TW202344480A - Modified metal oxide colloidal particles, and method for producing same - Google Patents

Abstract

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. 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 DEG 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 DEG C for 0.5-24 hours.

Description

Modified metal oxide colloidal particles and manufacturing method thereof

The present invention relates to coating the surface of metal oxide colloidal particles with a coating layer composed of 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, a method for producing the modified metal oxide colloidal particles, and a coating composition containing the modified metal oxide colloidal particles.

Plastic molded bodies are widely used due to their advantages such as light weight, easy processability, and impact resistance. However, they are easily injured due to insufficient hardness, easily corroded by solvents, attract dust due to being charged, and have insufficient heat resistance. shortcoming. Therefore, when the plastic molded article is used as spectacle lenses, window materials, etc., it has the above-mentioned practical disadvantages compared with the inorganic glass molded article. Therefore, a proposal has been made to provide a protective coat (protective film) to the plastic molded body. In fact, many types of coating compositions for use in protective coats have been proposed.

As a coating that imparts hardness close to that of an inorganic system, a coating composition containing an organosilicon compound or its hydrolyzate as a main component (resin component or coating film-forming component) is used for eyeglass lenses (Patent Document 1). The above-mentioned coating composition is still unsatisfactory in terms of scratch resistance, so it has also been proposed that silica sol dispersed in a colloidal state is further added thereto, and it is put into practical use as a spectacle lens (Patent Document 2).

However, in the past, plastic eyeglass lenses were mostly manufactured by casting polymerization of diethylene glycol bisallyl carbonate. However, the refractive index of this lens is about 1.50, which is lower than the refractive index of a glass lens, which is about 1.52. Therefore, when the lens is used for myopia, it has the disadvantage that the surrounding thickness becomes thicker. Therefore, in recent years, monomers with a higher refractive index than diethylene glycol bisallyl carbonate have been developed, and high refractive index resin materials with a refractive index in the range of 1.54 to 1.76 have been proposed (Patent Documents 3 and 4). For such a high refractive index resin lens, a method of using a colloidal dispersion of metal oxide fine particles of Sb and Ti as a coating material has been proposed (Patent Documents 5 and 6).

It is also disclosed that a colloidal particle (a) containing a silane coupling agent and a metal oxide having a primary particle diameter of 2 to 60 nm is used as a core, and the surface is coated with a coating (b) made of colloidal particles of an acidic oxide. The obtained particles (c) are coated, and (c) is contained in a ratio of 2 to 50% by mass in terms of metal oxide, and is then coated with a stable modified metal oxide sol having a primary particle diameter of 2 to 100 nm. coating composition. Then, as a specific example of the colloidal particles used, a modified titanium oxide-zirconia-second tin oxide composite colloid coated with antimony pentoxide containing an alkylamine is disclosed (Patent Document 7). There is also disclosed a titanium oxide-second tin oxide-zirconia composite colloid stabilized with an alkylamine or an oxycarboxylic acid (Patent Document 8).

Further having core particles and a shell layer, the core particles are composed of (a) an oxide containing as a main component one metal element selected from the group consisting of zirconium, tin, titanium, niobium, tungsten, antimony, indium, and lanthanum Core particles made of microparticles or composite oxide microparticles. The shell layer is (b) covering the aforementioned core particles and contains a composite oxide shell layer. The composite oxide shell layer contains a composite oxide of silicon and aluminum as the main components. things. The weight ratio (SiO ₂ /Al ₂ O ₃ ) of the silicon and aluminum oxides contained in the shell layer is in the range of 30 to 2000, and the weight of the composite oxide shell layer is relative to 100 parts by weight of the core particles. A dispersion liquid containing core-shell type oxide fine particles and a dispersion medium in a range of 5 to 100 parts by weight has been proposed (Patent Document 9). However, if the above-mentioned composite oxide shell layer contains metal elements other than silicon and aluminum, the surface charge of the core-shell type oxide fine particles may be reduced, or the coating rate of the core particle shell layer may be reduced. . In addition, when producing the above-mentioned core-shell type oxide fine particles, in order to suppress a decrease in the shell coverage ratio of the core particles or a decrease in the load on the surface of the core-shell type composite oxide fine particles, it is necessary to contain silane oxide and/or silicic acid. The silicon compound solution and the aluminate aqueous solution are added to the aqueous dispersion of core particles at a certain speed at the same time. [Prior art documents] [Patent documents]

[Patent Document 1] Japanese Patent Application Publication No. Sho 52-16586 [Patent Document 2] Japanese Patent Application Publication No. Sho 53-111336 [Patent Document 3] Japanese Patent Application Publication No. Sho 55-13747 [Patent Document 4] Japanese Patent Application Publication No. Sho 64-54021 [Patent Document 5] Japanese Patent Application Publication No. Sho 62-151801 [Patent Document 6] Japanese Patent Application Publication No. Sho 63-275682 [Patent Document 7] Japanese Patent Application Publication No. 2001-123115 [Patent Document 8] Japanese Patent Application Publication No. 10-306258 [Patent Document 9] Japanese Patent Application Publication No. 2015-143297

[Problem solved by the invention]

A coating film formed from a coating composition using metal oxide colloidal particles containing organic amines such as alkyl amines has a problem of being prone to yellowing caused by organic amines.

An object of the present invention is to provide modified metal oxide colloidal particles that can suppress yellowing of a cured film when used in a coating composition. [Means to solve the problem]

In order to solve the above-mentioned problems, the present inventors repeated detailed examinations and found that the surface of the metal oxide colloidal particles serving as the core is a composite oxide of at least one type of atom selected from the group consisting of Sn, Sb, and W via Si and Al. The resulting coating layer (B) is, in particular, a coating modified by Si and an unmodified composite oxide of at least one atom selected from the group consisting of Sn, Sb and W with aluminate. By coating the particles with layer (B), when the particles are added to the coating composition, a cured film that is resistant to yellowing can be formed, and when the particles are dispersed in an organic solvent, an organic solvent dispersion with excellent dispersion stability can be obtained. liquid, and then complete the present invention.

That is, the present invention relates to the modified metal oxide colloidal particle (C) as the first aspect, wherein the metal oxide colloidal particle (A) is used as a core, and the surface is made of Si and Al and a material selected from the group consisting of Sn, Sb and It is coated with a coating layer (B) composed of a composite oxide of at least one type of atom represented by W, and has an average particle diameter of 5 to 300 nm. The modified metal oxide colloidal particles (C) according to the first aspect as the second aspect, wherein the coating layer (B) is composed of Si and at least one atom selected from the group consisting of Sn, Sb and W. A layer of unmodified composite oxide modified with aluminate. The modified metal oxide colloidal particles (C) according to the first aspect or the second aspect as the third aspect, wherein the metal oxide colloidal particles (A) are selected from the group consisting of Ti, Mn, Fe, Cu, Zn, Colloidal particles of at least one metal oxide consisting of Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce. The fourth aspect is the modified metal oxide colloidal particles (C) described in any one of the first to third aspects, wherein the metal oxide colloidal particles (A) have an average primary particle diameter of 1 to 300 nm. Regarding the modified metal oxide colloidal particles (C) according to any one of the first to fourth aspects as the fifth aspect, the Al content (in terms of Al ₂ O ₃ ) in the coating layer (B) is Based on the total mass of the total metal oxide of the metal oxide colloidal particles (A) and the total composite oxide of the coating layer (B), it is 0.05 to 0.5 mass %. The modified metal oxide colloidal particles (C) according to any one of the first to fifth aspects as the sixth aspect, wherein the Al content (in terms of Al ₂ O ₃ ) in the coating layer (B) is , based on the mass of the total composite oxide of the coating layer (B), it is 0.1 to 10 mass %. Regarding the modified metal oxide colloidal particles (C) according to any one of the first to sixth aspects as the seventh aspect, wherein the total nitrogen derived from the organic amine in the modified metal oxide colloidal particles (C) The content of is 0.05% by mass or less based on the total mass of the total metal oxide of the metal oxide colloidal particles (A) and the total composite oxide of the coating layer (B). The modified metal oxide colloidal particles (C) according to any one of the first to seventh aspects as an eighth aspect, wherein at least a part of the surface of the modified metal oxide colloidal particles (C) is modified by the general formula (1) or the organosilicon compound represented by general formula (2) for surface modification. (In formula (1) and formula (2), R ^1' and R ^3' represent an alkyl group, a phenyl group, a vinyl group, an acryloxy group, a methacryloxy group, an epoxy group, a styryl group, and an isocyanate group. group, mercapto group, ureido group, acid anhydride group or an alkylene group with 1 to 10 carbon atoms containing these functional groups, and an alkylene group bonded to a silicon atom through a Si-C bond, R ^1' and R When ^3' each exists in the plural, each R ^1' and each R ^3' may be the same or different, and R ^2' and R ^4' represent an alkoxy group, a hydroxyl group or a halogen atom. When the hydrolyzable group R ^2' and R ^4' each exist in plural, each R ^2' and each R ^4' may be the same or different, and Y represents an alkylene group, an aryl group, an NH group or Oxygen atom. a ^' represents an integer from 1 to 3, d represents an integer from 0 to 3, and e represents an integer from 0 or 1).

Regarding the dispersion liquid of modified metal oxide colloidal particles (C) as a ninth aspect, the modified metal oxide colloidal particles (C) according to any one of the first to eighth aspects are dispersed in an aqueous medium. or organic solvents.

