion sol obtained in the step,
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. ² Represents an alkyl group having 1 to 8 carbon 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, and a + b is 0, 1 or 2 Represents an integer. ) And / or
Formula (II)
[(R ^Four ) _c Si (OX) _3-c ] ₂ Y (II)
(However, R ^Four 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 an alkylene group having 1 to 20 carbon atoms. , C represents an integer of 0 or 1. ) Or at least one compound selected from the group consisting of hydrolysates thereof, and the mass ratio of the organosilicon compound to the modified ceric oxide colloidal particles (C) is 0. A step of making a ratio of .01 to 0.5; and
(G) Step: Hydrophobic having a water solubility of 0.002 to 12% by mass of the dispersion medium of the hydrophilic solvent-dispersed sol of the surface hydrophobized ceric oxide colloidal particles (D) obtained in the step (f) Substituting with an organic solvent,
A method for producing a hydrophobic organic solvent sol having a water solubility of 0.002 to 12% by mass of the surface-hydrophobized ceric oxide colloidal particles (D) according to any one of the ninth aspect to the eleventh aspect ,
As a twenty-first aspect, 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 tertiary amine. A method for producing a hydrophobic organic solvent-dispersed sol having a water solubility of 0.002 to 12 mass% of the colloidal particles (D),
As a twenty-second aspect, 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 acetate, butyl acetate, methyl methacrylate, Isopropyl ether, toluene, triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH), tetraethylene glycol diheptanoate (4G7) and tetraethylene glycol di-2-ethyl 0.002 to 12% by mass of the surface-hydrophobized ceric oxide colloidal particles (D) according to the twentieth aspect or the twenty-first aspect, which is at least one compound selected from the group consisting of hexanoate (4GO) A method for producing a hydrophobic organic solvent-dispersed sol having water solubility.

The 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. Made of antimony and having a mass ratio of 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. In which it exhibits excellent characteristics of ceric oxide as adsorbents.
Moreover, 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. .
Further, the hydrophobic organic compound having a water solubility of 0.002 to 12% by 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 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.

Hereinafter, preferred embodiments of the present invention will be described.
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. Made of antimony oxide and having a mass ratio of silica / stannic oxide or silica / antimony pentoxide of 0.1 to 10 and M / (silica + stannic oxide) or M / (silica + antimony pentoxide) ( Wherein M represents an amine compound) and is coated with a silica-based composite colloidal particle (B) to which an amine compound having a molar ratio of 0.001 to 0.08 is bonded, and the cerium oxide 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.

In the present invention, 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. Alternatively, 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, and 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. When the amount of the amine compound bound to the silica-based composite colloidal particles (B) is less than 0.001 as the molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide), 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. Further, when the molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) exceeds 0.08, 0 of the surface hydrophobized cerium oxide colloidal particles (D). When obtaining a hydrophobic organic solvent-dispersed sol having a water solubility of 0.05 to 12% by mass, 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. When the molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound) is less than 0.1, the gel loses stability upon standing for several hours. Can not be used. When 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 ′). Even if the addition amount of the amine compound exceeds 1.0 as the molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound), the amine compound It is not efficient just to exist in excess.

As the alkali silicate aqueous solution, a sodium silicate aqueous solution or a potassium silicate aqueous solution can be used.
As the alkali stannate aqueous solution, a sodium stannate aqueous solution can be preferably used.
As the alkali antimonate aqueous solution, a potassium antimonate aqueous solution is preferably used.

As the 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.
Examples of 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. -Consisting of 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 M / (silica + antimony pentoxide) ) (Wherein M represents an amine compound) an aqueous sol of silica-based composite colloidal particles (B ′) stabilized with an amine compound having a molar ratio of 0.1 to 1.0, and a mass ratio (A) After obtaining an aqueous sol of modified cerium oxide colloidal particles (C ′) obtained by mixing so that / B (B ′) is 1 to 50, the amine compound is removed from the aqueous sol by cation exchange. , That Thereafter, 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. , 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 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). From the group consisting of 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.

