JP2010042947A - Dispersion of titanium oxide complex particle and method of manufacturing the dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a dispersion of titanium oxide complex particles that combines high weatherability, light resistance, photocatalytic activity restraining effect and a high refractive index and further excels in stability, acid resistance and transparency. <P>SOLUTION: The surfaces of core particles consisting of oxide fine particles of titanium or complex oxide fine particles comprising titanium and silicon and/or tin are coated with an amino group-containing complex which is obtained by polycondensation by simultaneously adding an aqueous solution containing a hydrolyzate of a metal alkoxide having an amino group, a silicic acid solution or an aqueous solution of a silicate, and an aqueous solution which has salts of one or more kinds of metal elements selected from among aluminum, zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium and yttrium dissolved therein. The surfaces of the resultant are further coated with a silica type oxide or silica type complex oxide to form the dispersion of the titanium oxide complex particles. The manufacturing method of the dispersion is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a dispersion of titanium oxide composite particles and a method for producing the dispersion. More specifically, a dispersion of titanium oxide composite particles obtained by dispersing titanium oxide composite particles having optical properties, coating strength properties, dielectric properties, catalytic properties, etc. in water and / or an organic solvent, and a method for producing the same It is about.

  Since titanium oxide fine particles have a high refractive index, they have been suitably used as a material for a coating solution for forming a high refractive index film such as a hard coat layer or primer layer of a plastic lens. However, since the photocatalytic activity of the titanium oxide fine particles themselves is high, the organic silicon compound or resin component of the film forming component is decomposed, or the film deteriorates on the surface of the base material, resulting in a decrease in adhesion between the base material and the film. was there.

As a method for solving such a problem, Patent Document 1 discloses composite oxide fine particles in which core particles made of oxide fine particles containing titanium and tin are coated with a composite oxide containing silicon, zirconium and / or aluminum. Has been. If a coating solution containing such composite oxide fine particles is used, a coating film having a high refractive index and excellent weather resistance and light resistance can be formed. However, depending on the use conditions, these can be further improved. It was necessary to let them.

On the other hand, surface treatment with a metal alkoxide having an amino group is generally performed as a means for hydrophobizing the surface of inorganic oxide particles and improving dispersibility in an organic solvent. Patent Document 2 describes a method of directly bonding an organic group to silicon in a composite oxide for the purpose of improving dispersibility of the composite oxide sol containing silica in an organic solvent and an organic resin.
JP 2000-204301 A Japanese Patent No. 3683070

  An object of the present invention is to provide a dispersion of titanium oxide-based composite particles having excellent transparency, including titanium oxide-based composite particles having suppressed photocatalytic activity, excellent weather resistance and light resistance, and high refractive index, and It is to provide a method for producing a dispersion.

  The dispersion of titanium oxide-based composite particles according to the present invention has at least an amino group on the surface of core particles composed of titanium oxide fine particles or composite oxide fine particles containing titanium and silicon and / or tin. An aqueous solution containing a hydrolyzate of metal alkoxide, an aqueous solution of silicic acid solution or silicate, and one or more selected from aluminum, zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium and yttrium Coated with an amino group-containing complex obtained by simultaneous polycondensation with an aqueous solution in which a metal element salt is dissolved, and further coated with a silica-based oxide or silica-based composite oxide. It is characterized by.

In the dispersion of titanium oxide composite particles according to the present invention, the number of moles of titanium contained in the core particles is represented by A, and the number of moles of amino groups contained in the amino group-containing composite is represented by B. The molar ratio (B / A) is preferably in the range of 0.001 to 0.04.
The metal alkoxide having an amino group includes γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-amino. Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyl One or more selected from trimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-phenylaminopropyltrimethoxysilane are preferable.
The average particle diameter of the titanium oxide-based composite particles is preferably in the range of 3 to 80 nm when measured by a dynamic light scattering method.

The method for producing a dispersion of titanium oxide composite particles according to the present invention includes:
(1) While heating an aqueous dispersion in which core fine particles composed of titanium oxide fine particles or composite oxide fine particles composed of titanium and silicon and / or tin are dispersed,
(A) an aqueous solution containing a hydrolyzate of a metal alkoxide having an amino group,
(B) an aqueous solution of a silicate solution or a silicate, and (C) a salt of one or more metal elements selected from aluminum, zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium and yttrium A step of coating the surface of the core particles with an amino group-containing complex comprising a polycondensate obtained by simultaneously adding a dissolved aqueous solution to the aqueous dispersion, and (2) from the step (1) While heating the obtained aqueous dispersion,
(D) a silicic acid solution, or (E) a silicic acid solution and a hydroxide of one or more metal elements selected from zirconium, antimony, tungsten, tin, aluminum, niobium, cerium and zinc; After adding an aqueous solution of an oxide, an alkoxide and / or an inorganic salt, a step of coating the surface of the particles coated with the amino group-containing composite with a silica-based oxide or a silica-based composite oxide by heating. It is characterized by including.

Furthermore, the method for producing a dispersion of titanium oxide composite particles according to the present invention preferably includes a step of subjecting the aqueous dispersion obtained in the step (2) to solvent substitution with an organic solvent.
Moreover, in the said process (1), it is preferable that the heating temperature of the aqueous dispersion of the said core particle exists in the range of 60-210 degreeC.
In the step (1), the pH of the dispersion when the aqueous solutions of the components (A), (B), and (C) are added simultaneously is adjusted to be in the range of 7-12. Is preferred.

Moreover, in the said process (1), the addition rate of the aqueous solution of the said component (A) is the range of 0.005-0.2 mol / Hr on the molar basis of the amino group which the metal alkoxide contained in this aqueous solution has. It is preferable that it exists in.
Moreover, in the said process (1), the addition rate of the aqueous solution of the said component (B) is 0.012-0.5 mol / on the molar reference | standard of the silicon which the silicic acid or silicate contained in this aqueous solution has. It is preferably in the range of Hr.
Moreover, in the said process (1), the addition rate of the aqueous solution of the said component (C) is the range of 0.005-0.2 mol / Hr on the molar basis of the metal element which the metal salt contained in this aqueous solution has. It is preferable that it exists in.

Moreover, in the said process (1), the density | concentration of the aqueous solution containing the hydrolyzate of the metal alkoxide which has the said amino group exists in the range of 0.2 to 20 weight%, and the density | concentration of the said silicic acid liquid or the aqueous solution of a silicate Is in the range of 0.5 to 6% by weight in terms of SiO ₂ , and one or more metal elements selected from aluminum, zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium and yttrium The concentration of the aqueous solution in which the salt is dissolved is preferably in the range of 0.01 to 5% by weight in terms of oxide.

The titanium oxide composite particles according to the present invention have excellent weather resistance, light resistance and photocatalytic activity suppression effect. Furthermore, in the coating film obtained by the coating liquid using the dispersion liquid of the titanium oxide composite particles, the resin composition obtained by using the dispersion liquid of the titanium oxide composite particles, Deterioration, discoloration and the like due to photocatalytic activity are greatly suppressed.
Such an effect is obtained because the photocatalytic activity of the titanium oxide-based composite particles is suppressed by covering the surface of the core particles with a composite containing an amino group.
Moreover, according to the composite containing an amino group, the above-mentioned photocatalytic activity suppressing effect can be obtained with a relatively low coating amount, and therefore the high refractive index property of the titanium oxide composite particles is rarely lowered.

Such an amino group is unstable and reacts only in a small amount even when trying to react with the surface of the core particle by using, for example, a silane coupling agent containing an amino group alone. By combining a hydrolyzate of a metal alkoxide having a group with another coating forming component, a relatively large amount of amino groups can be stably incorporated into the amino group-containing complex. By coating the particles, a dispersion of titanium oxide composite particles excellent in acid resistance stability and storage stability is provided.

  In addition, in order to further improve acid resistance, storage stability, and high dispersibility, the surface of the amino group-containing composite is further treated with silica-based oxide or silica-based composite oxide in the titanium oxide composite particles according to the present invention. It is covered. This silica-based oxide or silica-based composite oxide also has the effect of improving the light resistance and the photocatalytic activity suppressing effect of the titanium oxide-based composite particles. Moreover, in the titanium oxide composite particles of the present invention, the photocatalytic activity, weather resistance, and light resistance of the core particles are suppressed by coating the surface of the core particles with an amino group-containing composite. The coating amount of the composite oxide is relatively low, and the refractive index of the titanium oxide composite particles is hardly lowered.

The dispersion of the titanium oxide composite particles of the present invention is also excellent in transparency.
If this titanium oxide composite particle dispersion is blended with a coating liquid for forming a film and an organic resin, a coating film having a high weather resistance, light resistance, discoloration resistance, and photocatalytic activity suppression effect, a resin composition, etc. can get.
Moreover, since the said titanium oxide type composite particle maintains the high refractive index, it is suitable as a material of various high refractive index coating films and high refractive index resin compositions.

In addition, because it is a material having strength characteristics, conductivity, moderate ultraviolet absorption characteristics, catalytic activity, etc., various additives, or various high-refractive-index materials and hard coats mixed with or reacted with various inorganic compounds or organic compounds as raw materials Coating materials, UV absorbers, antifouling materials, antibacterial agents, deodorants, adhesives, masking materials, conductive materials, reflective materials, sealing materials, fillers, packaging materials, photocatalysts, antireflection film materials, fiber materials, electrodes It can be widely used for materials, building materials, paper, and other various paints.