A coating composition according to the tenth aspect, which contains (S) component: a silicon-containing substance of an organosilicon compound and/or its hydrolyzate, and (T) component: any one of the first to eighth aspects. In the modified metal oxide colloidal particles (C) described above, the organosilicon compound of the component (S) contains at least one compound selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula (II). 1 kind of organosilicon compound; (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 acryl group or a methacryl group. A monovalent organic group such as a mercapto group, a ureido group or a cyano group, and an organic group bonded to a silicon atom through a Si-C bond. R ² represents an alkyl group, aryl group, or aryl group having 1 to 8 carbon atoms. Alkyl group, alkoxyalkyl group or 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.) (In the formula, R ⁴ represents an alkyl group with 1 to 5 carbon atoms, X represents an alkyl group or hydroxyl group with 1 to 4 carbon atoms, Y represents a methylene group or an alkylene group with 2 to 20 carbon atoms, c an integer representing 0 or 1). A coating composition according to the eleventh aspect, which contains (K) component: at least one resin selected from the group consisting of a thermosetting resin, a thermoplastic resin, and an ultraviolet curing resin, and (T) component: as in the first aspect to Modified metal oxide colloidal particles (C) according to any one of the eighth aspects.

The cured film as a 12th viewpoint is produced using the coating composition as described in the 10th viewpoint or the 11th viewpoint. An optical member according to a thirteenth aspect has the cured film according to the twelfth aspect on the surface of the optical base material. An optical member according to a fourteenth aspect further includes an antireflection film on the surface of the cured film according to the thirteenth aspect.

The method for producing the modified metal oxide colloidal particles (C) according to the fifteenth aspect includes the following steps (a) to (d). (a) The step of mixing a dispersion containing metal oxide colloidal particles (A) and a dispersion of Si and at least one atom selected from the group consisting of Sn, Sb and W and unmodified composite oxide colloidal particles ( b) heating 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-type cation exchange resin In the contacting step (d), the mixed solution obtained in step (c) and the aluminate aqueous solution are mixed, and a heating step is performed at a temperature of 30 to 320°C for 0.5 to 24 hours. As a sixteenth aspect, there is a method for producing the modified metal oxide colloidal particles (C) as described in the fifteenth aspect, wherein the step (a) includes mixing a dispersion liquid containing the metal oxide colloidal particles (A), and A dispersion of Si and unmodified composite oxide colloidal particles of at least one atom selected from the group consisting of Sn, Sb and W, such that the mass of the total composite oxide of the unmodified composite oxide colloidal particles/metal oxide The mass of the total metal oxide of the colloidal particles (A) is in the range of 0.05 to 0.50. Regarding the manufacturing method of the modified metal oxide colloidal particles (C) according to the 15th aspect or the 16th aspect as the 17th aspect, the step (d) includes mixing the mixed solution obtained in the step (c) and aluminum The aqueous salt solution is a step in which the mass of the total composite oxide/the mass of the aluminate (in terms of Al ₂ O ₃ ) becomes 50 to 800. The method for producing the modified metal oxide colloidal particles (C) according to any one of the fifteenth to seventeenth aspects as an eighteenth aspect, wherein the heat treatment in step (b) is performed under hydrothermal conditions. [Effects of the invention]

When the modified metal oxide colloidal particles of the present invention are added to a coating composition, they are a composition that can form a cured film that is not prone to yellowing. In addition, the coating composition of the present invention can form a cured film that is less likely to yellow. Therefore, an optical member having a cured film made of a coating composition containing the modified metal oxide colloidal particles of the present invention can be used particularly as a material for glasses or a display.

An aqueous dispersion in which the modified metal oxide colloidal particles of the present invention are dispersed in an aqueous medium has excellent dispersion stability. In addition, the organic solvent dispersion in which the modified metal oxide colloidal particles of the present invention are dispersed in an organic solvent can be made by surface-modifying the surface of the modified metal oxide colloidal particles with an organosilicon compound, or without surface modification. Indicates those with excellent dispersion stability.

[Types of carrying out the invention] [Modified metal oxide colloidal particles (C)]

The modified metal oxide colloidal particle (C) of the present invention uses the metal oxide colloidal particle (A) as a core, and the surface is made of Si and Al and at least one selected from the group consisting of Sn, Sb and W. The particles are coated with a coating layer (B) made of a composite oxide of atoms, and have an average particle diameter of 5 to 300 nm. Furthermore, as a preferred aspect of the present invention, a metal oxide colloidal particle (A) is used as a core, and the surface is made of Si and at least one type of atom selected from the group consisting of Sn, Sb and W. The modified composite oxide is coated with a coating layer (B) modified with aluminate to form modified metal oxide colloidal particles (C) with an average particle diameter of 5 to 300 nm.

<Metal oxide colloidal particles (A)> Examples of the metal oxide colloidal particles (A) include those selected from the group consisting of Ti, Mn, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Colloidal particles of oxides of at least one metal consisting of Ta, W, Pb, Bi and Ce. The colloidal particles (A) of the metal oxide are colloidal particles of metal oxides with an atomic valence of 2 to 6. Examples of the form of these metal oxides include TiO ₂ , MnO, Fe ₂ O ₃ , and CuO. , ZnO, Y ₂ O ₃ , ZrO ₂ , Nb ₂ O ₅ , MoO ₃ , In ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Ta ₂ O ₅ , WO ₃ , PbO, Bi ₂ O ₃ , CeO _2, etc. . These metal oxides can be used individually or in combination of multiple types. Examples of the combination method include a method of mixing several types of metal oxides, a method of compounding the metal oxides, or a method of forming a solid solution of the metal oxides at the atomic level.

When the colloidal particles (A) of the metal oxide are composed of a plurality of metal oxides, for example, TiO ₂ particles and SnO ₂ particles are chemically bonded at the interface to _be composited. -SnO ₂ composite oxide colloidal particles, SnO ₂ particles and WO ₃ particles are chemically bonded at this interface to make the SnO ₂ -WO ₃ composite oxide colloidal particles, SnO ₂ particles and ZrO ₂ particles complex. TiO ₂ -ZrO 2 - is obtained by forming a solid solution between TiO ₂ and ZrO 2 and SnO _{2 at the atomic level. SnO 2 -ZrO 2 composite oxide colloidal} particles are composited by _chemical bonding at this interface. SnO ₂ composite oxide colloidal particles, etc. Therefore, these composite oxide colloidal particles are not just a mixture of metal oxide particles such as TiO ₂ particles and SnO ₂ particles. Furthermore, the colloidal particles (A) of the metal oxide can be used as a compound composed of a combination of metal components, and examples thereof include ZnSb ₂ O ₆ , InSbO ₄ , and ZnSnO ₃ .

The colloidal particles (A) of the metal oxide can be produced by a known method, for example, an ion exchange method, a degumming method, a hydrolysis method, or a reaction method. Examples of the ion exchange method include a method of treating an acidic salt of the metal with a hydrogen-type ion exchange resin, or a method of treating an alkaline salt of the metal with a hydroxyl-type anion exchange resin. As an example of the degelling method, a gel obtained by neutralizing an acidic salt of the metal with an alkali or neutralizing an alkaline salt of the metal with an acid is washed, and then the gel is washed with an acid. Or the method of degumming it with alkali. Examples of the hydrolysis method include a method of hydrolyzing an alkoxide of the aforementioned metal, or a method of hydrolyzing an alkali salt of the aforementioned metal under heating and then removing unnecessary acid. An example of the reaction method is a method of reacting the powder of the aforementioned metal with an acid. Furthermore, for example, composite metal oxide colloidal particles can be obtained by mixing metal oxide colloidal particles obtained by these known methods and an acidic salt of metal.

Furthermore, when the colloidal particles (A) of the metal oxide contain titanium oxide, the particles may be amorphous or may be crystals of anatase type, rutile type, brookite type, etc. In addition, it may also be an anorthopyroxene-type titanium compound such as barium titanate (represented by BaTiO ₃ or BaO･TiO _2. ). Among them, those in which the crystal form of the colloidal particles of the composite oxide containing titanium oxide as the main component is the rutile type is also preferred. When the colloidal particles (A) of the metal oxide contain zirconium oxide, the particles may be amorphous or may be crystals such as monoclinic crystals, tetragonal crystals, and cubic crystals.

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

<Coating Layer (B)> The coating layer (B) is a layer composed of a composite oxide of Si, Al and at least one atom selected from the group consisting of Sn, Sb and W. Preferably, it is Si and a compound oxide selected from the group consisting of Sn, Sb and W. A layer formed by modifying an unmodified composite oxide of at least one atom of Sn, Sb, and W with aluminate. However, the composite oxide is different from the metal oxide of the metal oxide colloidal particles (A). Examples of the coating layer (B) include SiO _{2 -SnO 2 composite oxide colloidal particles in which SiO 2 particles and SnO 2 particles are} chemically bonded at the interface and are composited with aluminate. The modified SiO ₂ -SnO ₂ -Al ₂ O ₃ coating layer, SiO ₂ particles and Sb ₂ O ₅ particles are chemically bonded at the interface to form a complex SiO ₂ -Sb ₂ O ₅ composite oxidation The SiO ₂ -Sb ₂ O ₅ -Al ₂ O ₃ coating layer of the colloid particles modified with aluminate, SiO ₂ particles and WO ₃ particles are chemically bonded at the interface to composite them. ₂ - _WO3 composite oxide colloidal particles are coated with _SiO2 - _WO3 - _Al2O3 modified with _aluminate , etc. Moreover, the coating layer (B) may be, for example, a SiO ₂ -SnO ₂ composite oxidation process in which the metal oxide colloid (A) is chemically bonded with SiO ₂ particles and SnO ₂ particles at the interface. After coating the colloid particles, they are modified with aluminate to form a SiO ₂ -SnO ₂ -Al ₂ O ₃ coating layer. The coating layer (B) is preferably a layer in which Si and an unmodified composite oxide of at least one atom selected from the group consisting of Sn, Sb and W are modified with aluminate. In addition, part or all of the unmodified composite oxide may be modified with aluminate, and it is preferable that all of the unmodified composite oxide be modified with aluminate. This can also be expressed when the modified metal oxide colloidal particles (C) provided with the coating layer (B) in which the unmodified composite oxide is modified with aluminate become a dispersion liquid in which an organic solvent is used as the medium. Good dispersion.

