WO2023100947A1

WO2023100947A1 - Modified metal oxide colloidal particles, and method for producing same

Info

Publication number: WO2023100947A1
Application number: PCT/JP2022/044245
Authority: WO
Inventors: 欣也小山; 智規古川
Original assignee: 日産化学株式会社
Priority date: 2021-12-03
Filing date: 2022-11-30
Publication date: 2023-06-08
Also published as: JPWO2023100947A1; TW202344480A

Abstract

[Problem] To provide: modified metal oxide colloidal particles which suppress the occurrence of yellowing of a cured film when blended into a coating composition; and a method for producing same. [Solution] Modified metal oxide colloidal particles (C) have an average particle diameter of 5-300 nm and are formed by having metal oxide colloidal particles (A) as a core and coating the surfaces thereof with a coating layer (B) composed of a composite oxide of Si, Al and at least one atom selected from the group consisting of Sn, Sb and W.　A method for producing the modified metal oxide colloidal particles (C) comprises the following steps (a) to (d) of: (a) mixing a dispersion containing metal oxide colloidal particles (A) with a dispersion of unmodified composite oxide colloidal particles of Si, and at least one atom selected from the group consisting of Sn, Sb and W; (b) heating the mixed solution obtained in step (a) at 30-320 °C for 0.5-24 hours; (c) bringing the mixed solution obtained in step (b) into contact with an H-type cation exchange resin; and (d) mixing the mixed solution obtained in step (c) and an aqueous aluminate solution and heating the mixture at 30-320 °C for 0.5-24 hours.

Description

Modified metal oxide colloid particles and method for producing the same

The present invention provides a modified metal oxide in which the surfaces of metal oxide colloidal particles are coated with a coating layer comprising a composite oxide of Si and Al and at least one atom selected from the group consisting of Sn, Sb and W. The present invention relates to a material colloidal particle, a method for producing the modified metal oxide colloidal particle, and a coating composition containing the modified metal oxide colloidal particle.

Plastic moldings are used in large quantities due to their advantages such as light weight, easy workability, and impact resistance. However, it has disadvantages such as insufficient heat resistance. Therefore, when plastic molded bodies are used as spectacle lenses, window materials, etc., there are practical drawbacks as described above, compared to inorganic glass molded bodies. Therefore, it has been proposed to apply a protective coat (protective coating) to the plastic molded article. A large variety of coating compositions have been proposed for use in protective coatings.

A coating composition containing an organosilicon compound or a hydrolyzate thereof as a main component (resin component or coating film-forming component) is used for spectacle lenses as a coating composition that provides a nearly inorganic hard coating (Patent Document 1). .
Since the above coating composition is still unsatisfactory in scratch resistance, it has been proposed to add a colloidally dispersed silicon dioxide sol to the coating composition, which has been put to practical use for spectacle lenses (Patent Document 2).

By the way, most conventional plastic spectacle lenses have been produced by cast polymerization of diethylene glycol bisallyl carbonate. However, because the lens has a refractive index of about 1.50, which is lower than the refractive index of glass lenses, which are about 1.52, the edge thickness is thicker for nearsighted lenses. has shortcomings. Therefore, in recent years, development of a monomer having a higher refractive index than diethylene glycol bisallyl carbonate has been promoted, and a high refractive index resin material having a refractive index in the range of 1.54 to 1.76 has been proposed (Patent Documents 3 and 4).
A method of using a colloidal dispersion of metal oxide fine particles of Sb and Ti as a coating material has also been proposed for such a high refractive index resin lens (Patent Documents 5 and 6).

In addition, a silane coupling agent and a colloidal particle (a) of a metal oxide having a primary particle diameter of 2 to 60 nm are used as nuclei, and the surface thereof is coated with a coating (b) composed of colloidal particles of an acidic oxide. A stable modified metal oxide sol containing the obtained particles (c), containing (c) in a proportion of 2 to 50% by mass in terms of metal oxide, and having a primary particle diameter of 2 to 100 nm. A coating composition is disclosed comprising: As a specific example of the colloid particles to be used, a modified titanium oxide-zirconium oxide-stannic oxide composite colloid coated with antimony pentoxide containing alkylamine is disclosed (Patent Document 7). Further, a titanium oxide-stannic oxide-zirconium oxide composite colloid stabilized with an alkylamine or an oxycarboxylic acid has been disclosed (Patent Document 8).

Furthermore, (a) core particles composed of oxide fine particles or composite oxide fine particles containing, as a main component, one kind of metal element selected from the group consisting of zirconium, tin, titanium, niobium, tungsten, antimony, indium, and lanthanum; and (b) a shell layer covering the core particles and containing a composite oxide shell layer containing a composite oxide of silicon and aluminum as a main component, wherein the oxide conversion of silicon and aluminum contained in the shell layer A core-shell having a reference weight ratio (SiO ₂ /Al ₂ O ₃ ) in the range of 30 to 2000, and a weight of the composite oxide shell layer in the range of 5 to 100 parts by weight with respect to 100 parts by weight of the core particles. A dispersion containing type oxide fine particles and a dispersion medium has been proposed (Patent Document 9).
However, if the composite oxide shell layer contains a metal element other than silicon and aluminum, the surface negative charge of the core-shell type oxide fine particles may decrease, or the coverage of the core particles with the shell layer may decrease. rice field. In the production of the above-mentioned core-shell type oxide microparticles, silicon alkoxide and/or silicon alkoxide and/or silica are used in order to suppress a decrease in the coating ratio of the core particles with the shell and a decrease in the amount of negative charge on the surface of the core-shell composite oxide microparticles. It was necessary to simultaneously add the acid-containing silicon compound solution and the aluminate aqueous solution to the aqueous dispersion of the core particles at a constant rate.

JP-A-52-16586 JP-A-53-111336 JP-A-55-13747 JP-A-64-54021 JP-A-62-151801 JP-A-63-275682 Japanese Patent Application Laid-Open No. 2001-123115 JP-A-10-306258 JP 2015-143297 A

A coating film formed from a coating composition that uses metal oxide colloidal particles containing organic amines such as alkylamines has the problem of being prone to yellowing due to organic amines.

An object of the present invention is to provide modified metal oxide colloid particles that suppress yellowing of cured films when applied to coating compositions.

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, the surface of the metal oxide colloidal particles serving as nuclei was coated with at least one atom selected from the group consisting of Si and Al and Sn, Sb and W. The coating layer (B) made of a composite oxide with, especially Si and at least one atom selected from the group consisting of Sn, Sb and W, is modified with an aluminate. By coating with the coating layer (B), when the particles are blended in a coating composition, a cured film that is resistant to yellowing can be formed, and when the particles are dispersed in an organic solvent, the particles have excellent dispersion stability. The inventors have found that an organic solvent dispersion can be obtained, and completed the present invention.

That is, the present invention provides, as a first aspect, a composite of Si and Al and at least one atom selected from the group consisting of Sn, Sb and W on the surface of which metal oxide colloidal particles (A) are used as nuclei. The present invention relates to modified metal oxide colloidal particles (C) having an average particle diameter of 5 to 300 nm and coated with a coating layer (B) made of an oxide.
As a second aspect, the coating layer (B) is formed by modifying an unmodified composite oxide of Si and at least one atom selected from the group consisting of Sn, Sb and W with an aluminate. It relates to the modified metal oxide colloidal particles (C) according to the first aspect, which is a layer.
As a third aspect, the metal oxide colloidal particles (A) are composed of Ti, Mn, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce The modified metal oxide colloidal particles (C) according to the first aspect or the second aspect, which are colloidal particles of at least one metal oxide selected from the group consisting of:
As a fourth aspect, the modified metal oxide colloidal particles (C) according to any one of the first to third aspects, wherein the metal oxide colloidal particles (A) have an average primary particle size of 1 to 300 nm. .
As a fifth aspect, the Al content (in terms of Al ₂ O ₃ ) in the coating layer (B) is the total metal oxide of the metal oxide colloid particles (A) and the total composite oxide of the coating layer (B). It relates to the modified metal oxide colloid particles (C) according to any one of the first to fourth aspects, which is 0.05 to 0.5% by mass based on the total mass.
As a sixth aspect, the Al content (in terms of Al ₂ O ₃ ) in the coating layer (B) is 0.1 to 10% by mass based on the mass of the total composite oxide of the coating layer (B). It relates to the modified metal oxide colloidal particles (C) according to any one of the first to fifth aspects.
As a seventh aspect, the content of total nitrogen derived from organic amines in the modified colloidal metal oxide particles (C) is equal to It relates to the modified metal oxide colloidal particles (C) according to any one of the first to sixth aspects, which is 0.05% by mass or less based on the total mass of the composite oxide.
As an eighth aspect, at least part of the surface of the modified metal oxide colloidal particles (C) is surface-modified with an organosilicon compound represented by general formula (1) or general formula (2). It relates to the modified metal oxide colloidal particles (C) according to any one of the aspect to the seventh aspect.
(R ^1′ ) _a′ Si(R ^2′ ) _4-a′ Formula (1)
[(R ^3′ ) _d Si(R ^4′ ) _3-d ] ₂ Y _e Formula (2)
(In formulas (1) and (2),
R ^1' and R ^3' are alkyl groups, phenyl groups, vinyl groups, acryloxy groups, methacryloxy groups, epoxy groups, styryl groups, isocyanate groups, mercapto groups, ureido groups, acid anhydride groups, or carbon atoms containing functional groups thereof. It is an alkylene group of numbers 1 to 10 and represents an alkylene group bonded to a silicon atom via a Si—C bond, and when there are a plurality of each of R ^1' and R ^3' , each R ^1' and each R ^{3 '} may be the same or different,
R ^2' ^and R ⁴ ^' each represents a hydrolyzable group consisting of ^an alkoxy group, an acyloxy group, or a halogen atom ^; may be the same or different,
Y represents an alkylene group, an arylene group, an NH group or an oxygen atom.
a′ represents an integer of 1 to 3, d represents an integer of 0 to 3, and e represents an integer of 0 or 1. )

A ninth aspect relates to a dispersion of modified metal oxide colloidal particles (C) in which the modified metal oxide colloidal particles (C) according to any one of the first to eighth aspects are dispersed in an aqueous medium or an organic solvent. .