Moreover, 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. And at least one compound selected from the group consisting of an organosilicon compound or a hydrolyzate thereof, and the organosilicon compound is bonded to the surface of the modified cerium oxide colloidal particles (C). A sol dispersed in a hydrophobic organic solvent having a water solubility of 0.002 to 12% by mass of cerium colloidal particles 0.

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. Or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group or a cyano group, and bonded to a silicon atom by a Si—C bond, and 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 a hydrolyzate thereof.

Formula (I)
(R ¹ ) _a (R ³ ) _b Si (OR ² ) _{4- (a + b)} (I)
In the case of R ¹ and R ³ , an organic silicon compound in the case where R ¹ and R ³ represent the same organic group or different organic groups, or a and b represent the same integer or different integers is included.

Examples of the organosilicon compound represented by the general formula (I) 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, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyl Trimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyl Triethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyl Triphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyl Triethoxysilane, δ- Glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl Tributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ -(3,4-D Xycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane Silane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-g Sidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane , Γ-glycidoxypropyl vinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, phenyltrimethoxy Silane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3 , 3, -trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloro Methyltriethoxysilane, N- (β-aminoethyl) γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β- Aminoethyl) γ-aminopropyltriethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldiethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyl Ethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxy Examples thereof include silane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, and methylvinyldiethoxysilane. These can be used alone or in combination of two or more.

As the organosilicon compound represented by the general formula (I) used in the present invention, methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane and hydrolysates thereof are particularly preferable.

Moreover, the 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. These hydrolysates of organosilicon compounds represented by general formula (I) can be used alone or in combination of two or more.

Examples of the organosilicon compound represented by the general formula (II) 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.
Moreover, 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.

In the present invention, 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.
Examples of 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. 9% by weight), butyl acetate (water solubility 1.9% by weight), methyl methacrylate (water solubility 1.1% by weight), diisopropyl ether (water solubility 0.55% by weight), dibutyl ether (water solubility 0.2). Mass%), toluene (water solubility 0.05 mass%), triethylene glycol di-2-ethylhexanoate (3GO) (water solubility 0.0025 mass%), triethylene glycol di-2-ethylbutyrate (3GH) (Water solubility 0.0054% by mass), tetraethylene glycol diheptanoate (4G7) (water solubility 0.0079% by mass) Fine tetraethylene glycol di-2-ethylhexanoate (4GO) (water solubility 0.038 wt%) and the like.

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. A step of obtaining an aqueous sol of silica-based composite colloidal particles (B ′) comprising stabilized silica-stannic oxide or silica-antimony pentoxide, comprising silica / stannic oxide or silica / antimony pentoxide First, 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 Rica + 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 step of stabilizing B ′),
(B) step: a step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C ′), wherein the aqueous sol of ceric oxide colloidal particles (A) having a primary particle diameter of 4 to 60 nm, The aqueous sol of silica-based composite colloidal particles (B ′) obtained in the step (a) is mixed so that the mass ratio of (A) / (B ′) is 1 to 50, and the second oxidized oxide is mixed. 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. ) A ratio of mass ratio (A) / (B ′) to 1 to 50,
Step (c): A step of cation exchange of the aqueous sol of the modified cerium oxide colloidal particles (C ′) obtained in the step (b), wherein the silica-based composite colloidal particles (C ') The step of removing the amine compound bonded to the step, and the step (d): a step of obtaining an aqueous sol of the modified cerium oxide colloidal particles (C), the modification obtained in the step (c) M / (silica + stannic oxide) or M / (silica + antimony pentoxide) or M / (silica + antimony pentoxide) with respect to the silica-based composite colloidal particles (B ′) (where M is an aqueous sol of cerium oxide colloid particles (C ′)) 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, and the outer surface is primary particles of 1 to 3 nm. 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.

In the step (a), 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. As the alkali 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.
As the alkali silicate aqueous solution, a sodium silicate aqueous solution or a potassium silicate aqueous solution can be used.
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. For example, Amberlite (registered trademark) 120B can be packed in a column and used. By carrying out this cation exchange, a silicic acid component and a stannic acid component or an antimonic acid component are polymerized, and 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.
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) It is necessary to prepare 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 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. When 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. In addition, even if 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.

In 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.