Although the detailed mechanism of modification by aluminate has not yet been elucidated, according to RALPH K.ILER, THE CHEMISTRY OF SILICA, JOHN WILEY & SONS, it is known that Si atoms and Al atoms both form 4 or 6 coordination for O atoms number, and both have almost the same atomic radius. Therefore, since the tetrahydroxide aluminate ion and the orthosilicate ion are geometrically similar, the tetrahydroxide aluminate ion is inserted between the Si-O bonds on the SiO ₂ surface, or the Al atom is formed by the Si atom Exchange, Si atoms and Al atoms are bonded through O atoms, and it is speculated that the unmodified composite oxide can be modified by aluminate.

The aforementioned 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 acidic salt of the above-mentioned atoms is treated with a hydrogen-form ion exchange resin. An example of the oxidation method is a method of reacting atoms or inorganic oxide powder 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 dispersion type fluorescence X-ray analyzer. The Al content (in Al ₂ O ₃ conversion) in the coating layer (B) is based on the total mass of the full metal oxide of the metal oxide colloidal particles (A) and the full composite oxide of the coating layer (B), for example It is in the range of 0.05 to 0.5 mass% or 0.08 to 0.5 mass%. Among them, the total mass of the total metal oxide of the metal oxide colloidal particle (A) and the total composite oxide of the coating layer (B) can be determined by the sintering method. In addition, the Al content (in terms of Al ₂ O ₃ ) in the cladding layer (B) depends on the mass of the total composite oxide of the cladding layer (B), and is, for example, in the range of 0.1 to 10% by mass.

＜Modified metal oxide colloidal particles (C)＞ The aforementioned modified metal oxide colloidal particles (C) are particles with an average particle diameter of 5 to 300 nm, which are formed by using the metal oxide colloidal particle (A) as a core and coating the surface with the aforementioned coating layer (B). . The average particle diameter of the modified metal oxide colloidal particles (C) can be measured by a dynamic light scattering method (DLS method). The average particle diameter is 5 to 300 nm, preferably 5 to 200 nm. In addition, since the modified metal oxide colloidal particles (C) are particles obtained by forming a chemical bond with the coating layer (B) on the surface of the metal oxide colloidal particles (A), the modified metal oxide The average primary particle diameter of the colloidal particles (C) as measured by a transmission electron microscope does not necessarily need to be larger than the average primary particle diameter of the metal oxide colloidal particles (A), and the chemical bonding may vary slightly. The average primary particle diameter of the modified metal oxide colloidal particles (C) measured by a transmission electron microscope is, for example, in the range of 5 to 300 nm or 5 to 200 nm.

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

The modified metal oxide colloidal particles (C) contain substantially no organic amine. Specifically, the total nitrogen content derived from the organic amine in the modified metal oxide colloidal particles (C) is determined by the total composite oxidation of the total metal oxide of the metal oxide colloidal particles (A) and the coating layer (B). When the total mass of substances is used as a basis, it is, for example, 0.05 mass% or less or 0.01 mass% or less. The total nitrogen content derived from the organic amine in the modified metal oxide colloidal particles (C) is quantified by proton chromatography, and the organic amine derived from the organic amine is calculated. It is obtained from the total nitrogen content. In addition, the total mass of the total metal oxide of the metal oxide colloidal particle (A) and the total composite oxide of the coating layer (B) can be determined by a sintering method.

<Modified metal oxide colloidal particles (C) surface-modified with an organosilicon compound> In the modified metal oxide colloidal particles (C), at least part of the surface can be modified by the general formula (1) or the general formula The organosilicon compound shown in (2) is surface modified. (In formula (1) and formula (2), R ^1' and R ^3' represent an alkyl group, a phenyl group, a vinyl group, an acryloxy group, a methacryloxy group, an epoxy group, a styryl group, and an isocyanate group. group, mercapto group, ureido group, acid anhydride group or an alkylene group with 1 to 10 carbon atoms containing these functional groups, and represents an alkylene group bonded to a silicon atom through a Si-C bond, R ^1' and When R ^3' each exists in a plural number, each R ^1' and each R ^3' may be the same or different. R ^2' and R ^4' represent an alkoxy group, a hydroxyl group or a halogen atom. Hydrolyzable group, when R ^2' and R ^4' each exist in plural, each R ^2' and each R ^4' may be the same or different, Y represents an alkylene group, an aryl group, or an NH group or oxygen atom. a ^' represents an integer from 1 to 3, d represents an integer from 0 to 3, and e represents an integer from 0 or 1).

Examples of the alkyl group include an alkyl group having 1 to 10 carbon atoms. Examples of the alkoxy group include an alkoxy group having 1 to 10 carbon atoms. Examples of the acyloxy group include an alkyl group having 1 to 10 carbon atoms. Examples of the halogen atom of the hydroxyl group having 1 to 10 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and examples of the arylyl group include an aryl group having 6 to 10 carbon atoms. In addition, the aforementioned epoxy group may be not only an epoxy group but also a group containing an epoxy group (glycidyl group, glycidyloxy group, epoxycycloalkyl group, etc.).

Specific examples of the organosilicon compound represented by the formula (1) include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane. , n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, phenyl Trimethoxysilane, phenyltriethoxysilane, dimethoxydiphenylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, methylvinyldimethoxysilane, methylethylene diethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Methyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxyoctyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane Silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane Silane (γ-glycidoxypropyltrimethoxysilane), 3-glycidoxypropylmethyldiethoxysilane, p-styrenetrimethoxysilane, 3-isocyanatepropyltrimethoxysilane Silane, 3-isocyanatepropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

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

These organosilicon compounds can be suitably selected 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 curing resins. and use. These organosilicon compounds are available from Shin-Etsu Chemical Industry Co., Ltd. or Tokyo Chemical Industry Co., Ltd.

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 the general formula (2), that is, on the modified metal oxide colloidal particles (C) When at least part of the surface of the organosilicon compound represented by the general formula (1) or the general formula (2) is bonded, for example, the aforementioned modified metal oxide colloidal particles (C) (for example, the modified metal oxide colloidal particles (C) Alcohol dispersion sol) and the organosilicon compound (or the alcohol solution) represented by the general formula (1) or the general formula (2) are mixed in a prescribed amount, and (if necessary) a prescribed amount of water is added, and if necessary, a hydrolysis solution such as dilute hydrochloric acid is added. After mixing, place it at room temperature for a set time or heat treatment.

In addition, at least part of the surface of the modified metal oxide colloid particle (C) is surface-modified with an organosilicon compound represented by the general formula (1) or the general formula (2), that is, in the modified metal oxide colloid Other methods in which at least part of the surface of the particle (C) is bonded to the organosilicon compound represented by the general formula (1) or the general formula (2), for example, the aforementioned modified metal oxide colloidal particles (C) (for example, modified metal oxide Aqueous dispersion of colloid 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, and the water is distilled off Distillation method is used to obtain an organic solvent dispersion of modified metal oxide colloidal particles (C) surface-modified with an organosilicon compound. At this time, the amount of water remaining in the organic solvent dispersion is preferably 0.1 mass % to 15 mass % by distillation.

The organosilicon compound represented by the general formula (1) or the general formula (2) bonded to the surface of the modified metal oxide colloidal particle (C) may be used individually by one type, or by mixing two or more types. Furthermore, when performing a surface modification treatment of bonding an organosilicon compound represented by the general formula (1) or the general formula (2) on the surface of the modified metal oxide colloidal particles (C), the aforementioned general formula may be performed in advance. (1) or the partial hydrolysis of the organosilicon compound represented by the general formula (2), or the surface modification treatment can be directly performed without hydrolysis. And after the surface modification treatment, the hydrolyzable group of the organosilicon compound represented by the general formula (1) or the general formula (2) reacts with the hydroxyl group on the surface of the modified metal oxide colloidal particle (C) in a state of reaction: It is good, but there is no problem if some of the hydroxyl groups remain untreated.

In addition, the bonding amount of the organosilicon compound represented by the general formula (1) or the general formula (2) on the surface of the modified metal oxide colloidal particles (C) is not particularly limited. For example, relative to the metal oxide colloidal particles The total mass (100% by mass) of the total metal oxide of (A) and the total composite oxide of the coating layer (B) is, for example, 0.01 to 20 mass%, preferably 0.1 to 20 mass%, and more preferably It is 0.1~15% by mass. In addition, the total mass of the total metal oxide of the metal oxide colloidal particle (A) and the total composite oxide of the coating layer (B) can also be determined by the sintering method.

[Dispersion of modified metal oxide colloidal particles (C)] The modified metal oxide colloidal particles (C) can be used as a dispersion dispersed in an aqueous medium or an organic solvent. A dispersion liquid using an organic solvent as a dispersion medium can be converted into an organic solvent dispersion liquid by replacing water in the dispersion medium of the dispersion liquid dispersed in an aqueous medium with an organic solvent. Moreover, when the dispersion liquid dispersed in an organic solvent is further replaced by another type of organic solvent, it can become an organic solvent dispersion liquid. This substitution can be performed by general methods such as distillation and extreme filtration.

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, propylene glycol monomethyl ether, Ethers such as propylene glycol monoethyl ether, ethyl cellosolve, glycols such as ethylene glycol, and hydrocarbons such as hexane, toluene, and cyclohexane.

The concentration of the modified metal oxide colloidal particles (C) contained in the dispersion liquid can be expressed as the total metal oxide concentration. Among them, the so-called total metal oxide concentration is defined as the metal oxide (such as SiO ₂ , Al ₂ O ₃ , The concentration of SnO ₂ , Sb ₂ O ₅ , WO _{3 ,} etc.) can be quantified by a calcining method calculated from the calcined residue obtained by calcining the dispersion at 800°C or higher for 30 minutes or more. The total metal oxide concentration in the dispersion liquid is, for example, in the range of 1 to 60 mass%, 20 to 60 mass%, or 30 to 60 mass%.

Moreover, the pH of the dispersion liquid is, for example, in the range of 1 to 14, 2 to 8, or 3 to 7.