As a tenth aspect, (S) component: an organosilicon compound and/or a silicon-containing substance that is a hydrolyzate thereof, and (T) component: the modified metal oxidation according to any one of the first to eighth aspects Colloidal particles (C)
A coating composition comprising
A coating composition in which the organosilicon compound as component (S) contains at least one organosilicon compound selected from the group consisting of compounds represented by the following formula (I) and compounds represented by the following formula (II): about things.
(R ¹ ) _a (R ³ ) _b Si(OR ² ) _4-(a+b) (I)
(In the formula,
R ¹ and R ³ each independently represent an alkyl group, an aryl group, a vinyl group, a halogenated alkyl group, a halogenated aryl group or an alkenyl group, or an epoxy group, an isocyanate group, an acryloyl group, a methacryloyl group, represents an organic group that is a monovalent organic group having a mercapto group, a ureido group, or a cyano group and is bonded to a silicon atom via a Si—C bond,
R ² represents an alkyl group having 1 to 8 carbon atoms, an aryl group, an aralkyl group, an alkoxyalkyl group, or an acyl group;
a and b each independently represent an integer of 0, 1, or 2, and a+b is an integer of 0, 1, or 2; )
[(R ⁴ ) _c Si(OX) _3-c ] ₂ Y (II)
(In the formula,
R ⁴ represents an alkyl group having 1 to 5 carbon atoms,
X represents an alkyl group or acyl group having 1 to 4 carbon atoms,
Y represents a methylene group or an alkylene group having 2 to 20 carbon atoms,
c represents an integer of 0 or 1; )
As an eleventh aspect, (K) component: at least one resin selected from the group consisting of thermosetting resins, thermoplastic resins and ultraviolet curable resins, and (T) component: any one of the first to eighth aspects Modified metal oxide colloid particles according to 1 (C)
It relates to a coating composition comprising

A twelfth aspect relates to a cured film produced using the coating composition according to the tenth or eleventh aspect.
A thirteenth aspect relates to an optical member having the cured film according to the twelfth aspect on the surface of an optical substrate.
A fourteenth aspect relates to an optical member having an antireflection film on the surface of the cured film according to the thirteenth aspect.

As a fifteenth aspect, it relates to a method for producing modified metal oxide colloidal particles (C) including the following steps (a) to (d).
(a) a dispersion containing metal oxide colloidal particles (A) and a dispersion of unmodified composite oxide colloidal particles containing Si and at least one atom selected from the group consisting of Sn, Sb and W; Step (b) of mixing the mixed solution obtained in step (a) at a temperature of 30 to 320 ° C. for 0.5 to 24 hours (c) Heating the mixed solution obtained in step (b) with H Step (d) of contacting with a type cation exchange resin, mixing the mixed solution obtained in the step (c) and an aluminate aqueous solution, and heating at a temperature of 30 to 320 ° C. for 0.5 to 24 hours. As a 16th aspect, in the step (a), the mass of the total complex oxide of the unmodified complex oxide colloidal particles/the mass of the total metal oxide of the metal oxide colloidal particles (A) is 0.05 to 0.50. Dispersion of unmodified composite oxide colloid particles with a dispersion containing metal oxide colloid particles (A) and Si and at least one atom selected from the group consisting of Sn, Sb and W so that It relates to the method for producing modified metal oxide colloidal particles (C) according to the fifteenth aspect, which is a step of mixing with a liquid.
As a seventeenth aspect, in the step (d), the mixed solution obtained in the step (c) is adjusted so that the mass of the total composite oxide/the mass of the aluminate (in terms of Al ₂ O ₃ ) is 50 to 800 and an aluminate aqueous solution.
An eighteenth aspect relates to the method for producing modified metal oxide colloidal particles (C) according to any one of the fifteenth to seventeenth aspects, wherein the heat treatment in step (b) is performed under hydrothermal conditions.

When the modified metal oxide colloidal particles of the present invention are blended in a coating composition, they can form a composition capable of forming a cured film that is resistant to yellowing.
Also, the coating composition of the present invention can form a cured film that is resistant to yellowing. Therefore, an optical member having a cured film produced from the coating composition containing the modified metal oxide colloidal particles of the present invention can be used particularly as spectacles, display materials, and the like.

An aqueous dispersion obtained by dispersing the modified metal oxide colloidal particles of the present invention in an aqueous medium has excellent dispersion stability.
In addition, in the organic solvent dispersion obtained by dispersing the modified metal oxide colloidal particles of the present invention in an organic solvent, the surface of the modified metal oxide colloidal particles may or may not be surface-modified with an organic silicon compound. Even without it, the dispersion stability is excellent.

[Modified metal oxide colloidal particles (C)]
The modified metal oxide colloidal particle (C) of the present invention has the metal oxide colloidal particle (A) as a nucleus, and the surface of the metal oxide colloidal particle (A) is Si, Al, and at least one atom selected from the group consisting of Sn, Sb and W. Particles having an average particle diameter of 5 to 300 nm, which are coated with a coating layer (B) comprising a composite oxide of
Further, as one of the preferred embodiments of the present invention, the metal oxide colloidal particles (A) are used as nuclei, and the surfaces thereof are unmodified with Si and at least one atom selected from the group consisting of Sn, Sb and W. Modified metal oxide colloid particles (C) having an average particle diameter of 5 to 300 nm, which are coated with a coating layer (B) obtained by modifying a complex oxide with an aluminate.

<Metal oxide colloidal particles (A)>
The metal oxide colloidal particles (A) are selected from the group consisting of Ti, Mn, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce. colloidal particles of at least one metal oxide. The colloidal particles (A) of metal oxides are colloidal _particles of oxides of metals having a valence _of _2-6 . , _Y2O3 _, _ZrO2 , _Nb2O5 _, _MoO3 , _In2O3 _, _SnO2 _, _Sb2O5 , _Ta2O5 , _WO3 , PbO, _Bi2O3 _, _CeO2 _, etc. can do. These metal oxides can be used either singly or in combination. Examples of the method of combination include a method of mixing several types of the metal oxides, a method of forming a composite of the metal oxides, and a method of forming a solid solution of the metal oxides at the atomic level.

When the colloidal particles (A) of metal oxides are composed of a plurality of kinds of metal oxides, for example, TiO ₂ -SnO in which TiO ₂ particles and SnO ₂ particles are chemically bonded at their interface to form a composite. ₂ composite oxide colloidal particles, SnO ₂ —WO ₃ composite oxide colloidal particles in which SnO ₂ particles and WO ₃ particles are chemically bonded at their interface to form a composite, SnO ₂ particles and ZrO ₂ particles SnO ₂ —ZrO ₂ composite oxide colloidal particles composited by chemical bonding at their interfaces, TiO ₂ —ZrO obtained by forming a solid solution of TiO ₂ , ZrO ₂ and SnO ₂ at the atomic level ₂ -SnO ₂ composite oxide colloidal particles and the like. Therefore, these composite oxide colloidal particles are not just a mixture of metal oxide particles such as _TiO2 particles, _SnO2 particles.
The colloidal particles (A) of metal oxide can also be used as a compound by combining metal components such as ZnSb ₂ O ₆ , InSbO ₄ and ZnSnO ₃ .

The colloidal particles (A) of metal oxide can be produced by known methods such as ion exchange, peptization, hydrolysis, and reaction methods. Examples of the ion exchange method include a method of treating an acid salt of the metal with a hydrogen-type ion exchange resin, or a method of treating a basic salt of the metal with a hydroxyl-type anion exchange resin. Examples of deflocculation include washing the gel obtained by neutralizing the acid salt of the metal with a base or neutralizing the basic salt of the metal with an acid, followed by peptization with an acid or a base. method. Examples of the hydrolysis method include a method of hydrolyzing the alkoxide of the metal, or a method of hydrolyzing the basic salt of the metal under heating and then removing unnecessary acid. Examples of the reaction method include a method of reacting the metal powder with an acid.
Also, for example, composite metal oxide colloid particles can be obtained by mixing metal oxide colloid particles obtained by these known methods with a metal acid salt.

When the colloidal particles (A) of the metal oxide contain titanium oxide, the particles may be amorphous or crystals such as anatase, rutile, and brookite. Further, it may be a perovskite titanium compound such as barium titanate (represented by BaTiO ₃ or BaO.TiO ₂ ). Among them, the crystal type of the colloidal particles of the composite oxide containing titanium oxide as a main component is preferably the rutile type.
Moreover, when the colloidal particles (A) of the metal oxide contain zirconium oxide, the particles may be amorphous or may be crystals such as monoclinic, tetragonal, or cubic.

The average primary particle size of the core metal oxide colloidal particles (A) can be measured by observation with a transmission electron microscope. The average primary particle size is, for example, in the range of 1-300 nm, or 3-200 nm, or 5-100 nm.

<Coating layer (B)>
The coating layer (B) is a layer made of a composite oxide of Si and Al and at least one atom selected from the group consisting of Sn, Sb and W, preferably Si, Sn, Sb and W It is a layer obtained by modifying an unmodified composite oxide with at least one atom selected from the group consisting of with an aluminate. However, the composite oxide is different from the metal oxide of the metal oxide colloidal particles (A).
As the coating layer (B), for example, SiO ₂ —SnO ₂ composite oxide colloidal particles, in which SiO ₂ particles and SnO ₂ particles are chemically bonded at their interface to form a composite, are coated with an aluminate. Modified SiO ₂ —SnO ₂ —Al ₂ O ₃ coating layer, SiO ₂ —Sb ₂ O ₅ composite in which SiO ₂ particles and Sb ₂ O ₅ particles are chemically bonded at their interfaces Oxide colloid particles form an aluminate-modified SiO ₂ —Sb ₂ O ₅ —Al ₂ O ₃ coating layer, and SiO ₂ particles and WO ₃ particles form a chemical bond at the interface to form a composite. SiO ₂ —WO ₃ —Al ₂ O ₃ coating layer obtained by modifying SiO ₂ _—WO 3 composite oxide colloidal particles with an aluminate.
The coating layer (B) is, for example, a metal oxide colloid (A), a SiO ₂ —SnO ₂ composite oxide in which SiO ₂ particles and SnO ₂ particles are chemically bonded at their interfaces. It can also be an aluminate-modified SiO ₂ —SnO ₂ —Al ₂ O ₃ coating layer after being coated with colloidal particles.
The coating layer (B) is a layer obtained by modifying an unmodified composite oxide of Si and at least one atom selected from the group consisting of Sn, Sb and W with an aluminate. preferable. Further, it is sufficient that part or all of the unmodified composite oxide is modified with an aluminate, and it is preferable that the entire unmodified composite oxide is modified with an aluminate. Such modified metal oxide colloid particles (C) provided with a coating layer (B) obtained by modifying an unmodified composite oxide with an aluminate are good even when they are dispersed in an organic solvent as a medium. It is possible to express a decent dispersion state.