As the amine compound, at least one compound selected from the group consisting of primary amines, secondary amines and tertiary amines is used.
Examples of 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. Examples of the alkali component used for the adjustment 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.

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. The 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.

(C) In 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.

In the step (d), 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). By adding 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. When the added amount of the amine compound is less than 0.001 as a molar ratio of M / (silica + stannic oxide) or M / (silica + antimony pentoxide) (where M represents an amine compound), the hydrophilicity of the present invention This 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).
In the step (e), 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.
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. , 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). .
In the 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. Or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group or a cyano group, and bonded to a silicon atom by a Si—C bond, and 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 group, and c represents an integer of 0 or 1. The mass ratio of the organosilicon compound to the dicerium colloid particles (C) is set to a ratio of 0.01 to 0.5.

Examples of the organosilicon compound represented by the general formula (I) and / or the general formula (II) used in the step (f) are as described above, and the modified second oxidized oxide obtained in the step (e). 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. By adding and aging the compound, the organosilicon compound is bonded to the surface of the modified cerium oxide colloidal particles (C).
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.

Aging is performed after the organosilicon compound is added. 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.

In addition, after 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).
In the 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. For example, in the case of the distillation method, 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.
In order to perform solvent substitution efficiently, 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.

Examples of the present invention are shown below. The present invention is not limited to these examples. The measuring method of physical properties is shown below.
(Transmission electron microscope observation)
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. In the dynamic light scattering method, 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.
〔specific gravity〕
It calculated | required by the float balance method (liquid temperature of 25 degreeC).
〔viscosity〕
It calculated | required with the B-type viscosity meter (liquid temperature of 25 degreeC).
〔moisture〕
It was determined by Karl Fischer titration.

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. After the addition was completed, 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. Next, 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. When 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 μS / 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. 5 kg of a cerium oxide aqueous sol having a content of 5.15% by mass, a pH of 9.3, an electric conductivity of 140 μS / cm, an average particle size of 43 nm by a dynamic light scattering method, and a primary particle size of 10 nm by observation with a transmission electron microscope was obtained.

Production Example 2
Sodium stannate (NaSnO ₃ · H ₂ O) (SnO) was added to an aqueous solution obtained by diluting 76.8 g of JIS 3 sodium silicate (containing 29.3 mass% as SiO ₂ , manufactured by Fuji Chemical Co., Ltd.) with 766.8 g of pure water. _{As a result,} 13.5 g of 55.4% by mass (made by Showa Kako Co., Ltd.) was dissolved. 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. Next, 9.0 g of diisopropylamine was added to the obtained acidic aqueous sol. The obtained sol was an alkaline aqueous sol of stannic oxide-silica composite colloidal particles. The molar ratio of diisopropylamine / (silica + stannic oxide) was 0.21, and the pH was 10.3. In the aqueous sol, colloidal particles having a primary particle diameter of 3 nm or less were observed with a transmission electron microscope.

Production Example 3
35.6 kg of potassium silicate aqueous solution (containing 19.9 mass% as SiO ₂ , manufactured by Nissan Chemical Industries, Ltd.) was diluted with 330.0 kg of pure water. After adding 18.1 kg of 48% potassium hydroxide aqueous solution and 3.2 kg of antimony trioxide (manufactured by Mikuni Seimitsu Co., Ltd.) to this diluted solution, and further adding 2.2 kg of 35 mass% hydrogen peroxide water with stirring. By reacting at 93 ° C. for 1 hour, an aqueous solution of potassium antimonate silicate was obtained. 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. Next, 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. In the aqueous sol, colloidal particles having a primary particle diameter of 3 nm or less were observed with a transmission electron microscope.

Production Example 4
34.1 g of JIS 3 sodium silicate (containing 29.3 mass% as SiO ₂ , manufactured by Fuji Chemical Co., Ltd.) was diluted with 251.4 g of pure water. The obtained aqueous solution was passed through a column packed with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and 290 g of an active silicic acid aqueous solution (pH 3.1, containing 3.5% by mass as SiO ₂₎ was added. Obtained. Subsequently, 3.0 g of diisopropylamine was added to this active silicic acid aqueous solution. The obtained aqueous solution was an aqueous solution containing an alkaline silicic acid oligomer, and the diisopropylamine / silica molar ratio was 0.18 and pH 10.2.