[Coating composition] The coating composition (also called coating liquid) of the present invention is composed of a silicon-containing substance containing (S) component: an organic silicon compound and/or a hydrolyzate, and (T) component: the aforementioned modified metal oxide colloid. Made of particles (C). Or the coating composition of the present invention is composed of (K) component: at least one resin selected from the group consisting of thermosetting resin, thermoplastic resin and ultraviolet curing resin, and (T) component: the aforementioned modified metal oxide colloid Made of particles (C). Hereinafter, each component constituting the coating composition of the present invention, particularly the (S) component and the (K) component, will be described in detail.

《(S)Component》 The (S) component according to the present invention is a silicon-containing substance of an organosilicon compound and/or a hydrolyzate thereof. Specifically, the organosilicon compound contains at least one organosilicon compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II) to be described later.

<Compound represented by formula (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 acryl group or a methacryl group. , a monovalent organic group of mercapto group, ureido group or cyano group, and an organic group bonded to a silicon atom through a Si-C bond, R ² represents an alkyl group, aryl group or aralkyl group having 1 to 8 carbon atoms. group, alkoxyalkyl group or 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.

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

Examples of the organosilicon compound represented by the formula (I) include tetramethoxysilane, tetraethoxysilane, tetran-propoxysilane, tetraisopropoxysilane, and tetran-butoxysilane. , tetraacetyloxysilane, methyltrimethoxysilane, methyltripropoxysilane, methyltributoxysilane, methylacetyloxysilane, methyltripentyloxysilane, methyltributoxysilane Phenoxysilane, methyltrityloxysilane, methyltriphenylethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltrimethoxysilane Ethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane , β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane Oxypropyltriphenoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethyl Oxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ- Glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxy ring Hexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3 ,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyl Tributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3, 4-Epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane Oxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane , α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane Silane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane Silane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethyl Oxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldibutoxysilane Phenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyl Dimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, isocyanatepropyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethyl Oxysilane, vinyltriethoxysilane, vinylacetoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylethyloxysilane, γ-chloropropyltrimethoxysilane silane, γ-chloropropyltriethoxysilane, γ-chloropropylacetyloxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacrylic acidoxypropyltrimethyl Oxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane Oxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldi Methoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiethyloxysilane, γ-methacrylic acidoxypropylmethyldimethoxysilane, γ-methacrylic acid Oxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, urea Methyltrimethoxysilane, 2-ureidoethyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltriethoxysilane, methylethylene methyldimethoxysilane, methylvinyldiethoxysilane, etc., these can be used alone or in combination of two or more types.

<Compound represented by formula (II)> In the formula, R ⁴ represents an alkyl group with 1 to 5 carbon atoms, X represents an alkyl group or hydroxyl group with 1 to 4 carbon atoms, Y represents a methylene group or an alkylene group with 2 to 20 carbon atoms, and c represents An integer of 0 or 1.

Examples of the organosilicon compound represented by the formula (II) include methylenebismethyldimethoxysilane, ethylidenebisethyldimethoxysilane, and propylenebisethyldiethoxysilane. Silane, butylbismethyldiethoxysilane, etc. can be used alone or in combination of two or more types.

The above-mentioned component (S) is preferably an organosilicon compound represented by formula (I). In particular, it satisfies the conditions that any 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 1 or 2. The organosilicon compound of formula (I) is preferred.

Preferable examples of the organosilicon compound represented by formula (I) include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, and α-glycidoxysilane. Ethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane , α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltrimethoxysilane hydroxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropyloxysilane silane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-cyclic Oxypropoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyl Triethoxysilane, 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-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane Silane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylethyldimethoxy silane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethyl Oxysilane. More preferably, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane , these can be used alone or as a mixture.

Furthermore, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane were used. In this case, a tetrafunctional compound corresponding to a+b=0 in formula (I) may be used in combination. Examples of compounds corresponding to tetrafunctional silane include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, and tetratertoxysilane. -Butoxysilane, tetrasec-butoxysilane, etc.

Moreover, 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-mentioned formula (I) and the compound represented by the formula (II), and the above-mentioned R ² (formula ( A compound in which part or all of I)) and X (formula (II)) are substituted by hydrogen atoms. The hydrolysates of the organosilicon compounds of the formula (I) and the formula (II) can each be used alone or in combination of two or more kinds. Hydrolysis can be performed by adding an acidic aqueous solution such as a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution, and an acetic acid aqueous solution to the above-mentioned organosilicon compound and then stirring.

"Coating composition containing component (S) and component (T)" Regarding the coating composition containing the component (S) and the component (T), the ratio of the component (S) to the component (T) is not particularly limited. For example, relative to the component (T), the modified metal oxide colloidal particles ( C) 100 parts by mass may contain the component (S) in a mass ratio of 25 to 400 parts by mass, and preferably contains 25 to 300 parts by mass.

"(K)Component" Component (K) in the present invention is at least one resin selected from the group consisting of thermosetting resins, thermoplastic resins and ultraviolet curing resins, and these resins can function as matrix forming components. As the matrix forming component, acrylic resin, melamine resin, urethane resin, polyester resin, epoxy resin, phosphagen resin, etc. are used. Among them, polyester resin or urethane resin is preferred.

"Coating composition containing component (K) and component (T)" Regarding the coating composition containing the above-mentioned component (K) and (T), the ratio of the above-mentioned component (K) to (T) is not particularly limited. For example, the ratio of the modified metal oxide colloidal particles relative to the component (T) is ( C) 100 parts by mass may contain component (K) in a mass ratio of 25 to 400 parts by mass.

"Other ingredients" The coating composition of the present invention may contain a curing catalyst (hardening agent) used to accelerate the curing reaction. The hardening catalyst (hardening agent) is, for example, 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 salt compounds. At least 1 hardening catalyst. The curing catalyst (hardening agent) is used to accelerate the curing of the silanol group (or epoxy group in the case of blending) of the (S) organosilicon compound contained in the coating composition. By using such a curing catalyst (hardening agent), the film formation reaction can be accelerated.

Specific examples of these include amino acids such as glycine; alkoxides of metals such as aluminum, zirconium or titanium; aluminum acetyl pyruvate, chromium acetyl pyruvate, titanium acetyl pyruvate, Metal chelating compounds such as cobalt acetyl pyruvate; organic acid metal salts such as sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, tin octylate; perchloric acid, ammonium perchlorate, Magnesium perchlorate and other perchloric acids or their salts; hydrochloric acid, phosphoric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, bromic acid, selenious acid, thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrous acid, Aluminic acid, carbonic acid, organic carboxylic acid, p-toluenesulfonic acid and other inorganic acids, organic acids or their salts; metal salts of Lewis acids such as SnCl ₂ , AlCl ₃ , FeCl ₃ , TiCl ₄ , ZnCl ₂ , SbCl ₃ and other wait.

These curing catalysts (hardening agents) can be used by appropriately adjusting the type and usage amount according to the composition of the coating composition of the present invention, etc. When a curing catalyst (hardening agent) is used, the upper limit of the usage amount is preferably 5 mass % or less based on the total solid content in the coating composition. In this specification, the term "total solid content" means all components of the coating composition excluding the solvent. Even if it is in liquid form, it can be regarded as "solid content" for convenience.

In the coating composition of the present invention, a solvent may be used for the purpose of adjusting fluidity, adjusting solid content concentration, surface tension, viscosity, evaporation rate, etc. The solvent used is water or organic solvent. 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, and methyl acetate. Esters, ethyl acetate, butyl acetate and other esters, diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, tetrahydrofuran and other ethers, acetone, methyl ethyl ketone and other ketones, dichloroethane Such as halogenated hydrocarbons and aromatic hydrocarbons such as toluene and xylene. Furthermore, the concentration of the total solid content in the coating composition of the present invention may be, for example, 20 to 40% by mass.

As will be described later, the coating composition of the present invention can be further used for the purpose of improving the wettability to the substrate and improving the smoothness of the cured film when forming a cured film on a substrate. It contains various surfactants. UV absorbers, antioxidants, antistatic agents, etc. can be added as long as they do not affect the physical properties of the cured film. Disperse dyes, oil-soluble dyes, fluorescent dyes, pigments, photochromic compounds, thixotropic agents, etc. can also be further added.

＜Cured film, optical components＞ The coating composition of the present invention can be coated on the surface of a substrate to form a cured film. Then, by further using a transparent base material (optical base material) suitable for optical applications, an optical member having a cured film can be obtained. This optical component is also an object of the present invention.

As the base material used, various base materials made of glass, plastic, etc. are used, and specific examples include eyeglass lenses, various optical lenses such as cameras, various display element filters, mirrors, window glass, paint films such as automobiles, automobiles, etc. Used lampshades, etc. A cured film (transparent coating) is formed on the surface of the base material as a hard coating film from the coating composition of the present invention. In addition to its use as a hard coating film, it can also be formed as a primer film for plastic lenses, etc.

The coating composition can be hardened by hot air drying or active energy ray irradiation. As the hardening conditions for hot air drying, it can be carried out in hot air at 70 to 200°C, especially 90 to 150°C. In addition, examples of active energy rays include infrared rays, ultraviolet rays, electron rays, etc. In particular, far-infrared rays can reduce damage caused by heat.

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

In addition, before the aforementioned coating composition is coated on the surface of the substrate, the surface of the substrate is physically treated with acid, alkali or various organic solvents or lotions by chemical treatment, plasma, ultraviolet light, etc., thereby improving the quality of the substrate. Adhesion to the hardened film. By further priming the surface of the base material with various resins, the adhesion between the base material and the cured film can be further improved.

In addition, the cured film formed by the coating composition of the present invention can be used as a high refractive index film for a reflective film, and can be used as a multifunctional film by adding functional components such as anti-fogging, photochromic, and antifouling.