Although the detailed mechanism of modification by aluminate has not been elucidated, RALPH K. et al. According to ILER, THE CHEMISTRY OF SILICA, JOHN WILEY & SONS, Si and Al atoms can have 4 or 6 coordination numbers to the O atom and both have approximately the same atomic radius. Therefore, the tetrahydroxidealuminate ion and the orthosilicate ion are geometrically similar, so that the tetrahydroxidealuminate ion is inserted between the Si—O bonds or the Al atom is exchanged with the Si atom on the _SiO2 surface, It is presumed that Si atoms and Al atoms form bonds through O atoms, and the unmodified composite oxide is modified with aluminate.

The unmodified composite oxide colloidal particles can be produced by known methods such as ion exchange method and oxidation method. An example of the ion exchange method is a method in which an acid salt of said atom is treated with a hydrogen ion exchange resin. Examples of oxidation methods include reacting atomic or inorganic oxide powders with hydrogen peroxide.

The Al content contained in the coating layer (B) can be determined by measuring the modified metal oxide colloidal particles (C) using a wavelength dispersive X-ray fluorescence analyzer.
The Al content (in terms of Al ₂ O ₃ ) in the coating layer (B) is based on the total mass of all metal oxides in the metal oxide colloidal particles (A) and all composite oxides in the coating layer (B), For example, it ranges from 0.05 to 0.5 mass %, or from 0.08 to 0.5 mass %. Here, the total mass of all metal oxides in the metal oxide colloidal particles (A) and all composite oxides in the coating layer (B) can be quantified by a calcination method.
Further, the Al content (in terms of Al ₂ O ₃ ) in the coating layer (B) is, for example, in the range of 0.1 to 10% by mass based on the mass of the total composite oxide in the coating layer (B). .

<Modified metal oxide colloidal particles (C)>
The modified metal oxide colloidal particles (C) are particles having an average particle size of 5 to 300 nm, which are formed by coating the surface of the metal oxide colloidal particles (A) with the coating layer (B).
The modified metal oxide colloidal particles (C) can be measured for the average particle size by a dynamic light scattering method (DLS method). The average particle size is 5-300 nm, preferably 5-200 nm.
In addition, since the modified metal oxide colloidal particles (C) are particles obtained by forming a chemical bond between the coating layer (B) and the surface of the metal oxide colloidal particles (A), the modified metal oxide The average primary particle size of the colloidal particles (C) as measured by a transmission electron microscope is not necessarily larger than the average primary particle size of the metal oxide colloidal particles (A), and may vary somewhat depending on their chemical bonds.
The average primary particle size of the modified metal oxide colloidal particles (C) as measured by a transmission electron microscope ranges, for example, from 5 to 300 nm, or from 5 to 200 nm.

The mass ratio of the composite oxide to be the coating layer (B) to the metal oxide colloidal particles (A) [mass of the composite oxide/mass of the metal oxide in the metal oxide colloidal particles (A)] is, for example, 0. 0.05 to 0.50, or 0.05 to 0.30, or 0.03 to 0.30.

Modified metal oxide colloidal particles (C) contain substantially no organic amine. Specifically, the content of total nitrogen derived from organic amines in the modified colloidal metal oxide particles (C) is the total composite For example, 0.05% by weight or less, or 0.01% by weight or less, based on the total weight of the oxides.
The total nitrogen content derived from the organic amine in the modified metal oxide colloidal particles (C) is determined by quantifying the organic amine contained in the modified metal oxide colloidal particles (C) by a cation chromatography method. It can be obtained by calculating the total nitrogen content.
Further, the total mass of all metal oxides in the metal oxide colloidal particles (A) and all composite oxides in the coating layer (B) can be quantified by a sintering method.

<Modified Metal Oxide Colloidal Particles (C) Surface-Modified with Organosilicon Compound>
At least part of the surface of the modified metal oxide colloidal particles (C) can be modified with an organosilicon compound represented by general formula (1) or general formula (2).
(R ^1′ ) _a′ Si(R ^2′ ) _4-a′ Formula (1)
[(R ^3′ ) _d Si(R ^4′ ) _3-d ] ₂ Y _e Formula (2)
(In formulas (1) and (2),
R ^1' and R ^3' are alkyl groups, phenyl groups, vinyl groups, acryloxy groups, methacryloxy groups, epoxy groups, styryl groups, isocyanate groups, mercapto groups, ureido groups, acid anhydride groups, or carbon atoms containing functional groups thereof. It is an alkylene group of numbers 1 to 10 and represents an alkylene group bonded to a silicon atom via a Si—C bond, and when there are a plurality of each of R ^1' and R ^3' , each R ^1' and each R ^{3 '} may be the same or different,
R ^2' ^and R ⁴ ^' each represents a hydrolyzable group consisting of ^an alkoxy group, an acyloxy group, or a halogen atom ^; may be the same or different,
Y represents an alkylene group, an arylene group, an NH group or an oxygen atom.
a ^′ represents an integer of 1 to 3, d represents an integer of 0 to 3, and e represents an integer of 0 or 1. )

The alkyl group includes an alkyl group having 1 to 10 carbon atoms, the alkoxy group includes an alkoxy group having 1 to 10 carbon atoms, and the acyloxy group includes an acyloxy group having 1 to 10 carbon atoms. The halogen atom includes fluorine atom, chlorine atom, bromine atom and iodine atom, and the arylene group includes an arylene group having 6 to 10 carbon atoms. The epoxy group includes not only epoxy groups but also groups containing epoxy groups (glycidyl group, glycidoxy group, epoxycycloalkyl group, etc.).

Specific examples of the organosilicon compound represented by formula (1) include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane. , hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydiphenylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, methylvinyldimethoxysilane Silane, methylvinyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxyoctyl trimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane ( γ-glycidoxypropyltrimethoxysilane), 3-glycidoxypropylmethyldiethoxysilane, p-styryltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-mercaptopropylmethyl dimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like.

Specific examples of the organosilicon compound represented by formula (2) include hexamethyldisiloxane and hexamethyldisilazane.

These organosilicon compounds are used for the purpose of improving the dispersibility of the modified metal oxide colloidal particles (C) in organic solvents, or improving the compatibility with resins such as thermosetting resins, thermoplastic resins and ultraviolet curable resins. can be selected and used as appropriate.
These organosilicon compounds are available from Shin-Etsu Chemical Co., Ltd. and Tokyo Chemical Industry Co., Ltd.

At least part of the surface of the modified metal oxide colloidal particles (C) is modified with an organosilicon compound represented by general formula (1) or general formula (2), that is, the modified metal oxide colloidal particles (C) In order to bond the organosilicon compound represented by general formula (1) or general formula (2) to at least part of the surface of the modified metal oxide colloid particles (C) (for example, modified metal oxide colloid An alcohol-dispersed sol of particles (C)) and an organosilicon compound represented by general formula (1) or general formula (2) (or an alcohol solution thereof) are mixed in a predetermined amount, and (if necessary) a predetermined amount of After adding water and, if necessary, a hydrolysis catalyst such as dilute hydrochloric acid, the mixture is allowed to stand at normal temperature for a predetermined time, or heat treatment may be performed.

In addition, at least part of the surface of the modified metal oxide colloidal particles (C) is surface-modified with an organosilicon compound represented by the general formula (1) or general formula (2), that is, the modified metal oxide colloidal particles ( Another method of bonding the organosilicon compound represented by general formula (1) or general formula (2) to at least part of the surface of C) is, for example, the modified metal oxide colloid particles (C) (for example, Aqueous dispersion of modified metal oxide colloidal particles (C)) and a solution of an organosilicon compound represented by general formula (1) or general formula (2) (for example, a hydrophilic organic solvent such as alcohol) are mixed in a predetermined amount. , an organic solvent dispersion of modified metal oxide colloidal particles (C) surface-modified with an organosilicon compound can be obtained by a distillation method in which water is distilled off.
At this time, it is preferable to distill off water until the amount of water remaining in the organic solvent dispersion becomes 0.1% by mass to 15% by mass.

The organosilicon compound represented by general formula (1) or general formula (2) to be bound to the surface of the modified metal oxide colloidal particles (C) may be used alone or in combination of two or more. may be used.
Further, when performing a surface modification treatment for binding the organosilicon compound represented by general formula (1) or general formula (2) to the surface of the modified metal oxide colloidal particles (C), the general formula The organosilicon compound represented by (1) or general formula (2) may be partially hydrolyzed, or the surface modification treatment may be performed without hydrolysis.
Furthermore, after the surface modification treatment, the hydrolyzable groups of the organosilicon compound represented by general formula (1) or general formula (2) reacted with the hydroxy groups on the surface of the modified metal oxide colloidal particles (C). This state is preferable, but there is no problem even if some hydroxyl groups remain untreated.

The amount of bonding of the organosilicon compound represented by general formula (1) or general formula (2) to the surface of the modified metal oxide colloidal particles (C) is not particularly limited. For example, 0.01 to 20% by mass, preferably 0.1 to 20% by mass, based on the total mass (100% by mass) of all metal oxides in A) and all composite oxides in coating layer (B) and more preferably 0.1 to 15% by mass.
Further, the total mass of all metal oxides in the metal oxide colloidal particles (A) and all composite oxides in the coating layer (B) can be quantified by a sintering method.

[Dispersion of Modified Metal Oxide Colloidal Particles (C)]
The modified metal oxide colloidal particles (C) can be used as a dispersion in an aqueous medium or an organic solvent. A dispersion using an organic solvent as a dispersion medium can be made into an organic solvent dispersion by replacing water, which is the dispersion medium of the dispersion in an aqueous medium, with an organic solvent. Alternatively, an organic solvent dispersion can be obtained by further substituting another type of organic solvent for the dispersion dispersed in the organic solvent. This substitution can be carried out by an ordinary method such as a distillation method or an ultrafiltration method.

Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; Glycols such as ethylene glycol, and hydrocarbons such as hexane, toluene and cyclohexane can be used.

The concentration of the modified metal oxide colloidal particles (C) contained in the dispersion can be expressed as the total metal oxide concentration. Here, the total metal oxide concentration means the metal oxide contained in the metal oxide colloidal particles (A) and the composite oxide in the coating layer (B) (e.g., SiO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ and WO ₃ ), and can be quantified by a calcination method in which the dispersion is calculated from the calcination residue obtained by calcining the dispersion at 800° C. or higher for 30 minutes or longer.
The total metal oxide concentration in the dispersion ranges, for example, from 1 to 60 wt%, or from 20 to 60 wt%, or from 30 to 60 wt%.

Also, the pH of the dispersion is, for example, in the range of 1-14, or 2-8, or 3-7.

[Coating composition]
The coating composition (also referred to as a coating liquid) of the present invention comprises (S) component: an organosilicon compound and/or a silicon-containing substance that is a hydrolyzate thereof, and (T) component: the modified metal oxide colloidal particles described above. (C).
Alternatively, the coating composition of the present invention includes component (K): at least one resin selected from the group consisting of thermosetting resins, thermoplastic resins and UV-curable resins, and component (T): the modified metal oxide described above. containing colloidal particles (C).
Each component, particularly the (S) component and the (K) component, constituting the coating composition of the present invention will be described in detail below.