Hereinafter, the present invention will be specifically described.
Titanium oxide fine particles, or core particles (nuclear particles) composed of composite oxide fine particles containing titanium and silicon and / or tin
As the core particles according to the present invention, conventionally known titanium oxide fine particles, or core particles composed of composite oxide fine particles containing titanium and silicon and / or tin can be used.
The crystal structure of the core particle may be any of anatase type, rutile type, or a mixed type thereof. Rutile-type core particles are particularly preferred because of their high refractive index, light resistance, and weather resistance.
A part of the crystal structure of the core particle can be schematically shown by a chemical formula as follows.

Example of nuclear particle structure

｜ ｜
-O-Ti-O-Ti-O-
｜ ｜

｜ ｜
-O-Ti-O-Si-O-
｜ ｜

｜ ｜
-O-Ti-O-Sn-O-
｜ ｜

｜ ｜ ｜
-O-Ti-O-Sn-O-Si-O-
｜ ｜ ｜

Amino group-containing composite In the titanium oxide composite particles according to the present invention, an intermediate coating layer made of an amino group-containing composite is formed on the surface of the core particles. The amino group-containing complex includes an aqueous solution containing a hydrolyzate of a metal alkoxide having an amino group, a silicic acid solution or an aqueous solution of silicate, aluminum, zirconium, zinc, cerium, tin on the surface of the core particle. , Lanthanum, magnesium, calcium, and yttrium, and an aqueous solution in which a salt of one or more metal elements is dissolved and simultaneously added and polycondensed.

  The amino group content contained in the amino group-containing composite is represented by A as the number of moles of titanium contained in the titanium oxide fine particles or the composite oxide fine particles containing titanium and silicon and / or tin. When the number of moles of amino groups contained in the amino group-containing complex is represented by B, the molar ratio (B / A) is in the range of 0.001 to 0.04, particularly in the range of 0.004 to 0.020. It is preferable that it exists in. The said molar ratio can be adjusted with the preparation amount of the metal alkoxide containing an amino group. When the molar ratio is less than 0.001, the light resistance, weather resistance, and photoactivity suppression effect of the titanium oxide composite particles according to the present invention are reduced, and when the molar ratio exceeds 0.04, the resulting titanium oxide composite particles are refracted. The amount of hydrolyzate of metal group-containing metal alkoxide decreases beyond the amount that can be stably combined in the titanium oxide composite particles, and is released to the outside of the titanium oxide composite particles. This is not preferable because the stability and acid resistance of the resin may decrease.

The metal alkoxide having an amino group is not particularly limited as long as it has an amino group, and known ones can be used. γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-phenylaminopropyltri Methoxysilane or the like can be preferably used. Moreover, you may mix and use these.

Also, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltriethoxysilane, 3-aminopropyldiisopropylethoxysilane, 1-amino-2- (dimethylethoxysilyl) propane, (aminoethyl Amino) -3-isobutyldimethylmethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl Dimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (6-aminohexyl) aminomethyltrimethoxysilane , N (6-aminohexyl) aminomethyltriethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, 11-aminoundecyltri Ethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane, m-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, (3-trimethoxysilylpropyl) diethylenetriamine, N-methylaminopropylmethyldimethoxysilane , N-methylaminopropyltrimethoxysilane, dimethylaminomethylethoxysilane, (N, N-dimethylaminopropyl) trimethoxysilane, (N-acetylglycidyl) -3-aminopropyltrimethoxysilane It may be used at least one member.

Here, the aqueous solution containing the hydrolyzate of metal alkoxide having an amino group is an aqueous solution in which the metal alkoxide having an amino group is mixed with stirring in water. The hydrolyzate of a metal alkoxide having an amino group is a product obtained by hydrolyzing a metal alkoxide having an amino group with stirring and mixing with water, and at least one of OR groups of the metal alkoxide having an amino group. It means one having a structure in which part is substituted with OH group.
The silicic acid solution here is an acidic silicic acid solution obtained by dealkalizing an aqueous solution of a water-soluble silicate with a cation exchange resin or the like, and an aqueous solution containing a low polymer of silicic acid. means.
In addition, the aqueous solution of silicate herein means a solution in which an alkali metal silicate such as sodium silicate or potassium silicate is dissolved in water.

The salt of any one or more metal elements selected from aluminum, zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium, and yttrium can be used without limitation as long as it is a water-soluble salt. Can do. As such a salt, for example, sodium aluminate salt, ammonium zirconium carbonate, peroxotitanium, potassium stannate, magnesium sulfate, zinc nitrate and the like can be suitably used.
The structure of the amino group-containing composite is composed of silica, an oxide of one or more metal elements selected from aluminum, zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium, and yttrium, and an amino group. And a hydrolyzate of a metal alkoxide containing a complex at a molecular level.

In the present invention, titanium oxide composite particles obtained by coating the surface of core particles comprising titanium oxide fine particles or composite oxide fine particles containing titanium and silicon and / or tin with an amino group-containing composite are obtained. The effect which the weather resistance, light resistance, and the photocatalytic activity suppression effect improve is acquired.
Although the reason for this is not clear, in the hydrolyzate of metal alkoxide having an amino group, the amino group dissociates to become NH ³⁺ and has a positive charge, OH group on the surface of the core particle, silica and aluminum Inactivates negative charges and interactions in complex oxides formed by oxides of one or more metal elements selected from zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium and yttrium It is thought that it is to make it.

Such a hydrolyzate of a metal alkoxide having an amino group is non-uniform and can be deposited only in a small amount when the surface treatment or coating is carried out on the surface of the core particle alone. Since it is present at the particle interface, the stability is low, and the hydrolyzate of metal alkoxide having an amino group is easily detached from the particle surface due to the influence of moisture or alkali. In addition, it is difficult to further coat with an inorganic oxide after the surface treatment of the metal alkoxide having an amino group on the core particles alone.
However, in the present invention, in addition to the coordination of the amino group with the negative charge in the complex as described above, the OH group contained in the hydrolyzate of the amino group-containing metal alkoxide contains the amino group-containing complex. In order to form a three-dimensional network structure at the molecular level by polycondensation with an OH group in a silicic acid monomer or a silicic acid polymer contained in a silicic acid solution or an aqueous solution of silicate that is sometimes added at the same time, A desired amount of amino groups can be stably immobilized in the body skeleton.

The above effects can improve the weather resistance, light resistance, and photocatalytic activity suppression effect of the resulting titanium oxide composite particles even with a relatively small coating amount, so that the high refractive index property of the titanium oxide composite particles can be improved. It can be kept high.
The coating amount of the amino group-containing complex with respect to the core particles is preferably in the range of 1 to 40 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the core particles.
When the coating amount is less than 1 part by weight relative to 100 parts by weight of the core particles, the weather resistance, light resistance and photocatalytic activity suppressing effect of the titanium oxide composite particles according to the present invention are reduced, and the coating amount is 40% by weight. If it exceeds the part, the refractive index of the titanium oxide composite particles according to the present invention is lowered, which is not preferable.

Silica-based oxide or silica-based composite oxide coating In the titanium oxide-based composite particles according to the present invention, a coating layer made of silica-based oxide or silica-based composite oxide is formed on the surface of the amino group-containing composite. Yes.
The coating amount of the silica-based oxide or silica-based composite oxide is preferably in the range of 0.5 to 30 parts by weight with respect to 100 parts by weight of the titanium oxide-based composite particles.
When the weight ratio is less than 0.5 parts by weight with respect to 100 parts by weight of the titanium oxide composite particles, the stability and acid resistance of the resulting dispersion of the titanium oxide composite particles may be reduced, or surface treatment may be performed. Since it may become difficult, it is not preferable. Moreover, when the said weight ratio exceeds 30 weight part with respect to 100 weight part of titanium oxide type composite particles, since the refractive index of the obtained titanium oxide type composite oxide particle falls, it may be unpreferable.

Here, the silica-based oxide is an oxide mainly composed of silicon dioxide, and the silica-based composite oxide is one selected from silicon and zirconium, antimony, tungsten, tin, aluminum, niobium, cerium, and zinc. Alternatively, it is a complex oxide with two or more metal elements. It is particularly preferable that the silica-based composite oxide contains zirconium because the refractive index of the titanium oxide-based composite particles according to the present invention is hardly lowered.
A part of such a silica-based composite oxide can be schematically shown by a chemical formula as follows.

Example of silica-based composite oxide

｜ ｜
-O-Si-O-Zr-O-
｜ ｜

｜ ｜
-O-Si-O-Al-O-
｜ ｜

In the titanium oxide-based composite particles according to the present invention, the surface of the amino group-containing composite is coated with the silica-based oxide or the silica-based composite oxide to obtain a titanium oxide-based composite particle in a dispersion. It has the effect of improving stability and acid resistance. Moreover, there exists an effect which suppresses that the surface treatment by the silane coupling agent etc. which the amino group which exists in part on the surface of an amino-group containing composite_body | complex later mentions. In addition, the light resistance, weather resistance and photocatalytic activity suppressing effect of the titanium oxide composite particles are also improved.
In the present invention, the formation of an amino group-containing complex on the surface of the core particle improves the light resistance, weather resistance, and photocatalytic activity suppression effect of the core particle. Is relatively small. Therefore, titanium oxide composite particles having a high refractive index can be obtained.