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

Furthermore, the optical member of the present invention has a cured film formed of the coating composition of the present invention on the surface of an optical base material, and an antireflection film made of a vapor-deposited film of an inorganic oxide can be formed on the cured film. The anti-reflection film is not particularly limited, and a single-layer or multi-layer vapor-deposited film of a conventionally known inorganic oxide can be used. Examples of the anti-reflection film include anti-reflection films disclosed in Japanese Patent Application Laid-Open No. 2-262104 and Japanese Patent Application Laid-Open No. 56-116003, and the like.

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

Step (a) in the manufacturing method of the present invention is to mix a dispersion containing metal oxide colloidal particles (A) and a dispersion of unmodified composite oxide colloidal particles.

As mentioned above, examples of the metal oxide colloidal particles (A) in the dispersion liquid containing the metal oxide colloidal particles (A) include those selected from the group consisting of Ti, Mn, Fe, Cu, Zn, Y, Zr, and Nb. , Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce colloidal particles of at least one metal oxide group, known methods such as ion exchange method, degumming method, hydrolysis method can be used , 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 to 50 mass%, 1 to 30 mass%, or 1 to 20 mass%. Furthermore, the metal oxide concentration of the metal oxide colloidal particles (A) can be quantified by a sintering method. Moreover, the pH of the dispersion liquid containing the metal oxide colloidal particles (A) is, for example, in the range of 1 to 14 or 1 to 12.

The unmodified composite oxide colloidal particles in the dispersion of the unmodified composite oxide colloidal particles are as mentioned above. For example, SiO ₂ particles and SnO ₂ particles are chemically bonded at the interface to make them Composite SiO ₂ -SnO ₂ composite oxide colloidal particles, SiO ₂ -Sb 2 O ₅ composite oxide colloidal particles are composited by chemical bonding between SiO ₂ particles and Sb ₂ O ₅ particles at the _interface . , SiO ₂ -WO _{3 composite oxide colloidal particles, etc., in which SiO 2 particles and WO 3 particles are} chemically bonded at the interface to form a complex. The aforementioned 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 acidic salt of the above-mentioned atoms is treated with a hydrogen-form ion exchange resin. An example of the oxidation method is a method of reacting atoms or powder of an inorganic oxide with hydrogen peroxide. This 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 concentration of the unmodified composite oxide in the dispersion is, for example, in the range of 1 to 30 mass%, 1 to 20 mass%, or 1 to 10 mass%. Furthermore, the unmodified composite oxide concentration of the unmodified composite oxide colloidal particles can be quantified by the sintering method.

In the aforementioned step (a), the mass of the total composite oxide of the unmodified composite oxide colloidal particles/the mass of the total metal oxide of the metal oxide colloidal particles (A) is to be 0.05 to 0.50, 0.05 to 0.30, or In the range of 0.03 to 0.30, a dispersion of a dispersion of metal oxide colloidal particles (A), Si and at least one atom selected from the group consisting of Sn, Sb and W and unmodified composite oxide colloidal particles is carried out. Mixers are better.

In step (b) of the manufacturing 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. It can be carried out at the aforementioned heating temperature in the range of 30 to 320°C, 50 to 320°C or 80 to 320°C. Especially when heating above 100°C, a pressure-resistant container can be used under hydrothermal conditions. Here, hydrothermal conditions mean high-temperature and high-pressure conditions of 100° C. or higher and 1 atmosphere or higher. The heating time may 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 addition, in this step (b), a known mixer or stirring device can be used for stirring and mixing.

Step (c) in the manufacturing method of the present invention is to contact the mixed solution obtained in step (b) with H-type cation exchange resin. The aforementioned H-type cation exchange resin is a cation exchange resin having a functional group capable of exchanging hydrogen ions with other cations. Sulfonic acid type H-type strongly acidic cation exchange resin or 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, Amber Light (registered trademark) IR-120B manufactured by Organic Co., Ltd. can be used.

The (d) step in the manufacturing method of the present invention is to mix the mixed solution obtained in the (c) step and the aluminate aqueous solution, and heat it at a temperature of 30 to 320°C for 0.5 to 24 hours. The aluminate is a compound containing aluminate ions and negative ions derived from an inorganic base. Examples of the inorganic base include sodium, potassium, lithium, and the like. Specific examples of metal salts containing aluminate ions and negative ions derived from inorganic bases include sodium aluminate, potassium aluminate, lithium aluminate, etc., and those sold on the market can also 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 aluminic acid concentration of the aluminate aqueous solution is, for example, in the range of 0.1 to 10 mass % or 0.1 to 5 mass % in terms of alumina. The aforementioned heating temperature is in the range of 30 to 320°C, 40 to 180°C, 40 to 150°C, or 40 to 100°C. The heating time may 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 aforementioned step (d), if you want to make the mass of the total composite oxide/the mass of the aluminate (converted to Al ₂ O ₃ ) into the range of 50 to 800, 100 to 700, or 150 to 700, you can mix it in step (c). The obtained mixed solution and aqueous aluminate solution are preferred. [Example]

Examples of the present invention are shown below. In addition, the present invention is not limited to these embodiments.

Physical properties were determined by the following measurement methods. [Moisture content] is determined by Karl Fischer titration. [Average primary particle diameter (particle diameter by transmission electron microscope)] dispersion was dropped on a copper mesh and dried, and 100 particles were observed using a transmission electron microscope (JEM-1010 manufactured by JEOL Ltd.) , calculate the average value of the primary particle diameter. [Average particle diameter (dynamic light scattering particle diameter)] The sol was diluted with a dispersion solvent and measured using a dynamic light scattering measuring device: Nano Laser Particle Size Analyzer S (trade name: MARVERN) using solvent parameters. [Specific gravity] is obtained by the float method (25°C). [Viscosity] is determined with a B-type viscometer (25°C). [pH] is obtained with a pH meter. When the dispersion medium is an organic solvent, the solution is measured by diluting it with pure water of the same mass as the dispersion liquid. [Stability evaluation] Store the dispersion at room temperature for one month, and visually confirm the change in particle size of the modified metal oxide colloidal particles by dynamic light scattering, the change in viscosity of the dispersion, and the presence of precipitates, based on the following Metrics evaluate dispersion stability. A: There is no change in particle size and viscosity, and there is no precipitation. B: There is a slight change (a slight increase in particle size and viscosity), and there is no precipitation. C: Significant changes (an increase in particle size, viscosity, and gelation). ion chromatography) or there is a precipitate [total nitrogen amount derived from organic amines], quantitative organic matter was determined using an ion chromatograph 761 Compact IC (manufactured by Metrohm Corporation) and a column for cation analysis Shodex IC YK-421 (manufactured by Showa Denko Co., Ltd.). amine. The total nitrogen content was calculated based on the obtained organic amine content. [Al ₂ O ₃ content] The obtained aqueous sol was dried to produce a dry powder, and the content was determined using a small fluorescent X-ray analyzer Supermini 200 (manufactured by Rigaku Co., Ltd.).

Production Example 1: Preparation of unmodified composite oxide to be the coating layer (B). Dissolve 36 g of JIS No. 3 sodium silicate (containing 29.8% by mass of SiO ₂ , manufactured by Fuji Chemical Co., Ltd.) in 400 g of pure water. 9.8 g of sodium stannate NaSnO ₃ ･H ₂ O (containing 55.1% by mass of SnO ₂ , manufactured by Showa Chemical Co., Ltd.) was dissolved. The obtained aqueous solution was passed through a column filled with hydrogen-type cation exchange resin (Amber Light (registered trademark) IR-120B) to obtain an aqueous sol of acidic second tin oxide-silica composite colloidal particles (pH 2. 4. Contains 0.44 mass% SnO ₂ , contains 0.87 mass% SiO ₂ , SiO ₂ /SnO ₂ mass ratio 2.0) 1240g. Next, 3.2 g of diisopropylamine was added to the obtained aqueous sol. The obtained sol is an aqueous sol of alkaline oxidation of the second tin-silica composite colloidal particles, and its pH is 8.0. In addition, colloidal particles with 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 metal oxide colloidal particles (A) as cores (ZrO ₂ -SnO ₂ composite oxide colloidal particles). Tetramethylammonium bicarbonate (Tama Chemical Industry (Tama Chemical Industry)) was put into a 1 m ³ tube (vessel). stock) system, containing 42.4% by mass when converted into tetramethylammonium hydroxide.) 251.85kg of aqueous solution and 95.6kg of pure water became a diluted aqueous solution. While stirring the aqueous solution, zirconium oxycarbonate powder (ZrOCO ₃ , manufactured by AMR, containing 40.11% by mass of 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 at 85°C, 8.23 kg of metastannic acid (manufactured by Showa Chemical Co., Ltd., containing 7.08 kg of SnO ₂ ) was gradually added, and the mixture was heated and aged at 105°C for 5 hours. At the end of the heating and aging time, the mixed liquid is in the form of a sol. Further, hydrothermal treatment was performed at 145°C for 5 hours. The product obtained after hydrothermal treatment was a sol containing colloidal particles of zirconium oxide-second tin oxide composite oxide, with a (ZrO ₂ +SnO ₂ ) concentration of 12.86 mass%, a specific gravity of 1.180, and a pH of 10.62. Then, the sol was washed and concentrated while adding pure water through an extreme filtration device to obtain a zirconium oxide-oxidized sol containing a (ZrO ₂ +SnO ₂ ) concentration of 6.03% by mass, a specific gravity of 1.052, and a pH of 9.43. The second sol of tin composite oxide colloidal particles is 3215kg. The average primary particle diameter of the obtained zirconium oxide-second tin oxide composite oxide colloidal particles is 5 to 15 nm.