<<(S) component>>
The (S) component according to the present invention is an organosilicon compound and/or a silicon-containing substance that is a hydrolyzate thereof. Specifically, the organosilicon compound includes at least one organosilicon compound selected from the group consisting of compounds represented by formula (I) and compounds represented by formula (II), which will be described later.

<Compound Represented by Formula (I)>
(R ¹ ) _a (R ³ ) _b Si(OR ² ) _4-(a+b) (I)
During the ceremony,
R ¹ and R ³ each independently represent an alkyl group, an aryl group, a vinyl group, a halogenated alkyl group, a halogenated aryl group or an alkenyl group, or an epoxy group, an isocyanate group, an acryloyl group, a methacryloyl group, represents an organic group that is a monovalent organic group having a mercapto group, a ureido group or a cyano group and is bonded to a silicon atom via a Si—C bond,
R ² represents an alkyl group having 1 to 8 carbon atoms, an aryl group, an aralkyl group, an alkoxyalkyl group, or an acyl group;
a and b each independently represents an integer of 0, 1, or 2, and a+b is an integer of 0, 1, or 2;

The organosilicon compound represented by the above formula (I) is an organosilicon compound in which R ¹ and R ³ are the same organic group or different organic groups, or in which a and b are the same integer or different integers. including.

Examples of the organosilicon compound represented by the above formula (I) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraacetoxysilane, methyltrimethoxysilane, Methyltripropoxysilane, Methyltributoxysilane, Methyltriacetoxysilane, Methyltriamyloxysilane, Methyltriphenoxysilane, Methyltribenzyloxysilane, Methyltriphenethyloxysilane, Glycidoxymethyltrimethoxysilane, Glycidoxymethyl Triethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyl Trimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Triethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyl Triethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyl triethoxysilane, (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)ethyltributoxysilane, β-(3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldimethoxysilane Ethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropyl methyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycid xypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ - glycidoxypropylvinyldiethoxysilane, isocyanatopropyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane. , phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane Silane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane , phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ- Mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, ureidomethyltrimethoxysilane, 2-ureidoethyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, ureidomethyltriethoxysilane , 2-ureidoethyltriethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, etc., and these can be used alone or in combination of two or more.

<Compound Represented by Formula (II)>
[(R ⁴ ) _c Si(OX) _3-c ] ₂ Y (II)
During the ceremony,
R ⁴ represents an alkyl group having 1 to 5 carbon atoms,
X represents an alkyl group or acyl group having 1 to 4 carbon atoms,
Y represents a methylene group or an alkylene group having 2 to 20 carbon atoms,
c represents an integer of 0 or 1;

Examples of the organosilicon compound represented by the formula (II) include methylenebismethyldimethoxysilane, ethylenebisethyldimethoxysilane, propylenebisethyldiethoxysilane, butylenebismethyldiethoxysilane, and the like. or in combination of two or more.

The (S) component is preferably an organosilicon compound represented by formula (I). In particular, either one of R ¹ and R ³ is an organic group having an epoxy group, R ² is an alkyl group or an aryl group, a and b are each independently 0 or 1, and a+b is Organosilicon compounds of formula (I) satisfying condition 1 or 2 are preferred.

Preferred examples of the organosilicon compound represented by formula (I) include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltri Ethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltri Methoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltriethoxysilane butoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltri methoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-Glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane , α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, Ethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycid xypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, and γ-glycidoxypropylvinyldiethoxysilane. More preferred are γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane, which can be used alone or as a mixture.

Further, when γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, or γ-glycidoxypropylmethyldiethoxysilane is used, 4 corresponding to a+b=0 in formula (I) A functional compound may be used in combination. Examples of tetrafunctional compounds include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-tert-butoxysilane, tetrasec-butoxysilane, and the like. be done.

The (S) component used in the coating composition of the present invention: the hydrolyzate of the organosilicon compound is obtained by hydrolyzing the compound represented by the above formula (I) and the compound represented by the formula (II). As a result, a compound in which part or all of R ² (formula (I)) and X (formula (II)) are substituted with hydrogen atoms is obtained. These organosilicon compound hydrolysates of formula (I) and formula (II) can be used alone or in combination of two or more. Hydrolysis is carried out by adding an acidic aqueous solution such as an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, an aqueous acetic acid solution, etc. to the organosilicon compound and stirring the mixture.

<<Coating Composition Containing Component (S) and Component (T)>>
In the coating composition containing the (S) component and the (T) component, the ratio of the (S) component and the (T) component is not particularly limited. Component (S) can be contained in a mass ratio of 25 to 400 parts by mass, preferably 25 to 300 parts by mass, per 100 parts by mass of C).

<<(K) component>>
The component (K) according to the present invention is at least one resin selected from the group consisting of thermosetting resins, thermoplastic resins and UV-curable resins, and these resins serve as matrix-forming components.
Examples of the matrix-forming component include acrylic resins, melamine resins, urethane resins, polyester resins, epoxy resins, phosphagen resins, and the like. Among them, a polyester resin or a urethane resin is preferable.

<<Coating composition containing component (K) and component (T)>>
In the coating composition containing the component (K) and the component (T), the ratio of the component (K) and the component (T) is not particularly limited. Component (K) can be contained at a mass ratio of 25 to 400 parts by mass with respect to 100 parts by mass of C).

《Other ingredients》
The coating composition of the present invention may contain a curing catalyst (curing agent) to accelerate the curing reaction. As the curing catalyst (curing agent), for example, at least one selected from the group consisting of amino acids, metal alkoxides, metal chelate compounds, organic acid metal salts, perchloric acids or salts thereof, acids or salts thereof, and metal chlorides. It is a kind of curing catalyst.
A curing catalyst (curing agent) is used to accelerate curing of silanol groups (and optionally epoxy groups) of the (S) organosilicon compound contained in the coating composition. By using these curing catalysts (curing agents), it is possible to speed up the film-forming reaction.

Specific examples thereof include amino acids such as glycine; alkoxides of metals such as aluminum, zirconium or titanium; metal chelate compounds such as aluminum acetylacetonate, chromium acetylacetonate, titanium acetylacetonate, cobalt acetylacetonate; Organic acid metal salts such as sodium, zinc naphthenate, cobalt naphthenate, zinc octylate, and tin octylate; perchloric acids such as perchloric acid, ammonium perchlorate, and magnesium perchlorate; , nitric acid, chromic acid, hypochlorous acid, boric acid, bromic acid, selenous acid, thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrous acid, aluminate, carbonic acid, organic carboxylic acid, p-toluenesulfonic acid, etc. Acids, organic acids, or salts thereof; Metal chlorides that are Lewis acids such as SnCl ₂ , AlCl ₃ , FeCl ₃ , TiCl ₄ , ZnCl ₂ and SbCl ₃ .

These curing catalysts (curing agents) can be used by appropriately adjusting the type and amount used according to the composition of the coating composition of the present invention. When a curing catalyst (curing agent) is used, the upper limit of the amount used is desirably 5% by mass or less relative to the total solid content in the coating composition. In the present specification, the term "total solid content" refers to all components of the coating composition excluding the solvent, and even if it is liquid, it is treated as "solid content" for the sake of convenience.

A solvent may also be used in the coating composition of the present invention for the purpose of imparting fluidity, adjusting the concentration of solids, adjusting surface tension, viscosity, evaporation rate, and the like. The solvents used are water or organic solvents.
Examples of organic solvents used include alcohols such as methanol, ethanol, isopropyl alcohol and butanol; cellosolves such as methyl cellosolve and ethyl cellosolve; glycols such as ethylene glycol; esters such as methyl acetate, ethyl acetate and butyl acetate; Ethers such as diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as dichloroethane; and aromatic hydrocarbons such as toluene and xylene. mentioned.
In addition, the concentration of the total solid content in the coating composition of the present invention can be, for example, 20 to 40% by mass.

Furthermore, as will be described later, the coating composition of the present invention is used for the purpose of improving the wettability to the substrate and improving the smoothness of the cured film when forming a cured film from the composition on the substrate. Various surfactants can be included. Furthermore, ultraviolet absorbers, antioxidants, antistatic agents, etc. can be added as long as they do not affect the physical properties of the cured film. Furthermore, disperse dyes, oil-soluble dyes, fluorescent dyes, pigments, photochromic compounds, thixotropic agents, etc. may be added.

<Cured film, optical member>
The coating composition of the present invention can be applied to a substrate surface to form a cured film. Further, by using a transparent substrate (optical substrate) suitable for optical applications, an optical member having a cured film can be obtained. The optical member is also an object of the present invention.

Various substrates made of glass, plastic, etc. are used as substrates, and specifically, spectacle lenses, various optical lenses such as cameras, various display element filters, looking glass, window glass, paints for automobiles, etc. Membranes, light covers used in automobiles and the like can be mentioned. A cured film (transparent film) is formed from the coating composition of the present invention as a hard coat film on the substrate surface. Alternatively, in addition to the application as a hard coat film, it may be formed as a primer film for plastic lenses or the like.

The coating composition can be cured by hot air drying or active energy ray irradiation. As the curing conditions for hot air drying, it is preferable to carry out in hot air at 70 to 200°C, particularly preferably 90 to 150°C. Further, active energy rays include infrared rays, ultraviolet rays, electron beams, and the like, and particularly far infrared rays can suppress damage due to heat.

As a method for applying the coating composition of the present invention to the surface of the base material, commonly used methods such as dipping, spinning, and spraying can be applied. Among them, the dipping method and the spin method are particularly preferable from the viewpoint of area degree.

In addition, before applying the coating composition to the substrate surface, the substrate surface is subjected to chemical treatment with acid, alkali, various organic solvents or detergents, physical treatment such as plasma, ultraviolet rays, etc., thereby curing the substrate. Adhesion to the film can be improved. Furthermore, the adhesiveness between the substrate and the cured film can be further improved by subjecting the surface of the substrate to a primer treatment using various resins.

The cured film formed from the coating composition of the present invention can be used as a reflective film as a high-refractive-index film, and can be used as a multifunctional film by adding functional components such as antifogging, photochromic, and antifouling properties. can also

Optical members having a cured film formed from the coating composition of the present invention can be used for spectacle lenses, camera lenses, automobile window glass, optical filters attached to liquid crystal displays, plasma displays, and the like. .