Titanium oxide composite particles The titanium oxide composite particles according to the present invention will be described below.
The titanium oxide composite particles according to the present invention have at least the surface of a core particle composed of titanium oxide fine particles or composite oxide fine particles containing titanium, silicon, and / or tin, hydrolyzed with a metal alkoxide having an amino group. An aqueous solution containing a decomposition product, an aqueous solution of a silicate solution or a silicate, and one or more metal elements selected from aluminum, zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium, and yttrium An aqueous solution in which a salt is dissolved is simultaneously coated with an amino group-containing complex obtained by polycondensation and the surface is further coated with silica-based oxide or silica-based composite oxide. .

The average particle diameter of the titanium oxide-based composite particles is preferably 3 to 80 nm, more preferably 5 to 30 nm when measured by a dynamic light scattering method.
If the average particle size is less than 3 nm, the stability of the dispersion of the titanium oxide composite particles is not preferable. If the average particle diameter exceeds 80 nm, the transparency of the dispersion of the titanium oxide composite particles may be unfavorable.
The shape of the titanium oxide composite particles is not particularly limited, but is preferably rod-shaped, granular, or spherical.

The specific surface area of the titanium oxide composite particles measured by the BET method is preferably 80 to 400 m ² / g, more preferably 150 to 300 m ² / g.
If the specific surface area is less than 80 m ² / g, the dispersion of the titanium oxide composite particles or the transparency of the coating obtained using the dispersion may be unfavorable. On the other hand, when the specific surface area exceeds 400 m ² / g, the stability may decrease when the dispersion of the titanium oxide composite particles is concentrated, which is not preferable.

Titanium oxide composite particle dispersion The titanium oxide composite particle dispersion according to the present invention is a dispersion containing the titanium oxide composite particles in water and / or an organic solvent.
The organic solvent is not particularly limited, but is preferably water-soluble, such as methanol, ethanol, isopropyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl. Ether, ethylene glycol, methyl methacrylate, styrene, vinyl acetate, ε-caprolactam, undecane lactam, lauryl lactam, hexamethylenediamine, adipic acid, sebacic acid, dipentaerythritol hexaacrylate, neopentyl glycol acrylic acid benzoate, 1 , 6-hexanediol diacrylate, tricyclodecane dimethylol diacrylate, γ-butyrolactone, N-methylpyrrolidone, methyl Ruisobutyl ketone and methyl ethyl ketone can be preferably used.
The solid content concentration of the dispersion is preferably 1 to 40% by weight, more preferably 10 to 30% by weight. If the solid content concentration is less than 1% by weight, the amount of the inorganic substance contained in the dispersion is insufficient, and the expected effect may not be obtained. When the solid content concentration exceeds 40% by weight, the stability of the dispersion is lowered and gelation tends to occur, which is not preferable.

Method for Producing Dispersion of Titanium Oxide Composite Particles A method for producing a dispersion containing titanium oxide composite particles according to the present invention will be described below.
A method for producing core particles (core particles) made of titanium oxide fine particles or composite oxide fine particles is not particularly limited, and known ones can be used. Such a core particle is preferably in the form of a dispersion in terms of production and performance. Such a core particle dispersion is, for example, a method for preparing a core particle dispersion described in JP-A-2000-204301. It can be produced by the method for preparing a titanium oxide sol described in JP-A-10-182152.

Method for coating amino group-containing complex As a method for coating the core particle with the amino group-containing complex, at least an amino group is contained under stirring while heating the aqueous dispersion of the core particle. Any one selected from the group consisting of an aqueous solution containing a hydrolyzate of metal alkoxide, an aqueous solution of silicate or silicate, and aluminum, zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium, yttrium Alternatively, a method in which an aqueous solution in which two or more kinds of metal element salts are dissolved is added to the aqueous dispersion of the core particles little by little at the same time and polycondensed on the core particle surface is preferable.

At this time, it is selected from an aqueous solution containing a hydrolyzate of a metal alkoxide containing the amino group, an aqueous solution of silicic acid or silicate, and aluminum, zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium, and yttrium. The aqueous solution in which the salt of one or more elements is dissolved is preferably added separately to the aqueous dispersion of core particles without mixing. Moreover, when using 2 or more types of the said salt of a metal element, it is preferable not to mix the aqueous solution of 2 or more types of salts but to add each to the said aqueous dispersion simultaneously. This is to suppress precipitation and aggregation of components in the aqueous solution.

The heating temperature of the aqueous dispersion of the core particles is preferably in the range of 60 to 210 ° C.
When the heating temperature is less than 60 ° C., the aqueous dispersion cannot be gelled or aggregated or a uniform amino group-containing complex cannot be formed.
When the heating temperature exceeds 210 ° C., the amino group contained in the amino group-containing metal alkoxide is denatured or decomposed, and the expected effect cannot be obtained.

Further, an aqueous solution containing a hydrolyzate of a metal alkoxide containing an amino group while heating the aqueous dispersion of the core particles, a silicic acid solution or an aqueous solution of silicate, aluminum, zirconium, zinc, cerium, tin, While adding an aqueous solution in which a salt of at least one element selected from lanthanum, magnesium, calcium, and yttrium is dissolved to the core particle dispersion at the same time, the pH of the dispersion is in the range of 7-12. It is preferable to add so that it becomes. When the pH of the aqueous dispersion is less than 7 or greater than 12, the dispersion is gelled, which is not preferable.
The pH conditions of the above dispersion are adjusted so that the pH of the aqueous dispersion of core particles is in the range of pH 7 to 12 in advance using an alkali such as NaOH, KOH, NH ₄ OH as a pH adjuster. Can be satisfied. Since the raw material of the amino group-containing composite is a small amount compared to the aqueous dispersion of the core particles, if the aqueous dispersion of the core particles is on the alkali side, the pH of the dispersion during the amino group-containing composite coating is formed. Does not fluctuate significantly.
In addition, when an acidic silicate solution is used as a raw material for an amino group-containing complex, a metal element salt that is alkaline at the same time is used, or an alkaline silicate aqueous solution is used. Adjustments such as using a metal element salt that shows acidity in water can also be made as necessary.

  The addition rate when adding an aqueous solution containing a hydrolyzate of a metal alkoxide having an amino group to the aqueous dispersion of the core particles is 0 on a molar basis of the amino group possessed by the metal alkoxide contained in the aqueous solution. It is preferable to add 0.005 to 0.2 mol / Hr, more preferably 0.02 to 0.15 mol / Hr. When the addition rate is less than 0.005 mol / Hr, there is no particular problem with the properties of the resulting amino group-containing composite, but it is not preferable because it takes an unnecessarily long time for the production process. On the other hand, when the addition rate exceeds 0.2 mol / Hr, the components contained in the aqueous dispersion gel or aggregate, and a uniform amino group-containing complex cannot be obtained.

  The addition rate when adding an aqueous solution of silicic acid or silicate to the aqueous dispersion of the core particles is in the range of 0.012 to 0.5 mol / Hr based on the molar amount of silicon contained in the aqueous solution. It is preferable to add so that it becomes. When the addition rate is slower than 0.012 mol / Hr, there is no particular problem with the properties of the resulting amino group-containing composite, but the production time is unnecessarily long, and the addition rate is 0.5. If it exceeds mol / Hr, the components contained in the aqueous dispersion gel or aggregate, and a uniform amino group-containing complex cannot be obtained.

Also, an aqueous solution in which a salt of one or more metal elements selected from aluminum, zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium and yttrium is dissolved is added to the aqueous dispersion of the core particles. The addition rate at that time is 0.005 to 0.2 mol / Hr, more preferably 0.02 to 0.15 mol / Hr, based on the molar amount of the metal element contained in the aqueous solution. It is preferable. When the addition rate is lower than 0.005 mol / Hr, there is no particular problem with the properties of the resulting amino group-containing composite, but the production time is unnecessarily long, and the addition rate is 0.2. If it exceeds mol / Hr, the components contained in the aqueous dispersion gel or aggregate, and a uniform amino group-containing complex cannot be obtained.

Moreover, it is preferable that the density | concentration of the aqueous solution containing the hydrolyzate of the metal alkoxide which has the said amino group exists in the range of 0.2 to 20 weight% in conversion standard of the metal alkoxide which has an amino group. When the concentration of the aqueous solution is less than 0.2% by weight, the amount of the reaction solution increases and the productivity is deteriorated. On the other hand, when the concentration is more than 20% by weight, the dispersion is easily gelled, and a uniform amino group-containing complex cannot be obtained.
The concentration of the aqueous solution in which a salt of one or more metal elements selected from aluminum, zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium and yttrium is dissolved is an oxide conversion standard of the metal element _{(Al 2 O 3, ZrO 2} , ZnO, CeO 2, SnO 2, La 2 O 3, MgO, CaO, Y 2 O 3 equivalent value) is preferably no greater than 0.01 to 5% by weight. If the concentration exceeds 5% by weight, the dispersion is easily gelled, and a uniform amino group-containing complex cannot be obtained.