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. Got. The obtained acidic aqueous sol had a total metal oxide concentration of 4.4% by mass and a pH of 2.7.
Next, 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. At this time, the molar ratio of diisopropylamine / (silica + stannic oxide) in the sol was 0.013, and the pH was 3.5. Subsequently, 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. Got. The obtained acidic aqueous sol had a total metal oxide concentration of 4.4% by mass and a pH of 2.7.
Next, 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. At this time, the molar ratio of diisobutylamine / (silica + stannic oxide) in the sol was 0.013, and the pH was 3.5. Subsequently, 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. 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. Subsequently, 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. Next, 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. At this time, the pH of the sol was 3.7, and the molar ratio of diisobutylamine / (silica + antimony pentoxide) was 0.065. Subsequently, 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. 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.

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. Next, 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. In addition, 240 g of an aqueous sol having an average particle diameter of 49 nm obtained by a dynamic light scattering method was obtained.

Comparative 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. Couldn'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.

〔Evaluation methods〕
The obtained sol was evaluated by the following method.
(1) Preparation of coating composition Using the sols obtained in Examples 1, 2, 3, 5 and Comparative Example 1, a coating composition was prepared by the following method.
The aqueous sol is mixed with the polyester emulsion WB-630-25 (manufactured by Sensho Kasei) so that the solid content ratio (total metal oxide: binder) = 1: 1, and the total solid content concentration is 20% by mass. A dispersion composition was added to prepare a coating composition. The organic solvent dispersion sol is composed of a silica-based binder (a mixture of γ-glycidoxypropyltrimethoxysilane partial hydrolyzate and aluminum acetylacetonate) and a solid content ratio (total metal oxide: binder). ) = 1: 1, and a sol dispersion medium was added so that the total solid content concentration was 20% by mass to prepare a coating composition.
(2) Production of cured film The coating composition prepared in (1) above was dropped on a glass substrate and spin-coated under the conditions of 300 rpm × 3 seconds and 1800 rpm × 8 seconds to form a film. Subsequently, after drying for 10 minutes at 80 degreeC using a hotplate, 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.
Hunter's color difference ΔE = [(L ₁ −L ₀ ) ² + (a ₁ −a ₀ ) ² + (b ₁ −b ₀ ) ² ] ^1/2
However, L ₀ , a ₀ , and b ₀ indicate color coordinate values before ultraviolet irradiation, and L ₁ , a ₁ , and b ₁ indicate color coordinate values after 30 minutes of ultraviolet irradiation.
The evaluation results of the coating composition are shown in Table 1-1, and the evaluation results of the cured film are shown in Table 1-2.
The sol of the modified cerium oxide colloidal particles has suppressed the increase of the color difference value, and particularly the modified cerium oxide colloidal particles coated with the stannic oxide-silica composite colloidal particles were excellent in 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.