The optical member of the present invention has a cured film formed from the coating composition of the present invention on the surface of the optical substrate. can be formed. The antireflection film is not particularly limited, and conventionally known single-layer or multi-layer deposition films of inorganic oxides can be used. Examples of the antireflection film include the antireflection films disclosed in JP-A-2-262104 and JP-A-56-116003.

<Method for Producing Modified Metal Oxide Colloidal Particles (C)>
The manufacturing method of the present invention includes the following steps (a) to (d).
(a) a dispersion containing metal oxide colloidal particles (A) and a dispersion of unmodified composite oxide colloidal particles containing Si and at least one atom selected from the group consisting of Sn, Sb and W; Step (b) of mixing the mixed solution obtained in step (a) at a temperature of 30 to 320 ° C. for 0.5 to 24 hours (c) Heating the mixed solution obtained in step (b) with H A step of contacting with a type cation exchange resin (d) A step of mixing the mixed solution obtained in the step (c) and an aluminate aqueous solution, and heating at a temperature of 30 to 320 ° C. for 0.5 to 24 hours.

In step (a) in the production method of the present invention, a dispersion containing metal oxide colloidal particles (A) and a dispersion of unmodified composite oxide colloidal particles are mixed.

As described above, the metal oxide colloid particles (A) in the dispersion containing the metal oxide colloid particles (A) include Ti, Mn, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Examples include colloidal particles of at least one metal oxide selected from the group consisting of Sn, Sb, Ta, W, Pb, Bi and Ce, and using known methods such as ion exchange, peptization, hydrolysis It can be produced by a method or a reaction method, and can be used in the form of a dispersion dispersed in an aqueous medium.
The metal oxide concentration of the dispersion is, for example, in the range of 1-50% by weight, or 1-30% by weight, or 1-20% by weight. The metal oxide concentration of the metal oxide colloidal particles (A) can be quantified by a calcination method.
Further, the pH of the dispersion containing the metal oxide colloidal particles (A) is in the range of 1-14 or 1-12, for example.

As described above, the unmodified colloidal colloidal oxide particles in the dispersion of the unmodified colloidal colloidal colloidal colloidal colloidal oxides are composed of, for example, _SiO2 particles and _SnO2 particles that are chemically bonded at their interfaces to form composites. SiO ₂ —Sb ₂ O 5 composite oxide colloid particles formed by SiO 2 —Sb 2 O 5 composite oxide particles, and SiO ₂ —Sb ₂ O ₅ composite oxide colloids in which SiO ₂ particles and Sb ₂ O ₅ particles are chemically bonded at their interfaces. particles, and SiO ₂ —WO ₃ composite oxide colloidal particles in which SiO ₂ particles and WO ₃ particles are chemically bonded at their interface to form a composite.
The unmodified composite oxide colloidal particles can be produced by a known method such as an ion exchange method or an oxidation method. An example of the ion exchange method is a method in which an acid salt of said atom is treated with a hydrogen ion exchange resin. Examples of oxidation methods include reacting atomic or inorganic oxide powders with hydrogen peroxide.
The dispersion can be used in the form of a dispersion in which these unmodified composite oxide colloidal particles are dispersed in an aqueous medium.
The unmodified complex oxide concentration of the dispersion is, for example, in the range of 1 to 30% by mass, 1 to 20% by mass, or 1 to 10% by mass. The unmodified composite oxide concentration of the unmodified composite oxide colloidal particles can be quantified by a calcination method.

In the step (a), the mass of the total composite oxide of the unmodified colloidal composite oxide particles/the mass of the total metal oxide of the metal oxide colloidal particles (A) is 0.05 to 0.50, or 0.05 to 0.50. 05 to 0.30, or 0.03 to 0.30, at least selected from the group consisting of a dispersion containing metal oxide colloidal particles (A), Si, and Sn, Sb and W It is preferable to mix a dispersion of unmodified composite oxide colloidal particles with one kind of atom.

In step (b) in the production method of the present invention, the mixed solution obtained in step (a) is heated at a temperature of 30 to 320° C. for 0.5 to 24 hours.
The heating temperature can be in the range of 30 to 320°C, 50 to 320°C, or 80 to 320°C. In particular, when heating at 100° C. or higher, it can be carried out under hydrothermal conditions using a pressure vessel. Here, the hydrothermal conditions refer to high temperature and high pressure conditions of 100° C. or higher and 1 atmospheric pressure or higher.
The heating time can be in the range of 0.5 to 24 hours, 0.5 to 15 hours, 0.5 to 10 hours, or 0.5 to 8 hours.
Further, in the step (b), stirring and mixing can be performed using a known stirrer or stirring device.

In the (c) step in the production method of the present invention, the mixed solution obtained in the (b) step is brought into contact with an H-type cation exchange resin.
The H-type cation exchange resin is a cation exchange resin having functional groups capable of exchanging hydrogen ions with other cations. A sulfonic acid type H-type strongly acidic cation exchange resin or a carboxylic acid type H-type weakly acidic cation exchange resin can be used. As the sulfonic acid type strongly acidic cation exchange resin, for example, Amberlite (registered trademark) IR-120B manufactured by Organo Corporation can be used.

In step (d) in the production method of the present invention, the mixed solution obtained in step (c) is mixed with an aluminate aqueous solution and heated at a temperature of 30 to 320° C. for 0.5 to 24 hours.
The aluminate is a compound containing an aluminate ion and an anion derived from an inorganic base. Inorganic bases include, for example, sodium, potassium, lithium and the like. Specific examples of the metal salt containing an aluminate ion and an anion derived from an inorganic base include sodium aluminate, potassium aluminate, lithium aluminate and the like, and commercially available ones can be used. For example, commercially available products of sodium aluminate include sodium aluminate #1219, #1819, #1919, #2019 manufactured by Asada Chemical Industry Co., Ltd., and the like.
The concentration of aluminate in the aluminate aqueous solution is, for example, in the range of 0.1 to 10% by mass or 0.1 to 5% by mass in terms of aluminum oxide.
The heating temperature is in the range of 30 to 320°C, or 40 to 180°C, or 40 to 150°C, or 40 to 100°C.
The heating time can be in the range of 0.5 to 24 hours, 0.5 to 15 hours, 0.5 to 10 hours, or 0.5 to 8 hours.
In the step (d), (c) so that the mass of the total composite oxide/the mass of the aluminate (in terms of Al ₂ O ₃ ) is in the range of 50 to 800, or 100 to 700, or 150 to 700 It is preferable to mix the mixed solution obtained in the step with the aluminate aqueous solution.

Examples of the present invention are shown below. However, the present invention is not limited to these examples.

Physical properties were obtained by the following measuring methods.
[Moisture content] Moisture content was obtained by Karl Fischer titration method.
[Average primary particle size (particle size determined by transmission electron microscope)] The dispersion was dropped onto a copper mesh, dried, and 100 particles were observed using a transmission electron microscope (manufactured by JEOL Ltd., JEM-1010). , the average value of the primary particle diameter was calculated.
[Average particle size (dynamic light scattering particle size)] The sol was diluted with a dispersion solvent, and measured using the parameters of the solvent with a dynamic light scattering measurement device: Zetasizer Nano S (trade name: manufactured by MARVERN). It was measured.
[Specific Gravity] Determined by the floating balance method (25°C).
[Viscosity] Determined with a Brookfield viscometer (25°C).
[pH] Measured with a pH meter. When the dispersion medium was an organic solvent, the measurement was performed with a solution diluted with the same mass of pure water as the dispersion.
[Evaluation of stability] The dispersion was stored at room temperature for one month, and the change in particle size of the modified metal oxide colloidal particles by the dynamic light scattering method, the change in viscosity of the dispersion, and the presence or absence of sediment were visually confirmed. Dispersion stability was evaluated according to the following indices.
A: No change in particle size and viscosity, and no sediment B: Slight change (slight increase in particle size and viscosity increase), and no sediment C: Significant change (increase in particle size, thickening, gel ) or sedimentation [total nitrogen content derived from organic amine] ion chromatograph 761 Compact IC (manufactured by Metrohm) using a column for cation analysis Shodex IC YK-421 (manufactured by Showa Denko K.K.) , to quantify organic amines. The total nitrogen content was calculated based on the obtained organic amine content.
[Al ₂ O ₃ content] The resulting aqueous sol was dried to prepare a dry powder, and the content was determined using a compact fluorescent X-ray analyzer Supermini 200 (manufactured by Rigaku Corporation).

Production Example 1 Preparation of Unmodified Composite Oxide for Coating Layer (B) 36 g of JIS No. 3 sodium silicate (containing 29.8% by mass of SiO ₂ , manufactured by Fuji Chemical Co., Ltd.) was dissolved in 400 g of pure water, Then, 9.8 g of sodium stannate NaSnO ₃ .H ₂ O (contains 55.1% by mass as SnO ₂ , manufactured by Showa Kako Co., Ltd.) was dissolved. The resulting aqueous solution was passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B) to give an aqueous sol of acidic stannic oxide-silica composite colloidal particles (pH 2.4, 1240 g containing 0.44% by mass of SnO ₂ and 0.87% by mass of SiO ₂ with a SiO ₂ /SnO ₂ mass ratio of 2.0 was obtained. Then, 3.2 g of diisopropylamine was added to the resulting aqueous sol. The obtained sol was an alkaline aqueous sol of stannic oxide-silica composite colloidal particles and had a pH of 8.0. Also, colloidal particles having an average primary particle diameter of 5 nm or less were observed with a transmission electron microscope. Moreover, the molar ratio of diisopropylamine/(SnO ₂ +SiO ₂ ) was 0.15.

Production Example 2: Preparation of Colloidal Metal Oxide ^Particles (A) (ZrO ₂ —SnO ₂ Composite Oxide Colloidal Particles) as Cores It contains 42.4% by mass in terms of tetramethylammonium oxide.) 251.85 kg of the aqueous solution and 95.6 kg of pure water were added to prepare a diluted aqueous solution. While stirring this aqueous solution, zirconium oxycarbonate powder (ZrOCO ₃ , manufactured by AMR, containing 40.11% by mass as ZrO ₂ ) was gradually added to the aqueous solution, and a total of 491.85 kg was added. After completion of the addition, after heating to 85°C, 8.23 kg of metastannic acid (manufactured by Showa Kako Co., Ltd., containing 7.08 kg of SnO ₂ ) was gradually added, and heat aging was carried out at 105°C for 5 hours. gone. At the end of this heat aging, the liquid mixture was in the form of a sol. Furthermore, hydrothermal treatment was performed at 145° C. for 5 hours. The product obtained after the hydrothermal treatment was a sol containing colloidal particles of zirconium oxide-stannic oxide composite oxide, having a (ZrO ₂ +SnO ₂ ) concentration of 12.86% by mass, a specific gravity of 1.180, and a pH of 10.0. was 62. Next _, the sol was washed _and concentrated with an ultrafiltration device while adding pure water, and the zirconium oxide- 3215 kg of sol containing stannic oxide composite oxide colloidal particles was obtained. The obtained colloidal particles of zirconium oxide-stannic oxide composite oxide had an average primary particle size of 5 to 15 nm.