The concentration of the silicate solution or silicate aqueous solution is preferably in the range of 0.5 to 6% by weight in terms of SiO ₂ . When the concentration is less than 0.5% by weight, the amount of the reaction solution increases and the productivity is poor. On the other hand, if the concentration exceeds 6% by weight, the dispersion is easily gelled, and a uniform amino group-containing complex cannot be obtained.
The stirring speed of the aqueous dispersion varies depending on the apparatus to be used, but an aqueous solution containing a hydrolyzate of metal alkoxide having an amino group, an aqueous solution of silicate or silicate, aluminum, zirconium, zinc It is preferable to appropriately adjust the stirring speed so that an aqueous solution in which a salt of one or more metal elements selected from cerium, tin, lanthanum, magnesium, calcium and yttrium is dissolved is instantaneously mixed. .
Further, the coating amount of the amino group-containing complex with respect to the core particles is desirably adjusted by the charging amount so as to be in the range of 1 to 40, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the core particles. .

Coating method of silica-based oxide or silica-based composite oxide An aqueous dispersion of core particles coated with the amino group-containing composite obtained above was prepared in a solid content concentration range of 1 to 3% by weight. After heating to a temperature range of 80 ° C. to 95 ° C., (D) silicic acid solution, or (E) silicic acid solution and one selected from zirconium, antimony, tungsten, tin, aluminum, niobium, cerium and zinc Alternatively, an aqueous solution of two or more metal element hydroxides, peroxides, alkoxides and / or inorganic salts is gradually added, followed by aging for 0.5 to 2 hours after completion of the addition.
Next, after adjusting the pH of the obtained dispersion to pH 7 to 10 by ion exchange, if necessary, the dispersion is put in an autoclave and heated at a temperature of about 160 to 170 ° C. for about 16 to 20 hours. An aqueous dispersion of titanium oxide composite particles is obtained.

If necessary, the obtained aqueous dispersion of titanium oxide composite particles is concentrated by an ultrafiltration membrane device to obtain a titanium oxide composite particle dispersion having a solid content concentration of about 10 to 30% by weight.
Further, the coating amount of the silica-based oxide or the silica-based composite oxide is adjusted by the charged amount so as to be in the range of 0.5 to 30 parts by weight with respect to 100 parts by weight of the titanium oxide-based composite particles. It is preferable.
The inorganic salt of the metal element is not particularly limited, and examples thereof include nitrates, acetates, hydrochlorides, carbonates and sulfates of the metal elements.

Solvent replacement of dispersion of titanium oxide composite particles The aqueous dispersion of titanium oxide composite particles obtained above is subjected to a solvent replacement device as necessary, and the water contained in the aqueous dispersion is contained. Can be replaced with an organic solvent.
As the solvent displacement device, a rotary evaporator, an ultrafiltration membrane, or other known devices can be used. At this time, the water may not be completely removed, but water and an organic solvent may be mixed in the solvent.
In the solvent replacement step, it is desirable to add the organic solvent to the solvent replacement device so that the solid content concentration of the resulting titanium oxide composite particle dispersion is 1 to 40% by weight.

In order to prevent aggregation of the titanium oxide composite particles when dispersed in a solution in which an organic solvent or resin is dispersed, the surface of the titanium oxide composite particles is subjected to a hydrophobic treatment using a surface treatment agent as necessary. Also good.
This surface hydrophobization treatment is a step of adding a surface treatment agent to the dispersion and performing heating or hydrothermal treatment as necessary. Even if it is performed before the solvent replacement operation, it is performed simultaneously with the solvent replacement or after the solvent replacement. Also good. At this time, a catalyst such as ammonia may be used as necessary.

Examples of the surface modifier include alkoxide compounds such as tetraethoxysilane and triisopropoxyaluminum, coupling agents such as silane coupling agents or titanium coupling agents, non-ionic or cationic or anionic low molecular or high molecular weight compounds. Known compounds such as molecular surfactants, metal soap salts such as fatty acid metal salts or metal salts of naphthenic acid can be used.
As a method of using the aqueous dispersion and / or organic solvent dispersion of the titanium oxide composite particles thus obtained in the coating liquid for coating formation, or a method of blending into the resin composition, a conventionally known method is used in a timely manner. be able to.

[Measuring method]
Evaluation methods and measurement methods used in Examples and other examples of the present invention are shown below.
[1] Refractive index of titanium oxide composite particles (1) Methanol dispersion or ethylene glycol dispersion of titanium oxide composite particles was subjected to an evaporator to evaporate the dispersion medium, and then dried at 120 ° C to obtain a powder. .
(2) Next, a few drops of a standard refractive index having a known refractive index are dropped on a glass substrate, and a dry powder of the titanium oxide-based composite particles is mixed therewith to prepare a mixed solution.
The operation of (2) is performed using standard refractive index liquids having various refractive indexes, and the refractive index of the standard refractive index liquid when the mixed liquid becomes transparent is defined as the particle refractive index of the titanium oxide composite particles. .

[2] Light Resistance Evaluation of Titanium Oxide Composite Particles Pure water is added to 0.90 g of a methanol dispersion or ethylene glycol dispersion of titanium oxide composite particles having a solid content concentration of 20% by weight deionized with a cation exchange resin. 11.2 g and 5.9 g of methanol were mixed to prepare 18.0 g of a sample having a solid concentration of 1.0% by weight, which was sealed in a quartz cell having a length of 1 mm, a width of 1 cm and a height of 5 cm. Using an ultraviolet lamp (SLUV-6 manufactured by AS ONE) in which the wavelength range of the I-line (wavelength 365 nm) is selected, the quartz cell is irradiated at an irradiation distance of 5.5 cm to an irradiation intensity of 0.4 mW / cm ² (converted to wavelength 365 nm). ) For 60 minutes. The color change of the sample during exposure was visually evaluated based on the following criteria.
○: No blue discoloration in 60 minutes Δ: Blue discoloration starts in 30 minutes to less than 60 minutes ×: Blue discoloration starts in less than 30 minutes

[3] Evaluation of photocatalytic activity suppression effect of titanium oxide composite particles 9.34 g of pure water was mixed with 0.66 g of methanol dispersion or ethylene glycol dispersion (solid content 20% by weight) of titanium oxide composite particles. 9.70 g of a glycerin solution of sunset yellow dye having a solid content of 0.02% by weight is mixed with 0.33 g of the sample having a solid content of 6.6% by weight. Next, this is put into a quartz cell having a length of 1 mm, a width of 1 cm, and a height of 5 cm. Next, using an ultraviolet lamp (SLUV-6 manufactured by AS ONE) in which the wavelength range of I-line (wavelength 365 nm) is selected, the quartz cell is irradiated with an irradiation distance of 5.5 m to an irradiation intensity of 0.4 mW / cm ² (wavelength). Irradiation with ultraviolet rays for 3 hours at a conversion of 365 nm. On the other hand, before and after ultraviolet irradiation, the absorbance (A ₀ and A ₃ ) of the sample at a wavelength of 490 nm was measured with an ultraviolet-visible light spectrophotometer (manufactured by JASCO, V-550). Calculate the rate of change.
Fading change rate (%) = A ₃ / A ₀ × 100

Furthermore, the photocatalytic activity of the particles is evaluated based on the following criteria. Here, the lower the fading change rate, the more the photocatalytic activity is suppressed.
○: Fading change rate is less than 20% △: Fading change rate is 20% or more and less than 50% ×: Fading change rate is 50% or more

[4] Weather resistance evaluation of titanium oxide composite particles 276.1 parts by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by Dow Corning Toray Co., Ltd., Z-6040) and 138.1 parts by weight of methanol were added. While maintaining the temperature of the reaction vessel at 10 ° C., 64.2 parts by weight of 0.01N HCl aqueous solution was gradually added dropwise with stirring. Further, this mixed solution was stirred for a whole day and night to hydrolyze γ-glycidoxypropyltrimethoxysilane to obtain a matrix forming component.
To the liquid containing the matrix-forming component, 1173.4 parts by weight of a methanol dispersion of titanium oxide composite particles having a solid content concentration of 20% by weight was added, and aluminum acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.03 parts by weight. Part and a leveling agent (L-7001, manufactured by Toray Dow Corning Co., Ltd.) were added, and the liquid was stirred and mixed well for a whole day to obtain a coating liquid for forming a hard coat film.
Next, a resin lens base material (Mitsui Chemicals, Inc .: MR-7 refractive index 1.67) was immersed in a 13% NaOH aqueous solution at 47 ° C. for several minutes and then sufficiently washed with water.
Next, the substrate was immersed in the coating solution, then pulled up at a pulling rate of 250 mm / min, dried at 90 ° C. for 10 minutes, and heat-cured at 110 ° C. for 2 hours to form a hard coat film.