Production Example 3: Preparation of metal oxide colloidal particles (A) as cores (TiO ₂ -ZrO ₂ composite oxide colloidal particles). Put 368.6 g of pure water and 35% tetraethylammonium hydroxide into a 2L separable flask. 487.7 g, and after mixing, 14.6 g of metastannic acid (manufactured by Showa Chemical Co., Ltd.) was added and dissolved. Next, 469.7 g of titanium tetraisopropoxide (containing 132.0 g in terms of TiO ₂ , manufactured by Kanto Chemical Co., Ltd.) was added with stirring, and was heated and dissolved at 60°C. Next, 108.4 g of oxalic acid dihydrate (manufactured by Ube Kosan Co., Ltd.) was added and dissolved. In the obtained mixed solution, the molar ratio of oxalic acid/titanium atoms was 0.5, and the molar ratio of tetraethylammonium hydroxide/oxalic acid was 1.43. 1,449 g of the mixed solution was maintained at 88 to 92° C. for 3 hours in an open system under atmospheric pressure, and the by-produced isopropyl alcohol was distilled off to prepare 1,240 g of an aqueous solution containing titanium. The TiO ₂ conversion concentration of the obtained titanium-containing aqueous solution was adjusted to 5.0 mass %. 2000 g of the titanium-containing aqueous solution was put into a 3L glass-lined high-pressure autoclave container, and hydrothermal treatment was performed at 140° C. for 5 hours. After cooling to room temperature, use a maximum filtration device to wash with pure water (PW) to remove oxalic acid. The obtained rutile titanium oxide sol had a specific gravity of 1.030, a pH of 11.7, a conductivity of 1044 μS/cm, and a TiO ₂ concentration of 3.8% by mass. 35.9 g of zirconium oxychloride (containing 21.19 mass % of ZrO ₂ , manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.) was diluted with 217 g of pure water to prepare 253 g of zirconium oxychloride aqueous solution (containing 3.0 mass % of ZrO ₂ ). , 1053 g of the water-dispersed sol of the above-mentioned rutile titanium oxide sol was added with stirring. Next, it is hydrolyzed by heating at 95° C. to obtain a sol containing titanium oxide-zirconia composite oxide colloidal particles. The pH of the obtained sol was 1.2, the total metal oxide concentration was 3.6% by mass, and the average primary particle diameter of the titanium oxide-zirconia composite oxide colloidal particles was 5 to 15 nm.

Production Example 4: Preparation of a composite oxide as the 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 dissolved Sodium NaSnO ₃ ･H ₂ O (containing 55.1% by mass of SnO ₂ , manufactured by Showa Chemical Co., Ltd.) 18.5 g, and further dissolved 1.35 g of liquid soda aluminate (0.27 g of Al ₂ O ₃ ). The obtained aqueous solution was passed through a column filled with hydrogen-type cation exchange resin (Amber Light (registered trademark) IR-120B) to obtain an aqueous sol containing acidic second tin oxide-silica-alumina composite colloidal particles ( pH 2.5, 1.09 mass% SnO ₂ , containing 2.2 mass% SiO ₂ , SiO ₂ /SnO ₂ mass ratio 2.0, 0.02 mass% Al ₂ O ₃ ) 1008g. Next, 6.0 g of diisopropylamine was added to the obtained aqueous sol. The obtained sol is an aqueous sol of alkaline second tin oxide-silica-alumina composite colloidal particles, with a pH of 8.2. Furthermore, colloidal particles with 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). 830 g of aqueous sol (containing 50 g of total metal oxide) of the zirconium oxide-second tin oxide composite oxide colloidal particles prepared in Production Example 2 was added. 577 g of the aqueous sol of the alkaline second tin oxide-silica composite colloidal particles prepared in Production Example 1 was thoroughly stirred. Next, heat aging was performed at 95° C. for 2 hours to obtain 1410 g of an aqueous sol of zirconium oxide-second tin oxide composite oxide colloidal particles coated with second tin oxide-silica composite colloidal particles. The pH of the obtained sol was 8.1, and the total metal oxide concentration was 4.1% by mass. Pass the obtained aqueous sol of zirconium oxide-second tin oxide composite oxide colloidal particles through a column filled with hydrogen-type cation exchange resin (Amber Light (registered trademark) IR-120B) to obtain acidic zirconium oxide-second tin oxide Aqueous sol of complex oxide colloidal particles 1880g. The pH of the obtained sol was 3.3, and the total metal oxide concentration was 3.0% by mass. In order to make the mass of the composite oxide of the acidic zirconium oxide-second tin oxide composite oxide colloidal particles/the mass of soda aluminate (in Al ₂ O ₃ conversion) 650, add 20 g of soda aluminate aqueous solution to the obtained acidic sol. (0.087g of Al ₂ O ₃ ), and heated at 95° C. for 2 hours, and then concentrated using an extreme filtration device. The dispersion containing the obtained modified zirconium oxide-second tin oxide composite oxide colloidal particles has a total metal oxide concentration of 30.5% by mass, a specific gravity of 1.332, a pH of 4.5, a B-type viscosity of 5.0mPa･s, and an average particle diameter of 17nm. . In addition, the Al ₂ O ₃ content contained in the cladding layer was 1.17% by mass based on the mass of the total composite oxide in the cladding layer. The physical properties of the obtained sol did not change even if it was left at room temperature for one month and it was stable. 164 g of 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 Industry Co., Ltd.) was added, and then methanol was gradually added The water was distilled off at 600 Torr to obtain 213 g of a methanol-dispersed sol of modified zirconium oxide-second tin oxide composite oxide colloidal particles modified with aluminate. The obtained methanol-dispersed sol has a total metal oxide concentration of 31.0 mass%, a B-type viscosity of 12.5 mPa･s, a pH of 5.7 (diluted with water of the same mass as the sol), a moisture content of 0.6%, and an average particle diameter of 17 nm. The physical properties of the obtained sol did not change even if it was left at room temperature for one month and it was stable.

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 the alkaline second tin oxide-silica prepared in Production Example 1 while stirring. 769g of water-dispersed sol of composite colloidal particles. Next, this liquid was passed through a column packed with 500 mL of negative ion exchange resin (Amber Light (registered trademark) IRA-410, manufactured by Organic Co., Ltd.). Next, the water-dispersed sol after flowing through the liquid was heated at 150° C. for 3 hours to obtain a water-dispersed sol of titanium oxide-zirconia composite oxide colloidal particles coated with the second tin oxide-silica composite colloidal particles. The obtained dispersed sol was 2788 g and the total metal oxide concentration was 2.2% by mass. The obtained water-dispersed sol was passed through a column filled with hydrogen-type cation exchange resin (Amber Light (registered trademark) IR-120B) to obtain 3427 g of an aqueous sol of acidic titanium oxide-zirconia composite oxide colloidal particles. The pH of the obtained sol was 2.4, and the total metal oxide concentration was 1.7% by mass. In order to make the mass of the composite oxide of the acidic titanium oxide-zirconia composite oxide colloidal particles/the mass of soda aluminate (in Al ₂ O ₃ conversion) 244, add 25 g (0.24 g) of soda aluminate aqueous solution to the obtained acidic sol. g of Al ₂ O ₃ ), heated at 95° C. for 2 hours, and then concentrated using an extreme filtration device. In the dispersion containing the obtained modified titanium oxide-zirconia composite oxide colloidal particles, the total metal oxide concentration was 30.8% by mass, the pH was 4.6, the B-type viscosity was 7.0mPa･s, and the average particle diameter was 21.0nm. The Al ₂ O ₃ content contained in the cladding layer was 2.4% by mass based on the mass of the total composite oxide in the cladding layer. The physical properties of the obtained sol did not change even if it was left at room temperature for one month and it was stable. 195 g of the obtained sol was put into an evaporator equipped with an eggplant-shaped flask, and 6.0 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added, while gradually adding methanol, while distilling off the water at 600 Torr, thereby obtaining 208 g of a methanol-dispersed sol of modified titanium oxide-zirconia composite oxide colloidal particles modified with aluminate. The obtained methanol-dispersed sol had a total metal oxide concentration of 30.6 mass%, a B-type viscosity of 4.2 mPa･s, a pH of 4.8 (diluted with water of the same mass as the sol), a moisture content of 1.7%, and an average particle diameter of 16 nm. The physical properties of the obtained sol did not change even if it was left at room temperature for one month and it was stable.

Example 3: Preparation of modified metal oxide colloidal particles (C) in 1880 g of an aqueous sol of acidic zirconium oxide-second tin oxide composite oxide colloidal particles obtained by the same procedure as in Example 1, and oxidized The mass of the composite oxide of the zirconium-second tin oxide composite oxide colloidal particles/the mass of the soda aluminate (in Al ₂ O ₃ conversion) becomes 650. Add 20 g of the soda aluminate aqueous solution (0.087 g of Al ₂ O ₃ ) and add Heating was performed at 95°C for 2 hours, and then concentrated using an extreme filtration device. In the dispersion containing the obtained modified zirconium oxide-second tin oxide composite oxide colloidal particles, the total metal oxide concentration was 30.6% by mass, the pH was 5.4, the B-type viscosity was 13.4mPa･s, and the average particle diameter was 14nm. In addition, the Al ₂ O ₃ content contained in the cladding layer was 1.17% by mass based on the mass of the total composite oxide in the cladding layer. The physical properties of the obtained sol did not change even if it was left at room temperature for one month and it was stable. 164 g of the obtained sol was put into an evaporator equipped with an eggplant-shaped flask, 5.0 g of γ-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added, and then methanol was gradually added. , while distilling off the water at 600 Torr, 213 g of a methanol-dispersed sol of modified zirconium oxide-second tin oxide composite oxide colloidal particles modified with aluminate was obtained. The obtained methanol-dispersed sol had a total metal oxide concentration of 31.0 mass%, a B-type viscosity of 5.3 mPa･s, a pH of 5.6 (diluted with water of the same mass as the sol), a moisture content of 0.8%, and an average particle diameter of 16 nm. The physical properties of the obtained sol did not change even if it was left at room temperature for one month and it was stable.