Production Example 3: Preparation of Metal Oxide Colloidal Particles (A) (TiO ₂ —ZrO ₂ Composite Oxide Colloidal Particles) as Cores 368.6 g of pure water and 487.7 g of 35% tetraethylammonium hydroxide were placed in a 2 L separable flask. After mixing, 14.6 g of metastannic acid (manufactured by Showa Kako Co., Ltd.) was added and dissolved. Then, 469.7 g of titanium tetraisopropoxide (contains 132.0 g of _TiO2 , manufactured by Kanto Kagaku Co., Ltd.) was added with stirring and dissolved by heating at 60°C. Then, 108.4 g of oxalic acid dihydrate (manufactured by Ube Industries, Ltd.) was added and dissolved. The obtained mixed solution had a molar ratio of oxalic acid/titanium atom of 0.5 and a molar ratio of tetraethylammonium hydroxide/oxalic acid of 1.43. 1449 g of the mixed solution was kept in an open system under atmospheric pressure at 88 to 92° C. for 3 hours, and by-product isopropanol was removed by distillation to prepare 1240 g of a titanium-containing aqueous solution. The TiO ₂ conversion concentration of the obtained titanium-containing aqueous solution was adjusted to 5.0% by mass. 2000 g of the titanium-containing aqueous solution was placed in a 3-liter glass-lined autoclave container and hydrothermally treated at 140° C. for 5 hours. After cooling to room temperature, the oxalic acid was removed by washing with pure water (PW) using an ultrafiltration device. The resulting rutile-type titanium oxide sol had a specific gravity of 1.030, a pH of 11.7, an electrical conductivity of 1044 μS/cm, and a TiO ₂ concentration of 3.8 mass %.
35.9 g of zirconium oxychloride (containing 21.19% by mass as _ZrO2 , manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) was diluted with 217 g of pure water to give 253 g of an aqueous zirconium oxychloride solution (3.0 mass % as _ZrO2 ). % content) was prepared, and 1053 g of the water-dispersed sol of the rutile type titanium oxide sol was added with stirring. Then, hydrolysis was performed by heating to 95° C. to obtain a sol containing titanium oxide-zirconium oxide composite oxide colloidal particles.
The obtained sol had a pH of 1.2, a total metal oxide concentration of 3.6% by mass, and an average primary particle size of the titanium oxide-zirconium oxide composite oxide colloidal particles of 5 to 15 nm.

Production Example 4 Preparation of Composite Oxide for Coating Layer (B) 69 g of JIS No. 3 sodium silicate (containing 29.8% by mass of SiO ₂ , manufactured by Fuji Chemical Co., Ltd.) was dissolved in 865 g of pure water, and then stannic acid was added. 18.5 g of sodium NaSnO ₃ ·H ₂ O (containing 55.1% by mass as SnO ₂ , manufactured by Showa Kako Co., Ltd.) was dissolved, and 1.35 g of liquid sodium aluminate (0.27 g as Al ₂ O ₃ ) was dissolved. was dissolved. The resulting aqueous solution was passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B) to give an aqueous sol (pH 2.0) of acidic stannic oxide-silica-aluminum oxide composite colloidal particles .5, containing 1.09% by weight as SnO ₂ and 2.2% by weight as SiO ₂ , a SiO ₂ /SnO ₂ weight ratio of 2.0, and 0.02% by weight as Al ₂ O ₃ ) (1008 g). Then, 6.0 g of diisopropylamine was added to the resulting aqueous sol. The obtained sol was an alkaline aqueous sol of stannic oxide-silica-aluminum oxide composite colloidal particles and had a pH of 8.2. Also, colloidal particles having an average primary particle diameter of 5 nm or less were observed with a transmission electron microscope.

Example 1: Preparation of modified metal oxide colloidal particles (C) 577 g of the aqueous sol of the alkaline stannic oxide-silica composite colloidal particles prepared in 1. was added and thoroughly stirred.
Then, the mixture was heated and aged at 95° C. for 2 hours to obtain 1410 g of an aqueous sol of zirconium oxide-stannic oxide composite oxide colloidal particles coated with stannic oxide-silica composite colloidal particles. The resulting sol had a pH of 8.1 and a total metal oxide concentration of 4.1% by mass.
The obtained aqueous sol of the zirconium oxide-stannic oxide composite oxide colloidal particles was passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and an acidic zirconium oxide-oxidized 1880 g of aqueous sol of colloidal particles of stannic compound oxide was obtained. The resulting sol had a pH of 3.3 and a total metal oxide concentration of 3.0% by mass.
An aqueous solution of sodium aluminate was added to the acidic sol so that the mass of the composite oxide of the acidic zirconium oxide-stannic oxide composite oxide colloidal particles/the mass of sodium aluminate (in terms of Al ₂ O ₃ ) was 650. 20 g (0.087 g as Al ₂ O ₃ ) was added and heated at 95° C. for 2 hours, then concentrated using an ultrafiltration device. The obtained dispersion containing the modified zirconium oxide-stannic oxide composite oxide colloidal particles had a total metal oxide concentration of 30.5% by mass, a specific gravity of 1.332, a pH of 4.5, and a B-type viscosity of 5.0 mPa s. , and the average particle size was 17 nm. Also, the Al ₂ O ₃ content contained in the coating layer was 1.17% by mass based on the mass of all composite oxides in the coating layer. The obtained sol was stable with no change in physical properties even after standing at room temperature for one month.
164 g of the obtained sol was charged into an evaporator equipped with an eggplant-shaped flask, 5.0 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and then methanol was gradually added. Water was distilled off at 600 Torr to obtain 213 g of a methanol-dispersed sol of aluminate-modified modified zirconium oxide-stannic oxide composite oxide colloidal particles. The resulting methanol-dispersed sol had a total metal oxide concentration of 31.0% by mass, a B-type viscosity of 12.5 mPa s, a pH of 5.7 (diluted with the same mass of water as the sol), a water content of 0.6%, and an average particle size of The diameter was 17 nm. The obtained sol was stable with no change in physical properties even after standing at room temperature for one month.

Example 2 Preparation of Modified Metal Oxide Colloidal Particles (C) 1388 g of the water-dispersed sol obtained in Production Example 3 was added to 769 g of the water-dispersed sol of the alkaline stannic oxide-silica composite colloidal particles prepared in Production Example 1. Added under stirring. Then, the solution was passed through a column packed with 500 mL of an anion exchange resin (Amberlite (registered trademark) IRA-410, manufactured by Organo Co., Ltd.).
Next, the water-dispersed sol after passing the liquid was heated at 150° C. for 3 hours to obtain a water-dispersed sol of titanium oxide-zirconium oxide composite oxide colloidal particles coated with stannic oxide-silica composite colloidal particles. The resulting water-dispersed sol was 2788 g and had a total metal oxide concentration of 2.2% by mass.
The resulting water-dispersed sol was passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B) to obtain 3427 g of an aqueous sol of acidic titanium oxide-zirconium oxide composite oxide colloidal particles. rice field. The resulting sol had a pH of 2.4 and a total metal oxide concentration of 1.7 mass %.
25 g of an aqueous sodium aluminate solution was added to the resulting acidic sol so that the mass of the composite oxide of the acidic titanium oxide-zirconium oxide composite oxide colloidal particles/the mass of sodium aluminate (in terms of Al ₂ O ₃ ) was 244 ( 0.24 g as Al ₂ O ₃ ) was added and heated at 95° C. for 2 hours, then concentrated using an ultrafiltration device. The obtained dispersion containing the modified titanium oxide-zirconium oxide composite oxide colloidal particles had a total metal oxide concentration of 30.8% by mass, a pH of 4.6, a B-type viscosity of 7.0 mPa·s, and an average particle diameter of 21.0 nm. Met. The Al ₂ O ₃ content contained in the coating layer was 2.4% by mass based on the mass of all composite oxides in the coating layer. The obtained sol was stable with no change in physical properties even after standing at room temperature for one month.
195 g of the obtained sol was charged into an evaporator equipped with an eggplant-shaped flask, 6.0 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and then methanol was gradually added to 600 Torr. 208 g of a methanol-dispersed sol of aluminate-modified modified titanium oxide-zirconium oxide composite oxide colloidal particles was obtained. The resulting methanol-dispersed sol had a total metal oxide concentration of 30.6% by mass, a B-type viscosity of 4.2 mPa s, a pH of 4.8 (diluted with the same mass of water as the sol), a water content of 1.7%, and an average particle size of The diameter was 16 nm. The obtained sol was stable with no change in physical properties even after standing at room temperature for one month.

Example 3 Preparation of Modified Metal Oxide Colloidal Particles (C) To 1880 g of aqueous sol of acidic zirconium oxide-stannic oxide colloidal particles obtained by the same procedure as in Example 1, zirconium oxide-oxidized 20 g of an aqueous sodium aluminate solution (0.087 g as Al ₂ O ₃ ) was added so that the mass of the composite oxide of the stannic composite oxide colloidal particles/the mass of sodium aluminate (in terms of Al ₂ O ₃ ) was 650. The mixture was added and heated at 95° C. for 2 hours, then concentrated using an ultrafiltration device. The obtained dispersion containing the modified zirconium oxide-stannic oxide composite oxide colloidal particles had a total metal oxide concentration of 30.6% by mass, a pH of 5.4, a B-type viscosity of 13.4 mPa s, and an average particle diameter of 14 nm. Met. Also, the Al ₂ O ₃ content contained in the coating layer was 1.17% by mass based on the mass of all composite oxides in the coating layer. The obtained sol was stable with no change in physical properties even after standing at room temperature for one month.
164 g of the obtained sol was charged into an evaporator equipped with an eggplant-shaped flask, 5.0 g of γ-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and then methanol was gradually added. 213 g of a methanol-dispersed sol of modified zirconium oxide-stannic oxide composite oxide colloidal particles modified with an aluminate was obtained by distilling off water at 600 Torr. The resulting methanol-dispersed sol had a total metal oxide concentration of 31.0% by mass, a B-type viscosity of 5.3 mPa s, a pH of 5.6 (diluted with the same mass of water as the sol), a water content of 0.8%, and an average particle size of The diameter was 16 nm. The obtained sol was stable with no change in physical properties even after standing at room temperature for one month.