The obtained base material with a hard coat film is subjected to an exposure acceleration test for 100 hours using a xenon weather meter (X-75, manufactured by Suga Test Instruments Co., Ltd.), and then an adhesion test is performed. In the adhesion test, eleven parallel scratches were made on the surface of the substrate with a knife at intervals of 1 mm each in length and width before exposure to make 100 squares, and after the accelerated exposure test, cellophane tape was applied to this. When the cellophane tape was peeled off after the adhesion, the film adhesion was evaluated based on the degree of the cells remaining without peeling off the coating. The evaluation criteria are as follows.
○: The number of remaining squares is 100/100 to 71/100
Δ: Number of remaining squares is 70/100 to 31/100
X: The number of remaining squares is 30/100 to 0/100

[5] Evaluation of acid resistance stability of titanium oxide-based composite particles 50 ml of methanol dispersion or ethylene glycol dispersion (solid concentration 20% by weight) of titanium oxide-based composite particles is weighed so that the solids concentration becomes 1% by weight. Dilute with methanol. The obtained solution is put into a transparent screw tube, a stirrer is added, and 0.1 g of 12% strength hydrochloric acid is added while stirring with a magnetic stirrer. Immediately after the addition, the transmittance when left in a room at room temperature for 1 hour and 1 day was measured by the method [6] below, and evaluated according to the following criteria.
○: Transmittance of 60% or more Δ: Transmittance of 30% or more and less than 60% ×: Transmittance of less than 30%

[6] Evaluation of Titanium Oxide Composite Particle Permeability The methanol dispersion or ethylene glycol dispersion (solid content concentration 20% by weight) of titanium oxide composite particles is diluted with pure water so that the solid content concentration becomes 5% by weight. After that, it was put in a quartz cell having a thickness of 10 mm, and the transmittance was measured by a transmittance measuring device (manufactured by JASCO Corporation: V-550, wavelength 550 nm).

[7] Average particle size measuring method Using a fine particle size measuring device by dynamic light scattering (Honeywell, Microtrac UPA), an aqueous dispersion of particles having a solid content concentration of 20% by weight, or a methanol dispersion, Alternatively, 7.0 g of an ethylene glycol dispersion was sampled and the particle size distribution was measured. The particle shape was spherical, the particle refractive index and particle density were the intrinsic values of each particle, and the solution refractive index was the theoretical refractive index of the solvent. The particle diameter value at a number frequency of 50% in the obtained particle size distribution measurement result was defined as the average particle diameter of the particles.

[8] Specific surface area of titanium oxide-based composite particles About 30 ml of dry powder of aqueous dispersion of titanium oxide-based composite particles is collected in a magnetic crucible (type B-2), dried at a temperature of 300 ° C. for 2 hours, and then used as a desiccator. Allow to cool to room temperature. Then the measurement sample was 1g collected, fully automatic surface area measuring device (manufactured by Yuasa Ionics Inc., Multisorb 12 type) with a ratio surface area (m ² / g) was measured by the BET method.

[9] Method for Measuring Titanium Content of Core Particles An aqueous dispersion of core particles was collected in zirconia balls, dried and fired, and then melted by adding Na ₂ O and NaOH. Furthermore, dissolved in H ₂ SO ₄ and HCl, diluted with pure water, ICP apparatus (Shimadzu Corp., ICPS-8100) was used to determine the content of titanium in terms of TiO ₂ standards.

[10] Crystal form of core particles About 30 ml of an aqueous dispersion of core particles is collected in a magnetic crucible (type B-2), dried at 110 ° C. for 12 hours, then placed in a desiccator and cooled to room temperature. Next, after grinding for 15 minutes in a mortar, the crystal form was measured using an X-ray diffractometer (RINT 1400, manufactured by Rigaku Corporation).

Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the scope described in these examples.

Preparation of Composite Oxide Fine Particles (Core Particles) Containing Titanium and Silicon 92.3 kg of an aqueous solution of titanium tetrachloride (manufactured by Sumitomo Titanium Co., Ltd.) having a concentration of 7.75 wt% in terms of TiO ₂ and a concentration of 15 wt. % Aqueous ammonia was mixed and neutralized, and then washed with pure water to obtain 53.8 kg of a hydrous titanate cake.
Next, after adding 6.2 kg of hydrogen peroxide water (hydrogen peroxide concentration: 35% by weight, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 13.6 kg of water to 5.52 kg of this hydrous titanate cake, 80 ° C. Was heated for 5 hours to obtain 25.3 kg of an aqueous solution of titanic acid peroxide having a TiO ₂ concentration of 2.0% by weight. This aqueous solution of titanic acid peroxide was transparent yellowish brown and had a pH of 8.1.

Then, silica sol having an average particle diameter measured by a dynamic light scattering method comprising 10nm of the silica fine particles are dispersed in water (SiO ₂ concentration of 15 wt% silica sol, JGC manufactured by Shokubai Kasei Co.) and 770 g, the 23.1 kg of an aqueous peroxide titanate solution and 28.0 kg of pure water were mixed and heated in an autoclave (manufactured by Ryoka Seisakusho) at 170 ° C. for 20 hours. As a result, an aqueous dispersion of composite oxide fine particles (core particles) containing titanium and silicon was obtained.
Subsequently, the obtained aqueous dispersion of core particles is concentrated by an ultrafiltration membrane device, and an aqueous dispersion of composite oxide fine particles (core particles) containing titanium and silicon having a solid content concentration of 10% by weight is 5.4 kg. Was prepared.

The appearance of this aqueous dispersion is transparent, pale blue-white, and the average particle diameter measured by the dynamic light scattering method of the composite oxide fine particles (core particles) containing titanium and silicon contained in the dispersion is 11 nm. Met. Further, when the complex oxide fine particles (nuclear particles) containing titanium and silicon were measured by the X-ray diffraction method, the crystal structure was anatase type.
The titanium content in 5.0 kg of the aqueous dispersion of composite oxide fine particles (core particles) containing titanium and silicon obtained above was 410 g (5.13 mol) in terms of TiO ₂ .

Method for coating amino group-containing composites 5.0 kg of pure water was mixed with 5.0 kg of the aqueous dispersion of the composite oxide fine particles (core particles) containing titanium and silicon obtained above, and 1% The pH was adjusted to 10.5 with an aqueous NaOH solution and heated to 80 ° C. While stirring this solution, 250 g of a 1.5 wt% sodium silicate aqueous solution and 250 g of a 2.2 wt% γ-aminopropyltriethoxysilane (molecular weight 221.4) aqueous solution (γ-amino) in terms of SiO ₂ propyltriethoxysilane 0.025 mol) and Al ₂ O ₃ equivalent value of 0.5 wt% sodium aluminate aqueous solution 500 g, was continuously added in portions over 30 minutes, respectively (at a constant rate) at the same time . Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.7 immediately after the addition and hardly changed thereafter. After completion of the addition, the reaction solution is cooled to room temperature, the liquid level is maintained using an ultrafiltration membrane apparatus, and pure water is continuously added, and when the pH reaches 10, the amino group is contained. An aqueous dispersion of core particles (solid content concentration 10% by weight) coated with the composite was obtained.

Method for coating silica-based oxide
<Preparation of silicic acid solution>
After diluting 1.7 kg of commercially available water glass (No. 3 water glass, AGC S-Tech Co., Ltd.) with pure water, it is dealkalized using a cation exchange resin (Mitsubishi Chemical Corporation), and SiO 2 _2. 22.9 kg of silicic acid solution having a concentration of 2% by weight was prepared. The pH of this aqueous silicic acid solution was 2.3.

<Preparation of titanium oxide composite particles>
To 5.0 kg of the aqueous dispersion of core particles coated with the amino group-containing complex prepared above, 20.0 kg of pure water and 16 g of 5% NaOH aqueous solution are added to adjust the solid content concentration to 2 wt%, Heated to 90 ° C. To this was added 3.13 kg of the above silicic acid solution (SiO ₂ concentration 2 wt%) (the coating amount with respect to 100 g of the solid content of the titanium oxide composite particles was 11.1 g in terms of SiO ₂ conversion) to prepare a mixed solution. .
Next, the mixed solution was put in an autoclave and subjected to heat treatment at a temperature of 170 ° C. for 18 hours. As a result, an aqueous dispersion of titanium oxide composite particles coated with a silica-based oxide was obtained after the core particles were coated with the amino group-containing composite.

Next, the obtained aqueous dispersion of titanium oxide composite particles was concentrated with an ultrafiltration membrane device to prepare 5.8 kg of an aqueous dispersion of titanium oxide composite particles having a solid content concentration of 10% by weight. The appearance of this aqueous dispersion is pale blue-white, and the average particle diameter measured by the dynamic light scattering method of the titanium oxide composite particles dispersed in the aqueous dispersion is 13 nm, and measured by the BET method. The specific surface area was 200 m ² / g.
After adding 75.0 g of a cation exchange resin (Mitsubishi Chemical Corporation) to 3.0 kg of the aqueous dispersion of the titanium oxide composite particles, the cation exchange resin is separated and removed, and cation exchange is performed. An aqueous dispersion (solid content concentration: 10% by weight) of the treated titanium oxide composite particles was obtained.

Next, the obtained aqueous dispersion of titanium oxide composite particles was cooled to room temperature. Next, 2.4 kg of methanol was mixed with 2.4 kg of this aqueous dispersion, 180 g of tetraethoxysilane was added as a surface modifier, and the mixture was heated for 2 hours while maintaining a temperature of 60 ° C. Then, using an ultrafiltration device, the dispersion medium is replaced by methanol, and the methanol dispersion 1 of titanium oxide composite particles in which titanium oxide composite particles having a solid content concentration of 20% by weight are dispersed in methanol. 4 kg was prepared. The appearance of this liquid composition was transparent pale blue white, and the average particle diameter of the titanium oxide composite particles contained in the methanol dispersion was 13 nm.
When the number of moles of titanium contained in the composite oxide fine particles containing titanium and silicon is represented by A, and the number of moles of amino groups contained in the amino group-containing composite is represented by B, the mole ratio (B / A ) Was 0.0048.