Example 4: Preparation of modified metal oxide colloidal particles (C) In 1880 g of an aqueous sol of acidic zirconium oxide-second tin oxide composite oxide colloidal particles obtained by the same procedure as in Example 1, zirconium oxide -The mass of the composite oxide of the second tin oxide composite oxide colloidal particles/the mass of the soda aluminate (converted to Al ₂ O ₃ ) becomes 650, add 20g of the soda aluminate aqueous solution (0.087g of Al ₂ O ₃ ) and mix at 95 The mixture was heated for 2 hours at ℃, and then concentrated using an extreme filtration device. In the dispersion containing the obtained modified zirconium oxide-second tin oxide composite oxide colloidal particles, the total metal oxide concentration was 30.6% by mass, the pH was 5.4, the B-type viscosity was 13.4mPa･s, and the average particle diameter was 14nm. In addition, the Al ₂ O ₃ content contained in the cladding layer was 1.17% by mass based on the mass of the total composite oxide in the cladding layer. The physical properties of the obtained sol did not change even if it was left at room temperature for one month and it was stable. 164 g of the obtained sol was put into an evaporator equipped with an eggplant-shaped flask, and methanol was gradually added while water was distilled off at 600 Torr to obtain a modified zirconium oxide-second tin oxide composite modified with aluminate. 149g of methanol-dispersed sol of oxide colloidal particles. The obtained methanol-dispersed sol had a total metal oxide concentration of 31.0 mass%, a B-type viscosity of 4.6 mPa･s, a pH of 5.7 (diluted with water of the same mass as the sol), a moisture content of 0.8%, and an average particle diameter of 16 nm. The physical properties of the obtained sol did not change even if it was left at room temperature for one month and it was stable.

Comparative example 1 To 830 g of the aqueous sol of zirconium oxide-second tin oxide composite oxide colloidal particles prepared in Production Example 2 (containing 50 g of all metal oxide), the basic second tin oxide-dioxide prepared in Production Example 1 was added. 577g of aqueous sol of silicon oxide composite colloidal particles, stir thoroughly. Next, after heating and aging at 95° C. for 2 hours, 1,400 g of an aqueous sol of zirconium oxide-second tin oxide composite oxide colloidal particles coated with second tin oxide-silica composite colloidal particles was obtained. The pH of the obtained sol was 8.1, and the total metal oxide concentration was 4.6% by mass. The obtained aqueous sol of zirconium oxide-second tin oxide composite oxide colloidal particles is passed through a column filled with hydrogen-type cation exchange resin (Amber Light (registered trademark) IR-120B) to obtain acidic zirconium oxide-second tin oxide Aqueous sol of complex oxide colloidal particles 1910g. The obtained sol had a pH of 3.3 and a total metal oxide concentration of 3.4% by mass. Next, after concentration using a limit filtration device, viscosity and gelation are performed during the concentration process.

Comparative example 2 To 830 g of the aqueous sol of the zirconium oxide-second tin oxide composite oxide colloidal particles prepared in Production Example 2 (containing 50 g of the total metal oxide), the second tin oxide-second tin oxide prepared in Production Example 1 was added. 577g of aqueous sol of silicon composite colloidal particles, stir thoroughly. Next, heat aging was performed at 95°C for 2 hours to obtain 1,400 g of an aqueous sol of zirconium oxide-second tin oxide composite oxide colloidal particles coated with second tin oxide-silica composite colloidal particles. The pH of the obtained sol was 8.1, and the total metal oxide concentration was 4.6% by mass. The obtained aqueous sol of zirconium oxide-second tin oxide composite oxide colloidal particles is passed through a column filled with hydrogen-type cation exchange resin (Amber Light (registered trademark) IR-120B) to obtain acidic zirconium oxide-second tin oxide Aqueous sol of complex oxide colloidal particles 1910g. The obtained 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 the mixture was concentrated to a total metal oxide concentration of 20.6% by mass using a maximum filtration device. The obtained sol had a pH of 3.9, a B-type viscosity of 7.0 mPa･s, and an average particle diameter of 24 nm. The physical properties of the obtained sol did not change even if it was left at room temperature for one month and it was stable. 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 Industry Co., Ltd.) was added, and then methanol was gradually added. , while distilling off the water at 600 Torr, obtaining 213 g of a methanol-dispersed sol of diisobutylamine-bonded zirconium oxide-second tin oxide composite oxide colloidal particles. The obtained methanol-dispersed sol had a total metal oxide concentration of 30.5 mass%, a B-type viscosity of 4.3 mPa･s, a pH of 4.9 (diluted with water of the same mass as the sol), a moisture content of 0.8%, and an average particle diameter of 19 nm. The physical properties of the obtained sol did not change even if it was left at room temperature for one month and it was stable.

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 the basic second tin oxide-silica composite colloidal particles prepared in Production Example 1 while stirring. Next, the liquid was passed through a column packed with 500 mL of negative ion exchange resin (Amber Light (registered trademark) IRA-410, manufactured by Organic Co., Ltd.). Next, the water-dispersed sol after flowing through the liquid was heated at 150° C. for 3 hours to obtain a water-dispersed sol of titanium oxide-zirconia composite oxide colloidal particles coated with the second tin oxide-silica composite colloidal particles. The obtained dispersed sol was 2788 g and the total metal oxide concentration was 2.2% by mass. The obtained water-dispersed sol of titanium oxide-zirconia composite oxide colloidal particles is passed through a column filled with hydrogen-type cation exchange resin (Amber Light (registered trademark) IR-120B) to obtain acidic titanium oxide-zirconia composite oxide. 3427g of water-dispersed sol of colloidal particles. The obtained 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 the mixture was concentrated to a total metal oxide concentration of 17.6% by mass using a maximum filtration device. The obtained sol had a B-type viscosity of 4.8 mPa･s, a pH of 4.2, and an average particle diameter of 27 nm. The physical properties of the obtained sol did not change even if it was left at room temperature for one month and it was stable. 337 g of the obtained sol was put into an evaporator equipped with an eggplant-shaped flask, and then methanol was gradually added while water was distilled off at 600 Torr to obtain diisobutylamine-bonded titanium oxide-zirconia composite oxide colloidal particles in methanol. Dispersed sol 196g. The obtained methanol-dispersed sol has a total metal oxide concentration of 30.0 mass%, a B-type viscosity of 3.9 mPa･s, a pH of 5.0 (diluted with water of the same mass as the sol), a moisture content of 0.8%, and an average particle diameter of 20 nm. The physical properties of the obtained sol did not change even if it was left at room temperature for one month and it was stable.

Comparative example 4 The second tin oxide-silicon dioxide prepared in Production Example 4 was added to 830 g of the aqueous sol of the zirconium oxide-second tin oxide composite oxide colloidal particles prepared in Production Example 2 (containing 50 g of all metal oxide). - 334g of aqueous sol of alumina composite colloidal particles, stir thoroughly. Next, heating and aging were performed at 95° C. for 2 hours to obtain 1,334 g of an aqueous sol of zirconium oxide-second tin oxide composite oxide colloidal particles coated with second tin oxide-silica-alumina composite colloidal particles. The pH of the obtained sol was 8.5, and the total metal oxide concentration was 4.5% by mass. The obtained aqueous sol of zirconium oxide-second tin oxide composite oxide colloidal particles is passed through a column filled with hydrogen-type cation exchange resin (Amber Light (registered trademark) IR-120B) to obtain acidic zirconium oxide-second tin oxide Aqueous sol of complex oxide colloidal particles 1348g. The obtained sol had a pH of 3.1 and a total metal oxide concentration of 4.4% by mass. The obtained acidic sol was concentrated using an extreme filtration device, but viscosity and gelation occurred on the way.

Comparative example 5 The second tin oxide-silicon dioxide prepared in Production Example 4 was added to 830 g of the aqueous sol of the zirconium oxide-second tin oxide composite oxide colloidal particles prepared in Production Example 2 (containing 50 g of all metal oxide). - 334g of aqueous sol of alumina composite colloidal particles, stir thoroughly. Next, the mixture was heated and matured at 95° C. for 2 hours to obtain 1,334 g of an aqueous sol of zirconium oxide-second tin oxide composite oxide colloidal particles coated with second tin oxide-silica-alumina composite colloidal particles. The pH of the obtained sol was 8.5, and the total metal oxide concentration was 4.5% by mass. The obtained aqueous sol of zirconium oxide-second tin oxide composite oxide colloidal particles is passed through a column filled with hydrogen-type cation exchange resin (Amber Light (registered trademark) IR-120B) to obtain acidic zirconium oxide-second tin oxide Aqueous sol of complex oxide colloidal particles 1348g. The obtained sol had a pH of 3.1 and a total metal oxide concentration of 4.4% by mass. 10.1 g of a 5% aqueous sodium hydroxide solution was added to the obtained acidic sol to adjust the pH to 5.2, and the mixture was concentrated to a total metal oxide concentration of 22.4% by mass using a limit filtration device. The obtained sol has a pH of 5.4 and a Type B viscosity of 4.6 mPa･s. , the average particle diameter is 16nm. The physical properties of the obtained sol did not change even if it was left at room temperature for one month and it was stable. 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 Industry Co., Ltd.) was added, and 2 Hours of heating. Next, while gradually adding methanol, water was distilled off at 600 Torr to obtain 173 g of a methanol-dispersed sol of zirconium oxide-second tin oxide composite oxide colloidal particles. In the obtained methanol-dispersed sol, the total metal oxide concentration was 31.0 mass%, the B-type viscosity was 3.4 mPa･s, the pH was 5.7 (diluted with water of the same mass as the sol), and the moisture content was 1.0%. The average particle diameter tends to agglomerate to 69nm. The resulting sol will become viscous and unstable after being left at room temperature for 1 month.