Example 4 Preparation of Modified Metal Oxide Colloidal Particles (C) To 1880 g of aqueous sol of acidic zirconium oxide-stannic oxide colloidal particles obtained by the same procedure as in Example 1, zirconium oxide-oxidized 20 g of an aqueous sodium aluminate solution (0.087 g as Al ₂ O ₃ ) was added so that the mass of the composite oxide of the stannic composite oxide colloidal particles/the mass of sodium aluminate (in terms of Al ₂ O ₃ ) was 650. The mixture was added and heated at 95° C. for 2 hours, then concentrated using an ultrafiltration device. The obtained dispersion containing the modified zirconium oxide-stannic oxide composite oxide colloidal particles had a total metal oxide concentration of 30.6% by mass, a pH of 5.4, a B-type viscosity of 13.4 mPa s, and an average particle diameter of 14 nm. Met. Also, the Al ₂ O ₃ content contained in the coating layer was 1.17% by mass based on the mass of all composite oxides in the coating layer. The obtained sol was stable with no change in physical properties even after standing at room temperature for one month.
164 g of the obtained sol was put into an evaporator equipped with an eggplant-shaped flask, and water was distilled off at 600 Torr while methanol was gradually added, whereby a modified zirconium oxide-stannic oxide composite oxide modified with aluminate was obtained. 149 g of a methanol-dispersed sol of colloidal particles was obtained. The resulting methanol-dispersed sol had a total metal oxide concentration of 31.0% by mass, a B-type viscosity of 4.6 mPa s, a pH of 5.7 (diluted with the same mass of water as the sol), a water content of 0.8%, and an average particle size of The diameter was 16 nm. The obtained sol was stable with no change in physical properties even after standing at room temperature for one month.

Comparative example 1
The alkaline stannic oxide-silica composite colloidal particles prepared in Production Example 1 were added to 830 g of the aqueous sol of the zirconium oxide-stannic oxide composite oxide colloidal particles prepared in Production Example 2 (containing 50 g of all metal oxides). 577 g of aqueous sol was added and thoroughly stirred.
Then, the mixture was heated and aged at 95° C. for 2 hours to obtain 1400 g of an aqueous sol of zirconium oxide-stannic oxide composite oxide colloidal particles coated with stannic oxide-silica composite colloidal particles. The resulting sol had a pH of 8.1 and a total metal oxide concentration of 4.6% by mass.
The obtained aqueous sol of the zirconium oxide-stannic oxide composite oxide colloidal particles was passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and an acidic zirconium oxide-oxidized 1910 g of an aqueous sol of colloidal particles of stannic compound oxide was obtained. The resulting sol had a pH of 3.3 and a total metal oxide concentration of 3.4% by mass.
Then, when an attempt was made to concentrate using an ultrafiltration device, the product thickened and gelled during the concentration.

Comparative example 2
830 g of the aqueous sol of the zirconium oxide-stannic oxide composite oxide colloidal particles prepared in Production Example 2 (containing 50 g of all metal oxides) was added to the aqueous sol of the stannic oxide-silica composite colloidal particles prepared in Production Example 1. 577 g was added and stirred well.
Then, the mixture was heated and aged at 95° C. for 2 hours to obtain 1400 g of an aqueous sol of zirconium oxide-stannic oxide composite oxide colloidal particles coated with stannic oxide-silica composite colloidal particles. The resulting sol had a pH of 8.1 and a total metal oxide concentration of 4.6% by mass.
The obtained aqueous sol of the zirconium oxide-stannic oxide composite oxide colloidal particles was passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and an acidic zirconium oxide-oxidized 1910 g of an aqueous sol of colloidal particles of stannic compound oxide was obtained. The resulting sol had a pH of 3.3 and a total metal oxide concentration of 3.4% by mass.
0.40 g of diisobutylamine was added to the obtained acidic sol, and concentrated to a total metal oxide concentration of 20.6% by mass using an ultrafiltration device. The resulting sol had a pH of 3.9, a B-type viscosity of 7.0 mPa·s, and an average particle size of 24 nm. The obtained sol was stable with no change in physical properties even after standing at room temperature for one month.
The obtained sol was put into an evaporator equipped with an eggplant-shaped flask, 5.0 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and then methanol was gradually added at 600 Torr. By distilling off water, 213 g of a methanol-dispersed sol of diisobutylamine-bonded zirconium oxide-stannic oxide composite oxide colloidal particles was obtained. The resulting methanol-dispersed sol had a total metal oxide concentration of 30.5% by mass, a B-type viscosity of 4.3 mPa s, a pH of 4.9 (diluted with the same mass of water as the sol), a water content of 0.8%, and an average particle size of The diameter was 19 nm. The obtained sol was stable with no change in physical properties even after standing at room temperature for one month.

Comparative example 3
1306 g of the water-dispersed sol obtained in Production Example 3 was added to 1076 g of the water-dispersed sol of alkaline stannic oxide-silica composite colloidal particles prepared in Production Example 1 with stirring. Then, the solution was passed through a column packed with 500 mL of an anion exchange resin (Amberlite (registered trademark) IRA-410, manufactured by Organo Co., Ltd.).
Next, the water-dispersed sol after passing the liquid was heated at 150° C. for 3 hours to obtain a water-dispersed sol of titanium oxide-zirconium oxide composite oxide colloidal particles coated with stannic oxide-silica composite colloidal particles. The resulting water-dispersed sol was 2788 g and had a total metal oxide concentration of 2.2% by mass.
The resulting water-dispersed sol of the colloidal particles of titanium oxide-zirconium oxide composite oxide was passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B) to give an acidic titanium oxide-zirconium oxide. 3427 g of a water-dispersed sol of colloidal composite oxide particles was obtained. The resulting sol had a pH of 2.4 and a total metal oxide concentration of 1.8% by mass.
1.54 g of diisobutylamine was added to the obtained acidic sol, and concentrated to a total metal oxide concentration of 17.6% by mass using an ultrafiltration device. The resulting sol had a B-type viscosity of 4.8 mPa·s, a pH of 4.2 and an average particle size of 27 nm. The obtained sol was stable with no change in physical properties even after standing at room temperature for one month.
337 g of the obtained sol was charged into an evaporator equipped with an eggplant-shaped flask, and then water was distilled off at 600 Torr while methanol was gradually added to obtain diisobutylamine-bonded titanium oxide-zirconium oxide composite oxide colloidal particles. 196 g of methanol-dispersed sol was obtained. The resulting methanol-dispersed sol had a total metal oxide concentration of 30.0% by mass, a B-type viscosity of 3.9 mPa s, a pH of 5.0 (diluted with the same mass of water as the sol), a water content of 0.8%, and an average particle size of The diameter was 20 nm. The obtained sol was stable with no change in physical properties even after standing at room temperature for one month.

Comparative example 4
830 g of the aqueous sol of the zirconium oxide-stannic oxide composite oxide colloidal particles prepared in Production Example 2 (containing 50 g of all metal oxides) was added to the stannic oxide-silica-aluminum oxide composite colloidal particles prepared in Production Example 4. was added and thoroughly stirred.
Then, the mixture was heated and aged at 95° C. for 2 hours to obtain 1334 g of aqueous sol of zirconium oxide-stannic oxide composite oxide colloidal particles coated with stannic oxide-silica-aluminum oxide composite colloidal particles. The resulting sol had a pH of 8.5 and a total metal oxide concentration of 4.5 mass %.
The obtained aqueous sol of the zirconium oxide-stannic oxide composite oxide colloidal particles was passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and an acidic zirconium oxide-oxidized 1348 g of aqueous sol of colloidal particles of stannic compound oxide was obtained. The resulting sol had a pH of 3.1 and a total metal oxide concentration of 4.4% by mass.
The acidic sol thus obtained was concentrated using an ultrafiltration device, but thickened and gelled on the way.

Comparative example 5
830 g of the aqueous sol of the zirconium oxide-stannic oxide composite oxide colloidal particles prepared in Production Example 2 (containing 50 g of all metal oxides) was added to the stannic oxide-silica-aluminum oxide composite colloidal particles prepared in Production Example 4. was added and thoroughly stirred.
Then, the mixture was heated and aged at 95° C. for 2 hours to obtain 1334 g of aqueous sol of zirconium oxide-stannic oxide composite oxide colloidal particles coated with stannic oxide-silica-aluminum oxide composite colloidal particles. The resulting sol had a pH of 8.5 and a total metal oxide concentration of 4.5 mass %.
The obtained aqueous sol of the zirconium oxide-stannic oxide composite oxide colloidal particles was passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and an acidic zirconium oxide-oxidized 1348 g of aqueous sol of colloidal particles of stannic compound oxide was obtained. The resulting sol had a pH of 3.1 and a total metal oxide concentration of 4.4% by mass.
10.1 g of a 5% sodium hydroxide aqueous solution was added to the resulting acidic sol to adjust the pH to 5.2, and then concentrated to a total metal oxide concentration of 22.4% by mass using an ultrafiltration device. The resulting sol had a pH of 5.4, a B-type viscosity of 4.6 mPa·s, and an average particle size of 16 nm. The obtained sol was stable with no change in physical properties even after standing at room temperature for one month.
The obtained sol was put into an evaporator equipped with an eggplant-shaped flask, 5.6 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was heated at 60° C. for 2 hours. Then, water was distilled off at 600 Torr while gradually adding methanol, thereby obtaining 173 g of methanol-dispersed sol of zirconium oxide-stannic oxide composite oxide colloidal particles. The resulting methanol-dispersed sol had a total metal oxide concentration of 31.0% by mass, a B-type viscosity of 3.4 mPa·s, a pH of 5.7 (diluted with the same mass of water as the sol), and a water content of 1.0%. . The average particle size was 69 nm and there was a tendency to aggregate. The resulting sol was unstable and thickened when left at room temperature for one month.

From the results shown in Table 1, the aqueous dispersion containing the modified metal oxide colloidal particles of the present invention was excellent in dispersion stability. Further, even if the surface of the modified metal oxide colloidal particles of the present invention is modified with an organosilicon compound or not, the organic solvent dispersion containing the modified metal oxide colloidal particles of the present invention can be , was excellent in dispersion stability.
On the other hand, from the results shown in Table 2, the aqueous dispersion containing metal oxide colloidal particles in which the coating layer (B) was not modified with sodium aluminate thickened and gelled during concentration (Comparative Example 1 ).
Further, an aqueous dispersion containing metal oxide colloidal particles using stannic oxide-silica-aluminum oxide composite colloidal particles as the coating layer (B) thickened and gelled during concentration (Comparative Example 4). .
Furthermore, as the coating layer (B), an organic solvent dispersion in which sodium hydroxide is added to metal oxide colloidal particles using stannic oxide-silica-aluminum oxide composite colloidal particles is thickened and dispersion stability is improved. It was inferior (Comparative Example 5).
From the above results, it can be seen that the modified metal oxide colloidal particles of the present invention employ the coating layer (B) obtained by modifying the unmodified composite oxide with an aluminate, so that the modified metal oxide colloidal particles It is clear that the aqueous dispersion and the organic solvent dispersion of are excellent in dispersion stability.