Claims

A cerium oxide colloidal particle (A) having a primary particle size of 4 to 60 nm is used as a nucleus, and its outer surface is made of silica-stannic oxide or silica-antimony pentoxide having a primary particle size of 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 is an amine) The silica-based composite of the cerium oxide colloidal particles (A) coated with silica-based composite colloidal particles (B) to which an amine compound having a molar ratio of 0.001 to 0.08 is bonded. Modified cerium oxide colloidal particles (C) having a mass ratio (A) / (B) of 1 to 50 with respect to the colloidal particles (B).
The modified ceric oxide colloidal particles (C) according to claim 1, wherein the amine compound is at least one compound selected from the group consisting of primary amines, secondary amines and tertiary amines.
An aqueous sol of the modified ceric oxide colloidal particles (C) according to claim 1 or 2.
A hydrophilic organic solvent-dispersed sol of the modified cerium oxide colloidal particles (C) according to claim 1 or 2.
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 ether, dipropylene The hydrophilic organic solvent-dispersed sol according to claim 4, which is at least one compound selected from the group consisting of glycol, propylene glycol monomethyl ether and propylene glycol monoethyl ether.
Surface hydrophobized ceric oxide colloidal particles (D) in which an organosilicon compound is bonded to the surface of the modified ceric oxide colloidal particles (C) according to claim 1 or 2.
A hydrophilic organic solvent-dispersed sol of surface-hydrophobized ceric oxide colloidal particles (D) according to claim 6.
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 ether, dipropylene The hydrophilic organic solvent-dispersed sol according to claim 7, which is at least one compound selected from the group consisting of glycol, propylene glycol monomethyl ether and propylene glycol monoethyl ether.
A hydrophobic organic solvent-dispersed sol having a water solubility of 0.002 to 12% by mass of the surface-hydrophobized cerium oxide colloidal particles (D) according to claim 6.
The surface hydrophobized cerium oxide colloidal particles (D) according to claim 6, wherein a mass ratio of the organosilicon compound to the modified cerium oxide colloidal particles (C) is 0.01 to 0.50. A hydrophobic organic solvent-dispersed sol having a water solubility of 002 to 12% by mass.
The organosilicon compound 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. Or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group or a cyano group, and bonded to a silicon atom by a Si—C bond, and 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) 7 is an at least one compound selected from the group consisting of an organosilicon compound represented by the formula (1), wherein c represents an integer of 0 or 1), or a hydrolyzate thereof. Surface hydrophobized ceric oxide colloidal particles (D).
The hydrophobic organic solvent having a water solubility of 0.002 to 12% by mass is at least one selected from the group consisting of ketones, esters, hydrocarbons, halogenated hydrocarbons, and polyoxyalkylene dicarboxylic acid alkyl esters. A hydrophobic organic solvent dispersion having a water solubility of 0.002 to 12 mass% of the surface-hydrophobized cerium oxide colloidal particles (D) according to any one of claims 9 to 11, which is a seed compound. Sol.
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 di-2-ethylhexa At least selected from the group consisting of noate (3GO), triethylene glycol di-2-ethylbutyrate (3GH), tetraethylene glycol diheptanoate (4G7) and tetraethylene glycol di-2-ethylhexanoate (4GO) A hydrophobic organic solvent having a water solubility of 0.002 to 12% by mass of the surface-hydrophobized cerium oxide colloidal particles (D) according to any one of claims 9 to 11, which is a single compound. Dispersed sol.
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. A step of obtaining an aqueous sol of silica-based composite colloidal particles (B ′) comprising stabilized silica-stannic oxide or silica-antimony pentoxide, comprising silica / stannic oxide or silica / antimony pentoxide First, 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 Rica + 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 step of stabilizing B ′),
(B) step: a step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C ′), wherein the aqueous sol of ceric oxide colloidal particles (A) having a primary particle diameter of 4 to 60 nm, The aqueous sol of silica-based composite colloidal particles (B ′) obtained in the step (a) is mixed so that the mass ratio of (A) / (B ′) is 1 to 50, and the second oxidized oxide is mixed. 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. ) A ratio of mass ratio (A) / (B ′) to 1 to 50,
Step (c): A step of cation exchange of the aqueous sol of the modified cerium oxide colloidal particles (C ′) obtained in the step (b), wherein the silica-based composite colloidal particles (C ') The step of removing the amine compound bonded to the step, and the step (d): a step of obtaining an aqueous sol of the modified cerium oxide colloidal particles (C), the modification obtained in the step (c) M / (silica + stannic oxide) or M / (silica + antimony pentoxide) or M / (silica + antimony pentoxide) with respect to the silica-based composite colloidal particles (B ′) (where M is an aqueous sol of cerium oxide colloid particles (C ′)) 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, and the outer surface is primary particles of 1 to 3 nm. 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 a mass ratio (A) / (B) of the cerium oxide colloidal particles (A) to the silica-based composite colloidal particles (B) to be 1 to 50;