In the coating step of the amino group-containing complex shown in Example 1, the same method as in Example 1 except that the concentration of the γ-aminopropyltriethoxysilane aqueous solution used was changed from 2.2% to 4.4%. Thus, an aqueous dispersion and a methanol dispersion of titanium oxide composite particles were prepared. Moreover, the average particle diameter measured by the dynamic light scattering method of the titanium oxide-based composite particles was 13 nm, and the specific surface area measured by the BET method was 210 m ² / g.
When the number of moles of titanium contained in the composite oxide fine particles containing titanium and silicon is represented by A, and the number of moles of amino groups contained in the amino group-containing composite is represented by B, the mole ratio (B / A ) Was 0.0096.

In the coating step of the amino group-containing complex shown in Example 1, the same method as in Example 1 except that the concentration of the γ-aminopropyltriethoxysilane aqueous solution used was changed from 2.2% to 6.6%. Thus, an aqueous dispersion and a methanol dispersion of titanium oxide composite particles were prepared. Moreover, the average particle diameter measured by the dynamic light scattering method of the titanium oxide-based composite particles was 13 nm, and the specific surface area measured by the BET method was 220 m ² / g.
When the number of moles of titanium contained in the composite oxide fine particles containing titanium and silicon is represented by A and the number of moles of amino groups contained in the amino group-containing composite is represented by B, the mole ratio (B / A ) Was 0.0144.

In the coating step of the amino group-containing complex shown in Example 1, the concentration of the γ-aminopropyltriethoxysilane aqueous solution used was changed from 2.2% to 6.6%, and the silica-based oxide coating step was used. An aqueous dispersion and a methanol dispersion of titanium oxide composite particles were prepared in the same manner as in Example 1 except that the silicic acid solution (concentration of 2% by weight) was changed from 3.13 kg to 2.0 kg. Moreover, the average particle diameter measured by the dynamic light scattering method of the titanium oxide-based composite particles was 13 nm, and the specific surface area measured by the BET method was 231 m ² / g.
When the number of moles of titanium contained in the composite oxide fine particles containing titanium and silicon is represented by A, and the number of moles of amino groups contained in the amino group-containing composite is represented by B, the mole ratio (B / A ) Was 0.0144.

In the coating step of the amino group-containing composite of Example 1, the concentration of the γ-aminopropyltriethoxysilane aqueous solution was changed from 2.2% to 6.6%, and 0.5% by weight on the basis of Al ₂ O ₃ conversion. The same method as in Example 1 except that instead of using the sodium aluminate aqueous solution 500, 515 g of a 0.9 wt% zirconylammonium carbonate {(NH ₄ ) ₂ ZrO (CO ₃ ) ₂ } aqueous solution in terms of ZrO ₂ was used. Thus, an aqueous dispersion (solid content concentration of 10% by weight) of titanium oxide composite particles and a methanol dispersion were obtained.
When the number of moles of titanium contained in the composite oxide fine particles containing titanium and silicon is represented by A, and the number of moles of amino groups contained in the amino group-containing composite is represented by B, the mole ratio (B / A ) Was 0.0144.

In the coating step of the amino group-containing composite of Example 1, the titanium oxide system was the same as in Example 1 except that the concentration of the γ-aminopropyltriethoxysilane aqueous solution was changed from 2.2% to 6.6%. An aqueous dispersion of composite particles (solid content concentration 10% by weight) was obtained.
Next, 2.2 kg of ethylene glycol was added to 3.0 kg of the aqueous dispersion of the titanium oxide composite particles, and the dispersion medium was replaced with water by using a rotary evaporator. The solid content concentration was 12% by weight. Then, 2.5 kg of an ethylene glycol dispersion obtained by dispersing titanium oxide composite particles in ethylene glycol was prepared. The appearance of this liquid composition was transparent light blue white, and the average particle diameter of the titanium oxide composite particles contained in the ethylene glycol dispersion was 13 nm.
Further, when the mole number of titanium contained in the composite oxide fine particles containing titanium and silicon is represented by A, and the mole number of amino groups contained in the amino group-containing composite is represented by B, the mole ratio (B / A) was 0.0144.

Preparation of composite oxide fine particles (core particles) containing titanium, silicon and tin 93.7 kg of titanium tetrachloride aqueous solution containing 7.75% by weight of titanium tetrachloride (produced by Osaka Titanium Technologies Co., Ltd.) in terms of TiO ₂ , A white slurry liquid having a pH of 9.5 was prepared by mixing 36.3 kg of ammonia water containing 15% by weight of ammonia (manufactured by Ube Industries).
Next, the slurry was filtered and then washed with pure water (manufactured by JGC Catalysts & Chemicals Co., Ltd.) to obtain 72.6 kg of a hydrous titanate cake having a solid content of 10% by weight.
Next, 83.0 kg of hydrogen peroxide containing 35% by weight of hydrogen peroxide (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 411.4 kg of pure water are added to the cake, and then at a temperature of 80 ° C. for 1 hour. The mixture was heated under stirring, and 159 kg of pure water was further added to obtain 726 kg of an aqueous solution of titanic acid peroxide containing 1% by weight of titanic acid peroxide on a TiO ₂ basis. This aqueous solution of titanic acid peroxide was transparent yellowish brown and had a pH of 8.5.

Subsequently, 3.5 kg of cation exchange resin was mixed with 72.9 kg of the aqueous solution of titanic acid peroxide, and stannic acid containing 1% by weight of potassium stannate (manufactured by Showa Kako Co., Ltd.) on the basis of SnO ₂ conversion. 9.11 kg of aqueous potassium solution was gradually added with stirring.
Next, a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) incorporating potassium ions and the like is separated, and then a silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd.) 1 containing 15% by weight of silica fine particles having an average particle diameter of 7 nm. .2 kg and 18.0 kg of pure water are mixed and heated in an autoclave (pressure-resistant glass industry, 120 L) at a temperature of 165 ° C. for 18 hours, thereby complex oxidation containing titanium, silicon and tin An aqueous dispersion of fine particles was obtained.

Next, after cooling the obtained aqueous dispersion to room temperature, it is concentrated with an ultrafiltration membrane device (ACV-3010, manufactured by Asahi Kasei Co., Ltd.), and an aqueous dispersion having a solid content of 10% by weight. 10.0 kg was obtained.
When the crystal form of the composite oxide fine particles containing titanium, silicon and tin contained in the aqueous dispersion thus obtained was measured by the above method, the composite oxide fine particles having a rutile crystal structure were found. It was.
The appearance of the aqueous dispersion was transparent, pale blue-white, and the average particle diameter of the composite oxide fine particles containing titanium, silicon, and tin contained in the dispersion was 16 nm.
The titanium content contained in 1 kg of the composite oxide fine particle aqueous dispersion obtained above was 73.7 g (0.922 mol).

Next, instead of 5.0 kg of the aqueous dispersion of composite oxide particles containing titanium and silicon prepared in Example 1, 5.0 kg of the aqueous dispersion of composite oxide particles containing titanium, silicon and tin prepared above. The amino group-containing composite containing silica, aluminum and the surface of the composite oxide fine particle containing titanium, silicon and tin is the same as the coating method of the amino group-containing composite described in Example 1 except that Coated with.
Next, a silica-based composite oxide was further coated on the surface of the amino group-containing composite by the following method.

Method for coating silica-based composite oxide
<Preparation of aqueous zirconate peroxide solution>
5.6 kg of zirconium oxychloride (manufactured by Taiyo Mining Co., Ltd.) was dissolved in 10.0 kg of pure water to prepare a zirconium oxychloride aqueous solution having a ZrO ₂ concentration of 2.0 wt%. An aqueous ammonia solution (concentration: 15% by weight) was added to this aqueous zirconium oxychloride solution and hydrolyzed to obtain a slurry having a pH of 8.5.
This slurry was washed by filtration to obtain a cake having a ZrO ₂ concentration of 10.0% by weight. Then, 3.6 kg of pure water is added to 1.4 kg of this cake, and 0.27 kg of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.) having a KOH purity of 86% by weight is added to make it alkaline. .6 kg (H ₂ O ₂ concentration 35% by weight) was added and dissolved by heating at a temperature of 50 ° C. to prepare 7.2 kg of an aqueous zirconate peroxide solution having a concentration of 2% by weight as ZrO ₂ .

<Preparation of titanium oxide composite particles>
25.0 kg of pure water was added to 5.0 kg of an aqueous dispersion of core particles coated with an amino group-containing composite containing silicon and aluminum prepared as described above to adjust the solid content concentration to 2% by weight, and a temperature of 90 Heated to ° C. To this was added 1.70 kg of the aqueous zirconate peroxide solution (ZrO ₂ concentration 2 wt%) prepared above and 1.33 kg of the silicic acid solution (SiO ₂ concentration 2 wt%) prepared by the method described in Example 1. The mixed solution was heated at 90 ° C. for 1 hour.
Next, the mixed solution was put in an autoclave and subjected to heat treatment at a temperature of 170 ° C. for 18 hours. As a result, an aqueous dispersion of titanium oxide composite particles coated with a silica-based composite oxide containing silicon and zirconium after the core particles were coated with the amino group-containing composite was obtained.