Using the modified metal oxide colloidal particles obtained in Examples 1 and 2 and the metal oxide colloidal particles obtained in Comparative Examples 2 and 3, a coating composition was prepared in the following procedure to produce an optical member. It was produced, and various physical properties were measured and evaluated.

Example 5
(Preparation of coating composition)
35.2 parts by mass of γ-glycidoxypropyltrimethoxysilane and 94.6 parts by mass of methanol were added to a glass container equipped with a magnetic stirrer, and 8.5 parts by mass of 0.01N hydrochloric acid was added while stirring. Dropped in 30 minutes. After the dropwise addition was completed, stirring was carried out for 2.0 hours to obtain a partially hydrolyzate solution of γ-glycidoxypropyltrimethoxysilane.
Next, 106.7 parts by mass of the methanol-dispersed sol of the modified metal oxide colloidal particles of Example 1 (containing 31.0% by mass in terms of total metal oxide concentration), and aluminum acetylacetonate as a curing agent. Add 0.3 parts by mass to 129.8 parts by mass of the partial hydrolyzate solution of γ-glycidoxypropyltrimethoxysilane described above, stir thoroughly, and then filter to obtain a coating composition for hard coating (coating liquid ) was prepared.
(Production of optical member)
3 mL of the coating liquid was added to a glass petri dish having a diameter of 30 mm, held at 80° C. for 30 minutes, and heat-treated at 120° C. for 2 hours to prepare an optical member.
The obtained optical member was evaluated for yellowness by the following measuring method. Table 3 shows the evaluation results.
(1) Degree of yellowing The degree of yellowing of the obtained optical members was visually examined. Judgment criteria are as follows.
A: No yellowing observed B: Some yellowing observed C: Significant yellowing observed

Example 6
In Example 5, a coating composition was prepared in the same manner as in Example 5, except that the methanol-dispersed sol of the modified metal oxide colloidal particles of Example 1 was changed to the methanol-dispersed sol of the modified metal oxide colloidal particles of Example 2. Preparation and production/evaluation of optical members were carried out.

Comparative example 6
In Example 5, a coating composition was prepared in the same manner as in Example 5, except that the methanol-dispersed sol of modified metal oxide colloidal particles of Example 1 was changed to the methanol-dispersed sol of metal oxide colloidal particles of Comparative Example 2. And the production and evaluation of optical members were carried out.

Comparative example 7
In Example 5, a coating composition was prepared in the same manner as in Example 5, except that the methanol-dispersed sol of the modified metal oxide colloidal particles of Example 1 was changed to the methanol-dispersed sol of the metal oxide colloidal particles of Comparative Example 3. And the production and evaluation of optical members were carried out.

From the results shown in Table 3, no yellowing was observed in the cured film formed from the coating composition using the modified metal oxide colloidal particles (C) of the present invention (Example 5 and Example 6).
On the other hand, from the results shown in Table 3, the cured film formed from the coating composition using the metal oxide colloidal particles containing an organic amine was markedly yellowed (Comparative Examples 6 and 7). ).

From the results shown in Tables 1 to 3, the modified metal oxide colloidal particles of the present invention employ the coating layer (B) obtained by modifying the unmodified composite oxide with an aluminate. Aqueous dispersions and organic solvent dispersions containing modified metal oxide colloidal particles are excellent in dispersion stability, and cured films formed from coating compositions containing the modified metal oxide colloidal particles do not yellow. It is clear that
On the other hand, aqueous dispersions and organic solvent dispersions of metal oxide colloidal particles containing organic amines were excellent in dispersion stability, but cured films formed from coating compositions containing the metal oxide colloidal particles were , markedly yellowed.

Claims

Using the metal oxide colloidal particles (A) as nuclei, the surfaces thereof are covered with a coating layer (B) comprising a composite oxide of Si and Al and at least one atom selected from the group consisting of Sn, Sb and W. Modified metal oxide colloidal particles (C) having an average particle size of 5 to 300 nm.
The coating layer (B) is a layer obtained by modifying an unmodified composite oxide of Si and at least one atom selected from the group consisting of Sn, Sb and W with an aluminate. Item 1. Modified metal oxide colloidal particles (C) according to item 1.
The metal oxide colloidal particles (A) are selected from the group consisting of Ti, Mn, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce. 3. The modified metal oxide colloidal particles (C) according to claim 1, which are colloidal particles of at least one metal oxide.
The modified metal oxide colloidal particles (C) according to any one of claims 1 to 3, wherein the metal oxide colloidal particles (A) have an average primary particle size of 1 to 300 nm.
The Al content (in terms of Al 2 O 3 ) in the coating layer (B) is based on the total mass of all metal oxides in the metal oxide colloidal particles (A) and all composite oxides in the coating layer (B). 5. The modified metal oxide colloidal particles (C) according to any one of claims 1 to 4, wherein the content is 0.05 to 0.5% by mass.
1 to 10, wherein the Al content (in terms of Al 2 O 3 ) in the coating layer (B) is 0.1 to 10% by mass based on the mass of the total composite oxide in the coating layer (B). Item 6. Modified metal oxide colloidal particles (C) according to any one of items 5.
The content of total nitrogen derived from organic amines in the modified colloidal metal oxide particles (C) is the sum of all metal oxides in the colloidal metal oxide particles (A) and all composite oxides in the coating layer (B). 7. The modified metal oxide colloidal particles (C) according to any one of claims 1 to 6, which is 0.05% by mass or less based on the mass.
Claims 1 to 7, wherein at least part of the surface of the modified metal oxide colloidal particles (C) is surface-modified with an organosilicon compound represented by general formula (1) or general formula (2). Modified metal oxide colloidal particles (C) according to any one of .
(R 1′ ) a′ Si(R 2′ ) 4-a′ Formula (1)
[(R 3′ ) d Si(R 4′ ) 3-d ] 2 Y e Formula (2)
(In formulas (1) and (2),
R 1' and R 3' are alkyl groups, phenyl groups, vinyl groups, acryloxy groups, methacryloxy groups, epoxy groups, styryl groups, isocyanate groups, mercapto groups, ureido groups, acid anhydride groups, or carbon atoms containing functional groups thereof. It is an alkylene group of numbers 1 to 10 and represents an alkylene group bonded to a silicon atom via a Si—C bond, and when there are a plurality of each of R 1' and R 3' , each R 1' and each R 3 ' may be the same or different,
R 2' and R 4 ' each represents a hydrolyzable group consisting of an alkoxy group, an acyloxy group, or a halogen atom ; may be the same or different,
Y represents an alkylene group, an arylene group, an NH group or an oxygen atom.
a′ represents an integer of 1 to 3, d represents an integer of 0 to 3, and e represents an integer of 0 or 1. )
A dispersion of modified metal oxide colloidal particles (C) in which the modified metal oxide colloidal particles (C) according to any one of claims 1 to 8 are dispersed in an aqueous medium or an organic solvent.
Component (S): an organosilicon compound and/or a silicon-containing substance that is a hydrolyzate thereof, and Component (T): the modified metal oxide colloid particles according to any one of claims 1 to 8 ( C)
A coating composition comprising
A coating composition in which the organosilicon compound as component (S) contains at least one organosilicon compound selected from the group consisting of compounds represented by the following formula (I) and compounds represented by the following formula (II): thing.
(R 1 ) a (R 3 ) b Si(OR 2 ) 4-(a+b) (I)
(In the formula,
R 1 and R 3 each independently represent an alkyl group, an aryl group, a vinyl group, a halogenated alkyl group, a halogenated aryl group or an alkenyl group, or an epoxy group, an isocyanate group, an acryloyl group, a methacryloyl group, represents an organic group that is a monovalent organic group having a mercapto group, a ureido group, or a cyano group and is bonded to a silicon atom via a Si—C bond,
R 2 represents an alkyl group having 1 to 8 carbon atoms, an aryl group, an aralkyl group, an alkoxyalkyl group, or an acyl group;
a and b each independently represent an integer of 0, 1, or 2, and a+b is an integer of 0, 1, or 2; )
[(R 4 ) c Si(OX) 3-c ] 2 Y (II)
(In the formula,
R 4 represents an alkyl group having 1 to 5 carbon atoms,
X represents an alkyl group or acyl group having 1 to 4 carbon atoms,
Y represents a methylene group or an alkylene group having 2 to 20 carbon atoms,
c represents an integer of 0 or 1; )
(K) component: at least one resin selected from the group consisting of thermosetting resins, thermoplastic resins and ultraviolet curable resins, and (T) component: any one of claims 1 to 8 Modified metal oxide colloidal particles (C)
A coating composition comprising:
A cured film produced using the coating composition according to claim 10 or claim 11.
An optical member having the cured film according to claim 12 on the surface of an optical substrate.
An optical member further comprising an antireflection film on the surface of the cured film according to claim 13.
A method for producing modified metal oxide colloidal particles (C), comprising the following steps (a) to (d).
(a) a dispersion containing metal oxide colloidal particles (A) and a dispersion of unmodified composite oxide colloidal particles containing Si and at least one atom selected from the group consisting of Sn, Sb and W; Step (b) of mixing the mixed solution obtained in step (a) at a temperature of 30 to 320 ° C. for 0.5 to 24 hours (c) Heating the mixed solution obtained in step (b) with H A step of contacting with a type cation exchange resin (d) A step of mixing the mixed solution obtained in the step (c) and an aluminate aqueous solution, and heating at a temperature of 30 to 320 ° C. for 0.5 to 24 hours.
In the step (a), the weight of the total composite oxide of the unmodified composite oxide colloidal particles/the weight of the total metal oxide of the metal oxide colloidal particles (A) is adjusted to 0.05 to 0.50. , a dispersion containing metal oxide colloidal particles (A) and a dispersion of unmodified composite oxide colloidal particles containing Si and at least one atom selected from the group consisting of Sn, Sb and W are mixed. 16. The method for producing modified metal oxide colloidal particles (C) according to claim 15, which is a step of
In the step (d), the mixed solution obtained in the step (c) and the aqueous aluminate solution are mixed so that the mass of the total composite oxide/the mass of the aluminate (in terms of Al 2 O 3 ) is 50 to 800. 17. The method for producing modified metal oxide colloidal particles (C) according to claim 15 or 16, which is a step of mixing with.
18. The method for producing modified metal oxide colloidal particles (C) according to any one of claims 15 to 17, wherein the heat treatment in step (b) is performed under hydrothermal conditions.