The manufacturing method of the aqueous | water-based sol of the modified cerium oxide colloidal particle (C) of Claim 3 containing this.
The aqueous sol of modified ceric oxide colloidal particles (C) according to claim 14, wherein the amine compound is at least one compound selected from the group consisting of primary amines, secondary amines and tertiary amines. Manufacturing method.
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. A step of obtaining an aqueous sol of silica-based composite colloidal particles (B ′) comprising stabilized silica-stannic oxide or silica-antimony pentoxide, comprising silica / stannic oxide or silica / antimony pentoxide First, 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 Rica + 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 step of stabilizing B ′),
(B) step: a step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C ′), wherein the aqueous sol of ceric oxide colloidal particles (A) having a primary particle diameter of 4 to 60 nm, The aqueous sol of silica-based composite colloidal particles (B ′) obtained in the step (a) is mixed so that the mass ratio of (A) / (B ′) is 1 to 50, and the second oxidized oxide is mixed. 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. ) A ratio of mass ratio (A) / (B ′) to 1 to 50,
Step (c): A step of cation exchange of the aqueous sol of the modified cerium oxide colloidal particles (C ′) obtained in the step (b), wherein the silica-based composite colloidal particles (C ') The step of removing the amine compound bound to
Step (d): A step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C), wherein the aqueous sol of modified ceric oxide colloidal particles (C ′) obtained in the step (c) 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. A silica-stannic oxide or silica-antimony pentoxide having a primary particle size of 1 to 3 nm with the addition of an amine compound of 08 and using the cerium oxide colloidal particles (A) as nuclei 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 The silica-based composite colloidal particles (B) coated with silica-based composite colloidal particles (B) to which an amine compound having a molar ratio of 0.001 to 0.08 is bonded. A step of adjusting the mass ratio (A) / (B) to 1 to 50 with respect to the composite colloidal particles (B), and a step (e): the modified ceric oxide colloidal particles obtained in the step (d) ( A step of replacing the dispersion medium of the aqueous sol of C) with a hydrophilic organic solvent,
A process for producing a hydrophilic organic solvent-dispersed sol of the modified ceric oxide colloidal particles (C) according to claim 4.
A method for producing a hydrophilic solvent-dispersed sol of surface hydrophobized ceric oxide colloidal particles (D),
(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. A step of obtaining an aqueous sol of silica-based composite colloidal particles (B ′) comprising stabilized silica-stannic oxide or silica-antimony pentoxide, comprising silica / stannic oxide or silica / antimony pentoxide First, 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 Rica + 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 step of stabilizing B ′),
(B) step: a step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C ′), wherein the aqueous sol of ceric oxide colloidal particles (A) having a primary particle diameter of 4 to 60 nm, The aqueous sol of silica-based composite colloidal particles (B ′) obtained in the step (a) is mixed so that the mass ratio of (A) / (B ′) is 1 to 50, and the second oxidized oxide is mixed. 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. ) A ratio of mass ratio (A) / (B ′) to 1 to 50,
Step (c): A step of cation exchange of the aqueous sol of the modified cerium oxide colloidal particles (C ′) obtained in the step (b), wherein the silica-based composite colloidal particles (C ') The step of removing the amine compound bound to
Step (d): A step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C), wherein the aqueous sol of modified ceric oxide colloidal particles (C ′) obtained in the step (c) 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. A silica-stannic oxide or silica-antimony pentoxide having a primary particle size of 1 to 3 nm with the addition of an amine compound of 08 and using the cerium oxide colloidal particles (A) as nuclei 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 The silica-based composite colloidal particles (B) coated with silica-based composite colloidal particles (B) to which an amine compound having a molar ratio of 0.001 to 0.08 is bonded. A step of adjusting the mass ratio (A) / (B) to 1 to 50 with respect to the composite colloidal particles (B);
Step (e): Step of replacing the dispersion medium of the aqueous sol of the modified cerium oxide colloidal particles (C) obtained in Step (d) with a hydrophilic organic solvent, and Step (f): The organosilicon compound is A step of obtaining a hydrophilic solvent-dispersed sol of surface-hydrophobized cerium oxide colloidal particles (D) bonded to the surface of the modified cerium oxide colloidal particles (C), the hydrophilicity obtained in the step (e) In the organic solvent dispersion sol,