Next, the obtained aqueous dispersion of titanium oxide composite particles was concentrated with an ultrafiltration membrane device to prepare 5.8 kg of an aqueous dispersion of titanium oxide composite particles having a solid content concentration of 10% by weight. The appearance of this aqueous dispersion is pale blue white, and the average particle diameter measured by the dynamic light scattering method of the titanium oxide composite particles dispersed in the aqueous dispersion is 17 nm, and measured by the BET method. The specific surface area was 200 m ² / g.
Next, the obtained aqueous dispersion of titanium oxide composite particles was concentrated with an ultrafiltration membrane device to prepare an aqueous dispersion of titanium oxide composite particles having a solid content concentration of 10% by weight.

After adding 75.0 g of a cation exchange resin (Mitsubishi Chemical Corporation) to 3.0 kg of the aqueous dispersion of the titanium oxide composite particles, the cation exchange resin is separated and removed, and cation exchange is performed. An aqueous dispersion (solid content concentration: 10% by weight) of the treated titanium oxide composite particles was obtained.
Next, the obtained aqueous dispersion of titanium oxide composite particles was cooled to room temperature. Next, 2.4 kg of methanol was mixed with 2.4 kg of this aqueous dispersion, 180 g of tetraethoxysilane was added as a surface modifier, and the mixture was heated with stirring for 2 hours while maintaining a temperature of 60 ° C. Then, using an ultrafiltration device, the dispersion medium is replaced by methanol, and the methanol dispersion 1 of titanium oxide composite particles in which titanium oxide composite particles having a solid content concentration of 20% by weight are dispersed in methanol. 4 kg was prepared. The appearance of this liquid composition was transparent pale blue white, and the average particle diameter of the titanium oxide composite particles contained in the methanol dispersion was 17 nm.

When the mole number of titanium contained in the composite oxide fine particles containing titanium, silicon and tin is represented by A, and the mole number of amino groups contained in the amino group-containing composite is represented by B, the mole ratio (B / A) was 0.0054.
The average particle diameter of the titanium oxide composite particles measured by the dynamic light scattering method was 17 nm, and the specific surface area measured by the BET method was 221 m ² / g.

Except that 1.70 kg of the aqueous zirconate peroxide solution (ZrO ₂ concentration 2% by weight) prepared in Example 7 was changed to 0.5 kg, and 1.33 kg of the silicic acid solution (SiO ₂ concentration 2% by weight) was changed to 1.50 kg. In the same manner as described in Example 7, the composite oxide fine particles containing titanium, silicon and tin were coated with the amino group-containing composite containing silicon and aluminum, and then the silica-based composite oxidation containing silicon and zirconium. An aqueous dispersion and a methanol dispersion of titanium oxide composite particles coated with the product were prepared.
The average particle diameter measured by the dynamic light scattering method of the titanium oxide composite particles dispersed in the aqueous dispersion of the titanium oxide composite particles is 17 nm, and the specific surface area measured by the BET method is 225 m ₂ / g. there were.
When the mole number of titanium contained in the composite oxide fine particles containing titanium, silicon and tin is represented by A, and the mole number of amino groups contained in the titanium oxide composite particles is represented by B, the mole ratio (B / A) was 0.0054.

In the coating step of the amino group-containing complex shown in Example 1, N-β (aminoethyl) γ-aminopropyl at 6.6% concentration was used instead of 250 g of 2.2% strength γ-aminopropyltriethoxysilane aqueous solution. An aqueous dispersion and a methanol dispersion of titanium oxide composite particles in the same manner as in Example 1, except that 250 g of an aqueous solution of trimethoxysilane (molecular weight 222 of N-β (aminoethyl) γ-aminopropyltrimethoxysilane) was used. Was prepared. Moreover, the average particle diameter measured by the dynamic light scattering method of the titanium oxide-based composite particles was 13 nm, and the specific surface area measured by the BET method was 223 m ² / g.
When the number of moles of titanium contained in the composite oxide fine particles containing titanium and silicon is represented by A, and the number of moles of amino groups contained in the amino group-containing composite is represented by B, the mole ratio (B / A ) Was 0.0144.

Comparative Example 1

2.4 kg of methanol is mixed with 2.4 kg of the aqueous dispersion (solid content concentration: 10% by weight) of the composite oxide fine particles containing titanium and silicon prepared in Example 1, and 180 g of tetraethoxysilane is added as a surface modifier. After the addition, the mixture was heated for 2 hours while maintaining the temperature at 60 ° C.
Then, using an ultrafiltration membrane device, the dispersion medium was replaced from water to methanol, and a methanol dispersion of core particles having a solid content concentration of 20% by weight was obtained. The appearance of this dispersion was transparent light blue white, and the average particle diameter of the composite oxide fine particles containing titanium and silicon contained in the methanol was 13 nm.

Comparative Example 2

20.0 kg of pure water was added to 5.0 kg of the aqueous dispersion of composite oxide fine particles containing titanium and silicon prepared in Example 1 to adjust the solid content concentration to 2.0 wt%, and the temperature was 90 ° C. Heated.
To this, 3.13 kg of the silicic acid solution (SiO ₂ concentration 2.0 wt%) prepared in Example 1 was added to prepare a mixed solution.

Next, the mixed solution was put in an autoclave and subjected to heat treatment at a temperature of 170 ° C. for 18 hours. As a result, an aqueous dispersion of inorganic oxide particles obtained by coating the surface of the composite oxide fine particles containing titanium and silicon with a silica-based oxide was obtained. Subsequently, the obtained aqueous dispersion was concentrated by an ultrafiltration membrane device to obtain an aqueous dispersion of inorganic oxide particles having a solid content concentration of 10% by weight. Next, 2.4 kg of methanol was mixed with 2.4 kg of this aqueous dispersion, 180 g of tetraethoxysilane was added as a surface modifier, and the mixture was heated for 2 hours while maintaining a temperature of 60 ° C.
Then, using an ultrafiltration membrane device, the dispersion medium was replaced with water by methanol, and a methanol dispersion of inorganic oxide particles having a solid content concentration of 20% by weight was obtained. The appearance of this dispersion was transparent light blue white, and the average particle diameter of the inorganic oxide particles contained in the methanol was 13 nm.

Comparative Example 3

After 5.0 kg of the aqueous dispersion (solid content concentration: 10% by weight) of the composite oxide fine particles containing titanium and silicon prepared in Example 1 was deionized using a cation exchange resin, γ-aminopropyltriethoxy was obtained. After adding 5.5 g of silane to 244.5 g of dissolved methanol, the mixture was heated at a temperature of 50 ° C. for 3 hours.
Next, this aqueous dispersion was cooled to room temperature, and then the dispersion medium was replaced from water to methanol using an ultrafiltration membrane device.

Further, the obtained methanol dispersion was concentrated with an ultrafiltration membrane device, and 3.0 kg of a methanol dispersion of surface-treated particles obtained by surface-treating composite oxide fine particles containing titanium and silicon with γ-aminopropyltriethoxysilane. (Solid content concentration 10% by weight) was prepared.
When the number of moles of titanium contained in the composite oxide fine particles containing titanium and silicon is represented by A and the number of moles of amino groups used for the surface treatment is represented by B, the mole ratio (B / A) is 0. .0048.

Comparative Example 4

5.0 kg of pure water in 5.0 kg (containing 5.13 moles of titanium as TiO ₂ ) of an aqueous dispersion of composite oxide fine particles (core particles) containing titanium and silicon prepared by the method described in Example 1 Were adjusted to pH 10.5 with 1% NaOH aqueous solution and heated to 80 ° C. While stirring this solution, 250 g of a 1.5 wt% sodium silicate aqueous solution on the basis of SiO ₂ and 500 g of a 0.5 wt% sodium aluminate aqueous solution on the basis of Al ₂ O ₃ were slightly added simultaneously over 30 minutes. Sequentially added. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.7 immediately after the addition and hardly changed thereafter. After completion of the addition, the reaction solution is cooled to room temperature, kept at the liquid surface using an ultrafiltration membrane device, continuously added with pure water, and concentrated to pH 10 to obtain silicon and aluminum. An aqueous dispersion of the core particles coated with the composite oxide containing (solid content concentration of 10% by weight) was obtained.

20.0 kg of pure water was added to 5.0 kg of an aqueous dispersion of the core particles coated with a composite oxide containing silicon and aluminum (solid content 10 wt%) to adjust the solid content concentration to 2 wt%. And heated to 90 ° C. To this, 0.5 kg of an aqueous zirconate peroxide solution (ZrO ₂ concentration 2 wt%) prepared in Example 6 and 1.5 kg of the silicic acid solution (SiO ₂ concentration 2 wt%) prepared in Example 1 were added. A mixed solution was prepared. Next, the mixed solution was put in an autoclave and subjected to heat treatment at a temperature of 170 ° C. for 18 hours. As a result, the surface of the composite oxide fine particles (core particles) containing titanium and silicon is coated with a composite oxide containing aluminum and silicon, and further coated with a silica-based composite oxide containing silicon and zirconium. An aqueous dispersion of inorganic oxide particles was obtained. Next, the obtained aqueous dispersion of inorganic oxide particles was concentrated with an ultrafiltration membrane device to prepare 5.4 kg of an aqueous dispersion of inorganic oxide particles having a solid content concentration of 10% by weight. The appearance of this aqueous dispersion is pale blue white, the average particle diameter of the inorganic oxide particles dispersed in the aqueous dispersion measured by the dynamic light scattering method is 13 nm, and the specific surface area measured by the BET method is 200 m. ² / g.

A cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was added to 3.0 kg of the aqueous dispersion of inorganic oxide particles obtained above (225 g on a TiO ₂ basis, that is, containing 2.82 moles of titanium). After adding 0 g and stirring, the cation exchange resin was separated and removed to obtain an aqueous dispersion of the inorganic oxide particles subjected to the cation exchange treatment. After adding 150 g (γ-aminopropyltriethoxysilane: 0.015 mol) of an aqueous solution of 2.2% γ-aminopropyltriethoxysilane (molecular weight 221.4) to 3.0 kg of this solution, a temperature of 50 ° C. For 3 hours.
Next, this aqueous dispersion was cooled to room temperature, and then the dispersion medium was replaced from water to methanol using an ultrafiltration membrane device.

Further, the obtained methanol dispersion is concentrated with an ultrafiltration membrane device, and the composite oxide fine particles (core particles) containing titanium and silicon are coated with the composite oxide containing silicon and aluminum, and the surface thereof is further covered. 1.4 kg of methanol dispersion of surface-treated inorganic oxide particles obtained by surface-treating inorganic oxide particles coated with a composite oxide containing silicon and zirconium with γ-aminopropyltriethoxysilane (solid content concentration 20% by weight) Was prepared. The average particle diameter of the surface-modified inorganic oxide particles contained in the methanol dispersion was 13 nm.
When the number of moles of titanium contained in the composite oxide fine particles containing titanium and silicon is represented by A and the number of moles of amino groups used for the surface treatment is represented by B, the mole ratio (B / A) is 0. .0053.

Comparative Example 5

In the coating step of the amino group-containing complex shown in Example 1, the same method as in Example 1 except that the concentration of the γ-aminopropyltriethoxysilane aqueous solution used was changed from 2.2% to 6.6%. To obtain an aqueous dispersion of the core particles coated with the amino group-containing complex (solid content concentration 10% by weight).
Next, 2.4 kg of methanol was mixed with 2.4 kg of this aqueous dispersion, 180 g of tetraethoxysilane was added as a surface modifier, and the mixture was heated for 2 hours while maintaining a temperature of 60 ° C. Then, using an ultrafiltration membrane device, the dispersion medium was replaced with water to methanol to obtain a methanol dispersion of core particles coated with an amino group-containing complex having a solid content concentration of 20% by weight. The external appearance of this dispersion was transparent light blue white, and the average particle diameter of the core particles coated with the amino group-containing complex contained in methanol was 17 nm.

Comparative Example 6

In the coating step of the amino group-containing complex shown in Example 1, except that the concentration of the γ-aminopropyltriethoxysilane aqueous solution used was changed from 2.2% to 42%, the same method as in Example 1, An aqueous dispersion and a methanol dispersion of titanium oxide composite particles were prepared. The average particle diameter of the titanium oxide composite particles measured by the dynamic light scattering method was 13 nm, and the specific surface area measured by the BET method was 215 m ² / g.
When the number of moles of titanium contained in the composite oxide fine particles containing titanium and silicon is represented by A, and the number of moles of amino groups contained in the amino group-containing composite is represented by B, the mole ratio (B / A) Was 0.09.

Comparative Example 7

In the step of coating methods of the amino group-containing composite of Example 1, an aqueous sodium silicate solution of 1.5 wt% in terms of SiO ₂ based 250g and 2.2% concentrations of γ- aminopropyltriethoxysilane (molecular weight 221. 4) When 250 g of an aqueous solution (γ-aminopropyltriethoxysilane: 0.025 mol) and 500 g of a 0.5 wt% sodium aluminate aqueous solution are added simultaneously at a constant rate over 2 minutes in terms of Al ₂ O ₃ The mixed solution gelled.

For the aqueous dispersions, methanol dispersions or ethylene glycol dispersions of the particles of Examples 1 to 9 and Comparative Examples 1 to 6 thus obtained, the refractive index, light resistance, The photocatalytic activity inhibitory effect, weather resistance, acid stability, and transmittance were evaluated. The results are shown in Table 1. However, the weather resistance evaluation was not performed for the ethylene glycol dispersion liquid of the titanium oxide composite particles of Example 6. Further, Comparative Example 7 was not evaluated because the dispersion was gelled. In Table 1, TE0S represents tetraethoxysilane, γ-APTS represents γ-aminopropyltriethoxysilane, and N-AEγ represents N-β (aminoethyl) γ-aminopropyltrimethoxysilane.

Claims (12)

  An aqueous solution containing at least a hydrolyzate of a metal alkoxide having an amino group on the surface of a core particle made of titanium oxide fine particles or composite oxide fine particles containing titanium and silicon and / or tin, and a silicic acid solution Alternatively, an aqueous solution of silicate and an aqueous solution in which a salt of one or more metal elements selected from aluminum, zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium and yttrium are dissolved are added simultaneously. A dispersion of titanium oxide-based composite particles, which is coated with an amino group-containing composite obtained by polycondensation and further coated with a silica-based oxide or a silica-based composite oxide.   When the number of moles of titanium contained in the core particles is represented by A and the number of moles of amino groups contained in the amino group-containing complex is represented by B, the mole ratio (B / A) is 0.001 to 0. The dispersion of titanium oxide composite particles according to claim 1, wherein the dispersion is in the range of 0.04.   The metal alkoxide having an amino group is γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-amino. Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyl It is one or more selected from trimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-phenylaminopropyltrimethoxysilane. Claim 1 or Claim 2 Dispersion of titanium oxide-based composite particles.   4. The titanium oxide composite according to claim 1, wherein an average particle diameter of the titanium oxide composite particles is in a range of 3 to 80 nm when measured by a dynamic light scattering method. 5. Particle dispersion. (1) While heating an aqueous dispersion in which core fine particles composed of titanium oxide fine particles or composite oxide fine particles composed of titanium and silicon and / or tin are dispersed,
(A) an aqueous solution containing a hydrolyzate of a metal alkoxide having an amino group,
(B) an aqueous solution of a silicate solution or a silicate, and (C) a salt of one or more metal elements selected from aluminum, zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium and yttrium A step of coating the surface of the core particles with an amino group-containing complex comprising a polycondensate obtained by simultaneously adding a dissolved aqueous solution to the aqueous dispersion, and (2) from the step (1) While heating the obtained aqueous dispersion,
(D) a silicic acid solution, or (E) a silicic acid solution and a hydroxide of one or more metal elements selected from zirconium, antimony, tungsten, tin, aluminum, niobium, cerium and zinc; After adding an aqueous solution of an oxide, an alkoxide and / or an inorganic salt, a step of coating the surface of the particles coated with the amino group-containing composite with a silica-based oxide or a silica-based composite oxide by heating. The manufacturing method of the dispersion liquid of the titanium oxide type composite particle in any one of Claims 1-4 characterized by the above-mentioned. Furthermore, the manufacturing method of the dispersion liquid of the titanium oxide type composite particle of Claim 5 including the process of carrying out solvent substitution of the water dispersion liquid obtained from the said process (2) with the organic solvent.   In the step (1), the heating temperature of the aqueous dispersion of the core particles is in the range of 60 to 210 ° C. The dispersion of the titanium oxide-based composite particles according to claim 5 or 6, Production method.   In the step (1), the pH of the dispersion when the aqueous solutions of the components (A), (B), and (C) are added simultaneously is adjusted to be in the range of 7-12. The manufacturing method of the dispersion liquid of the titanium oxide type composite particle in any one of Claims 5-7.   In the step (1), the addition rate of the aqueous solution of the component (A) is in the range of 0.005 to 0.2 mol / Hr based on the molar basis of the amino group held by the metal alkoxide contained in the aqueous solution. The method for producing a dispersion of titanium oxide composite particles according to any one of claims 5 to 8.   In the step (1), the addition rate of the aqueous solution of the component (B) is 0.012 to 0.5 mol / Hr based on the molar amount of silicon contained in the silicic acid or silicate contained in the aqueous solution. The method for producing a dispersion of titanium oxide composite particles according to any one of claims 5 to 8, wherein the dispersion is in a range.   In the step (1), the addition rate of the aqueous solution of the component (C) is in the range of 0.005 to 0.2 mol / Hr based on the molar amount of the metal element held by the metal salt contained in the aqueous solution. The method for producing a dispersion of titanium oxide composite particles according to any one of claims 5 to 8. In the step (1), the concentration of the aqueous solution containing the hydrolyzate of the metal alkoxide having an amino group is in the range of 0.2 to 20% by weight, and the concentration of the silicic acid solution or the aqueous silicate solution is SiO. _2. A salt of one or more metal elements selected from aluminum, zirconium, zinc, cerium, tin, lanthanum, magnesium, calcium and yttrium, in a range of 0.5 to 6% by weight based on ₂ conversion standards. The production of a dispersion of titanium oxide composite particles according to any one of claims 5 to 11, wherein the concentration of the aqueous solution in which the aqueous solution is dissolved is in the range of 0.01 to 5% by weight on an oxide conversion basis. Method.