As shown in Table 1, the aqueous dispersion containing the modified metal oxide colloidal particles of the present invention has excellent dispersion stability. Furthermore, even if the surface of the modified metal oxide colloidal particles of the present invention is surface-modified with an organosilicon compound or is not surface-modified, the dispersion stability of the organic solvent dispersion containing the modified metal oxide colloidal particles of the present invention is also Excellent. On the other hand, as shown in the results shown in Table 2, the aqueous dispersion containing the metal oxide colloidal particles in which the coating layer (B) was not modified by soda aluminate increased in viscosity and gelation during concentration (Comparative Example 1). Furthermore, as the coating layer (B), an aqueous dispersion containing metal oxide colloidal particles using second tin oxide-silica-alumina composite colloidal particles became viscous and gelled during concentration (Comparative Example 4 ). Furthermore, as the coating layer (B), when an organic solvent dispersion of sodium hydroxide is added to metal oxide colloidal particles using second tin oxide-silica-alumina composite colloidal particles, the viscosity will increase and the dispersion stability will deteriorate. (Comparative Example 5). It can be seen from the above results that the modified metal oxide colloidal particles of the present invention adopt a coating layer (B) obtained by modifying an unmodified composite oxide with aluminate. The modified metal oxide The aqueous dispersion and organic solvent dispersion of colloidal particles have excellent 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 according to the procedure shown below, and an optical member was produced and measured. Each physical property and evaluation.

Example 5 (Preparation of coating composition) In a glass container equipped with a magnetic stirrer, 35.2 parts by mass of γ-glycidoxypropyltrimethoxysilane and 94.6 parts by mass of methanol were added, and 8.5 parts by mass of 0.01 equivalent of hydrochloric acid was added dropwise over 30 minutes while stirring. After completion of the dropwise addition, stirring was performed for 2.0 hours to obtain a partial hydrolyzate solution of γ-glycidoxypropyltrimethoxysilane. Continuing, 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 when converted to a total metal oxide concentration), and 0.3 parts by mass of aluminum acetate pyruvate as a hardener 129.8 parts by mass of the partial hydrolyzate solution of γ-glycidoxypropyltrimethoxysilane was added, and after sufficient stirring, the mixture was filtered and a coating composition (coating liquid) for hard coating was prepared. (Production of optical components) 3 mL of the aforementioned coating liquid was added to a glass dish with a diameter of 30 mm, and after being stored at 80° C. for 30 minutes, heat treatment was performed at 120° C. for 2 hours to produce an optical member. About the obtained optical member, the yellowness was evaluated by the measurement method shown below. The evaluation results are shown in Table 3. (1) Yellowing degree The degree of yellowing of the obtained optical member was visually inspected. The judgment criteria are as follows. A: I haven’t seen any yellow-transformers at all. B: Slightly yellowed person is seen C: Those who see significant yellowing

Example 6 In Example 5, the coating composition was implemented in the same manner as in Example 5, except that the methanol-dispersed sol of modified metal oxide colloidal particles in Example 1 was changed to the methanol-dispersed sol of modified metal oxide colloidal particles in Example 2. Modulation and production and evaluation of optical components.

Comparative example 6 In Example 5, the 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 2. and production and evaluation of optical components.

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

[table 3] Yellowness Example 5 A Example 6 A Comparative example 6 C Comparative example 7 C

According to the results shown in Table 3, it can be seen that no yellowing was observed at all in the cured film formed from the coating composition using the modified metal oxide colloidal particles (C) of the present invention (Examples 5 and 6). ). On the other hand, according to the results shown in Table 3, significant yellowing was seen in the cured film formed from the coating composition using metal oxide colloidal particles containing organic amines (Comparative Examples 6 and 7) .

According to the results shown in Tables 1 to 3, it can be seen that when the modified metal oxide colloidal particles of the present invention are coated with a coating layer (B) obtained by modifying an unmodified composite oxide with aluminate, , the aqueous dispersion and the organic solvent dispersion containing the modified metal oxide colloidal particles have excellent dispersion stability, and the cured film formed by the coating composition containing the modified metal oxide colloidal particles does not show yellowing. . On the other hand, although aqueous dispersions and organic solvent dispersions of metal oxide colloidal particles containing organic amines have excellent dispersion stability, the cured film formed from a coating composition containing the metal oxide colloidal particles is significantly Yellowing.

Claims (18)

A modified metal oxide colloidal particle (C) in which the metal oxide colloidal particle (A) is used as a core, and the surface is made of Si and Al and at least one kind of atom selected from the group consisting of Sn, Sb and W. It is coated with a coating layer (B) made of a composite oxide, and has an average particle diameter of 5 to 300 nm. The modified metal oxide colloidal particles (C) of claim 1, wherein the coating layer (B) is an unmodified composite oxide of Si and at least one atom selected from the group consisting of Sn, Sb and W. A layer modified with aluminate. Such as the modified metal oxide colloidal particles (C) of claim 1 or 2, wherein the aforementioned metal oxide colloidal particles (A) are selected from the group consisting of Ti, Mn, Fe, Cu, Zn, Y, Zr, Nb, Mo, In , Colloidal particles of at least one metal oxide grouped by Sn, Sb, Ta, W, Pb, Bi and Ce. The modified metal oxide colloidal particles (C) of any one of claims 1 to 3, wherein the average primary particle diameter of the metal oxide colloidal particles (A) is 1 to 300 nm. Modified metal oxide colloidal particles (C) as claimed in any one of claims 1 to 4, wherein the Al content (in Al ₂ O ₃ conversion) in the aforementioned coating layer (B) is expressed as the metal oxide colloidal particles ( The total mass of the total metal oxide of A) and the total composite oxide of the coating layer (B) is 0.05 to 0.5 mass % as a basis. Modified metal oxide colloidal particles (C) as claimed in any one of claims 1 to 5, wherein the Al content (in Al ₂ O ₃ conversion) in the aforementioned coating layer (B) is expressed as the coating layer (B) The mass of the total composite oxide is 0.1 to 10% by mass as a basis. Modified metal oxide colloidal particles (C) as claimed in any one of claims 1 to 6, wherein the total nitrogen content from the organic amine in the aforementioned modified metal oxide colloidal particles (C) is expressed as the metal oxide The total mass of the total metal oxide of the colloidal particle (A) and the total composite oxide of the coating layer (B) is 0.05% by mass or less as a basis. Modified metal oxide colloidal particles (C) as claimed in any one of claims 1 to 7, wherein at least part of the surface of the aforementioned modified metal oxide colloidal particles (C) is modified by the general formula (1) or the general formula (2) The organosilicon compound shown is surface-modified; (In formula (1) and formula (2), R ^1' and R ^3' represent an alkyl group, a phenyl group, a vinyl group, an acryloxy group, a methacryloxy group, an epoxy group, a styryl group, or an isocyanate group. group, mercapto group, ureido group, acid anhydride group or an alkylene group with carbon atoms of 1 to 10 containing these functional groups, and an alkylene group bonded to a silicon atom through a Si-C bond, R ^1' and When R ^3' each exists in a plural number, each R ^1' and each R ^3' may be the same or different. R ^2' and R ^4' represent an alkoxy group, a hydroxyl group or a halogen atom. Hydrolyzable group, when R ^2' and R ^4' each exist in plural, each R ^2' and each R ^4' may be the same or different, Y represents an alkylene group, an aryl group, or an NH group or oxygen atom; a ^' represents an integer from 1 to 3, d represents an integer from 0 to 3, and e represents an integer from 0 or 1). A dispersion of modified metal oxide colloidal particles (C), which disperses the modified metal oxide colloidal particles (C) according to any one of claims 1 to 8 in an aqueous medium or an organic solvent. A coating composition, which contains (S) component: a silicon-containing substance of an organosilicon compound and/or its hydrolyzate, and (T) component: a modified metal oxide colloid according to any one of claims 1 to 8 In the case of particles (C), the organosilicon compound of the component (S) contains at least one organosilicon compound selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula (II); (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 acryl group or a methacryl group. A monovalent organic group such as a mercapto group, a ureido group or a cyano group, and an organic group bonded to a silicon atom through a Si-C bond. R ² represents an alkyl group, aryl group, aromatic group with 1 to 8 carbon atoms. Alkyl, alkoxyalkyl or 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) (In the formula, R ⁴ represents an alkyl group with 1 to 5 carbon atoms, X represents an alkyl group or hydroxyl group with 1 to 4 carbon atoms, Y represents a methylene group or an alkylene group with 2 to 20 carbon atoms, c an integer representing 0 or 1). A coating composition containing (K) component: at least one resin selected from the group consisting of thermosetting resin, thermoplastic resin and ultraviolet curing resin, and (T) component: any one of claims 1 to 8 Modified metal oxide colloidal particles (C). A cured film produced using the coating composition according to claim 10 or 11. An optical member having the cured film according to claim 12 on the surface of the optical base material. An optical member further having an anti-reflection film on the surface of the cured film according to claim 13. A method for manufacturing modified metal oxide colloidal particles (C), which includes the following steps (a) to (d); (a) A step of mixing a dispersion containing metal oxide colloidal particles (A) and a dispersion of Si and at least one atom selected from the group consisting of Sn, Sb and W and unmodified composite oxide colloidal particles (b) heating the mixed solution obtained in step (a) at a temperature of 30 to 320°C for 0.5 to 24 hours (c) The step of contacting the mixed solution obtained in step (b) with H-type cation exchange resin (d) A step of mixing the mixed solution obtained in step (c) and the aqueous aluminate solution, and heating at a temperature of 30 to 320° C. for 0.5 to 24 hours. The manufacturing method of modified metal oxide colloidal particles (C) as claimed in claim 15, wherein the aforementioned step (a) is to mix a dispersion containing metal oxide colloidal particles (A), and Si and a material selected from the group consisting of Sn, Sb and A dispersion of unmodified composite oxide colloidal particles composed of at least one atom grouped by W, such that the mass of the total composite oxide of the unmodified composite oxide colloidal particles/the total metal of the metal oxide colloidal particles (A) The quality of the oxide becomes a step from 0.05 to 0.50. The manufacturing method of modified metal oxide colloidal particles (C) as claimed in claim 15 or 16, wherein the aforementioned step (d) is to mix the mixed solution obtained in step (c) and the aluminate aqueous solution to form a fully composite oxide The mass/mass of aluminate (in Al ₂ O ₃ conversion) becomes a step of 50 to 800. The method for producing modified metal oxide colloidal particles (C) according to any one of claims 15 to 17, wherein the heating treatment in step (b) is performed under hydrothermal conditions.