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. Or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group or a cyano group, and bonded to a silicon atom by a Si—C bond, and 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 group, and c represents an integer of 0 or 1. A step of adjusting the mass ratio of the organosilicon compound to the dicerium colloid particles (C) to be 0.01 to 0.5;
A method for producing a hydrophilic organic solvent-dispersed sol of surface-hydrophobized cerium oxide colloidal particles (D) according to claim 7.
The method for producing a hydrophilic organic solvent-dispersed sol according to claim 16 or 17, wherein 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 ether, dipropylene The method for producing a hydrophilic organic solvent-dispersed sol according to claim 16 or 17, which is at least one compound selected from the group consisting of glycol, propylene glycol monomethyl ether and propylene glycol monoethyl ether.
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. A step of obtaining an aqueous sol of silica-based composite colloidal particles (B ′) comprising stabilized silica-stannic oxide or silica-antimony pentoxide, comprising silica / stannic oxide or silica / antimony pentoxide First, 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 Rica + 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 step of stabilizing B ′),
(B) step: a step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C ′), wherein the aqueous sol of ceric oxide colloidal particles (A) having a primary particle diameter of 4 to 60 nm, The aqueous sol of silica-based composite colloidal particles (B ′) obtained in the step (a) is mixed so that the mass ratio of (A) / (B ′) is 1 to 50, and the second oxidized oxide is mixed. 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. ) A ratio of mass ratio (A) / (B ′) to 1 to 50,
Step (c): A step of cation exchange of the aqueous sol of the modified cerium oxide colloidal particles (C ′) obtained in the step (b), wherein the silica-based composite colloidal particles (C ') The step of removing the amine compound bound to
Step (d): A step of obtaining an aqueous sol of modified ceric oxide colloidal particles (C), wherein the aqueous sol of modified ceric oxide colloidal particles (C ′) obtained in the step (c) 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. A silica-stannic oxide or silica-antimony pentoxide having a primary particle size of 1 to 3 nm with the addition of an amine compound of 08 and using the cerium oxide colloidal particles (A) as nuclei 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 The silica-based composite colloidal particles (B) coated with silica-based composite colloidal particles (B) to which an amine compound having a molar ratio of 0.001 to 0.08 is bonded. A step of adjusting the mass ratio (A) / (B) to 1 to 50 with respect to the composite colloidal particles (B);
(E) step: a step of replacing the dispersion medium of the aqueous sol of the modified cerium oxide colloidal particles (C) obtained in the step (d) with a hydrophilic organic solvent,
(F) Step: A step of obtaining a hydrophilic solvent-dispersed sol of surface-hydrophobized cerium oxide colloidal particles (D) in which an organosilicon compound is bonded to the surface of the modified cerium oxide colloidal particles (C), (E) To the hydrophilic organic solvent dispersion sol obtained in the step,
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. Or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group or a cyano group, and bonded to a silicon atom by a Si—C bond, and 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 group, and c represents an integer of 0 or 1. The step of adjusting the mass ratio of the organosilicon compound to the dicerium colloidal particles (C) to be 0.01 to 0.5, and the step (g): the surface hydrophobized second oxide obtained in the step (f) Replacing the dispersion medium of the hydrophilic solvent-dispersed sol of the cerium colloid particles (D) with a hydrophobic organic solvent having a water solubility of 0.002 to 12% by mass;
A method for producing a hydrophobic organic solvent sol having a water solubility of 0.002 to 12% by mass of the surface-hydrophobized cerium oxide colloidal particles (D) according to any one of claims 9 to 11 .
The surface-hydrophobized cerium oxide colloidal particles (D) according to claim 20, wherein the amine compound is at least one compound selected from the group consisting of a primary amine, a secondary amine class and a tertiary amine. A method for producing a hydrophobic organic solvent-dispersed sol having a water solubility of 0.002 to 12% by mass.
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 ether, dipropylene And at least one compound selected from the group consisting of glycol, propylene glycol monomethyl ether and propylene glycol monoethyl ether, and 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 Tellurium, toluene, triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH), tetraethylene glycol diheptanoate (4G7) and tetraethylene glycol di-2-ethylhexa The surface hydrophobized cerium oxide colloidal particles (D) of 0.002 to 12% by mass of water according to claim 20 or 21, which are at least one compound selected from the group consisting of noate (4GO). A method for producing a hydrophobic organic solvent-dispersed sol having solubility.